Polymer brush with chain ends functionalized with metal coordinated two heterogeneous elements for selective surface modification

Abstract

A polymer of structure (A) having two end groups R3p and R4p, and a polymer chain (R) having a repeating unit of structure (Ip) or (IIp). R3p is a C-1 to C-8 alkyl group, a moiety of structure (IIIp), or a moiety of structure (IIIp1). If the repeating unit is (IIp), then R3p is a C-1 to C-8 alkyl group. If the repeating unit has (Ip), then R3p is structure (IIIp) or structure (IIIp1). R4p is a capping moiety, such as H, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2). R3p and R4p cannot be both, respectively, part of the structures (IIIp) and (IVp), part of the structures (IIIp) and (IVp1), or part of the structures (IIIp) and (IVp2). The polymer of structure (A) must contain a grafted end group moiety selected from structure (IIIp), (IVp), (IVp1) or (IVp2). This composition with a solvent is used in a DSA process. # imgabs0 #

Description

Technical Field

[0001] The disclosed subject matter relates to novel graftable polymers having narrow polydispersity and one reactive end group selective for metal substrates, containing two heteroatoms, and compositions thereof in organic spin coating solvents, and methods of using these compositions to form polar or nonpolar brushes on substrates and using these brushes for directed self-assembly. Novel compounds useful for preparing these polymers are also disclosed. The present invention also relates to methods of using these compositions to form polar or nonpolar brushes on substrates and using these brushes for directed self-assembly (DSA). Background Art

[0002] In conventional photolithography, ultraviolet (UV) radiation can be used to expose to a photoresist layer coated on a substrate or layered substrate through a mask. Positive or negative photoresists are available, and these can also contain refractory elements such as silicon to achieve dry development of conventional integrated circuit (IC) plasma processing. In positive photoresists, UV radiation through the mask causes a photochemical reaction in the photoresist, so that the exposed area is removed with a developer solution or by conventional IC plasma processing. On the contrary, in negative photoresists, UV radiation through the mask causes the area exposed to the radiation to become less removable with a developer solution or by conventional IC plasma processing. Then integrated circuit features such as gates, through holes or interconnects are etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional photolithography exposure processes, the feature size of integrated circuit features is limited. Due to the limitations associated with aberrations, focus, proximity effects, the minimum achievable exposure wavelength and the maximum achievable numerical aperture, it is difficult to achieve further reduction of pattern size with radiation exposure. Directed self-assembly is a promising approach that has attracted attention in overcoming some of the shortcomings of conventional photolithography as outlined above.

[0003] Specifically, directed self-assembly of block copolymers is a method for generating very small patterned features for manufacturing microelectronic devices in which critical dimensions (CD) of nanoscale features, typically in the range of 10 nm to 50 nm, can be achieved. It is challenging to achieve feature sizes below 10 nm using conventional methods for directed self-assembly of block copolymers. Directed self-assembly methods of block copolymers such as those based on graphoepitaxy and chemical epitaxy are desirable for extending the resolution capabilities of photolithography.

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

[0005] Known examples of block copolymers suitable for directed self-assembly are block copolymers that can microphase separate and contain carbon-rich blocks (such as styrene or containing certain other elements such as Si, Ge and Ti) that resist plasma etching and highly plasma etchable or removable blocks, which can provide high-resolution pattern definition. Examples of highly etchable blocks can include monomers that are rich in oxygen and do not contain refractory elements and can form highly etchable blocks, such as methyl methacrylate. The plasma etching gas used in the etching method for defining the self-assembly pattern is typically those used in the method for manufacturing integrated circuits (ICs). In this way, patterns that are very fine compared to conventional photolithography techniques can be created on typical IC substrates, thereby achieving pattern multiplication.

[0006] In the directional self-assembly method of graphoepitaxy, block copolymers are self-organized on a substrate pre-patterned with conventional photolithography (ultraviolet, deep UV and electron beam, extreme UV (EUV) exposure source) to form topographic features, such as line / space (L / S) or contact hole (CH) patterns. In the example of L / S directional self-assembly array, block copolymers can form self-aligned layered regions with sub-lithographic spacing in the grooves between the sidewalls of the pre-pattern, thereby enhancing pattern resolution by subdividing the space between the topographic lines in the grooves into finer patterns. Similarly, features such as contact holes can be made denser by using graphoepitaxy, in which suitable block copolymers are self-arranged in an array of pre-patterned holes or pre-patterned columns defined by conventional photolithography by directional self-assembly, thereby forming a denser array of regions of etchable and anti-etching domains, which produce a denser array of contact holes when etching. In addition, block copolymers can form a single and smaller etchable domain at the center of a pre-pattern hole of appropriate size, and provide potential shrinkage and rectification of holes in the pre-pattern. Thus, graphoepitaxy has the potential to provide both pattern rectification and pattern multiplication.

[0007] In chemical epitaxy (chemical epitaxy) (chemoepitaxy) DSA method, the self-assembly of block copolymers occurs on the surface of the region with different chemical affinities but no morphology or very slight morphology to guide the self-assembly process. For example, photolithography (UV, deep UV, electron beam, EUV) and nanofabrication processes can be used to manufacture chemical pre-patterns to create surfaces with different chemical affinities in line and spacer (L / S) patterns. These regions may have almost no morphological differences, but there are indeed surface chemical patterns to direct the self-assembly of block copolymer domains. This technology allows the precise setting of these block copolymer domains whose spatial frequencies are higher than the spatial frequencies of pre-patterns. After plasma or wet etching treatment, the aligned block copolymer domains can be patterned and transferred to the lower substrate subsequently. In addition, chemical epitaxy has the advantages that block copolymer self-assembly can rectify the surface chemistry, size and roughness changes of the lower chemical pattern to produce improved line-edge roughness and CD control in the final self-assembly block copolymer domain pattern. Other types of patterns such as contact hole (CH) arrays can also be generated or rectified using chemical epitaxy.

[0008] The ability of BCPs to phase separate 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, due to the lower interaction parameter (χ) between PS and PMMA, the minimum half-spacing of PS-b-PMMA is limited to about 10 nm. To achieve further feature miniaturization, block copolymers with larger interaction parameters (higher χ) between the two blocks are highly desirable.

[0009] For photolithography applications, the orientation of the block copolymer domain perpendicular to the substrate is desired. For conventional block copolymers, such as PS-b-PMMA, wherein two blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermally annealing the block copolymer on the layer of non-preferential or neutral materials grafted or crosslinked at the polymer-substrate interface. Due to the greater difference in the interaction parameters between the domains of higher χ block copolymers, it is important to control both BCP-air and BCP-substrate interactions. Many orientation control strategies for generating vertically oriented BCP domains have been implemented with higher χBCP. For example, solvent vapor annealing has been used for the orientation control of polystyrene-b-polyethylene oxide (PS-b-PEO), polystyrene-b-polydimethylsiloxane (PS-b-PDMS), polystyrene-b-poly (2-vinyl pyridine) (PS-b-P2VP), polylactide-b-poly (trimethylsilyl styrene) PLA-b-PTMSS and PDMS-b-PHOST. The introduction of solvent vapor chambers and the kinetics of solvent vapor annealing may complicate the DSA process. Alternatively, combinations of neutral underlayers and topcoat materials have been applied to PS-b-P2VP, PS-b-PTMSS, and PLA-b-PTMSS to achieve vertical orientation of polymer domains. However, additional topcoat materials may increase process cost and complexity. Therefore, there is a need for higher χBCP systems with no topcoat on a range of preferential and non-preferential substrates using simple thermal annealing.

[0010] The grafted polymers forming covalently bound films on the surface of the substrate can be prepared by plasma deposition, electrochemical deposition or self-assembly. The strength of the covalent bond predicts the adhesion of the film; however, these films are generally much more adherent than films that interact with the surface of the substrate only by secondary forces (such as those prepared by spin coating). Therefore, due to the higher adhesion formation of the grafted polymer film on the substrate material, it is available for a variety of applications. Among these are the following examples: one example is a biomaterial, in which the substrate is made biocompatible by grafting polymers at the surface of the material (such as a medical prosthesis) without compromising the overall mechanical properties. Another example is that the polymers on the surface of the substrate have also been used to impart anti-biofouling to these surfaces or improve their corrosion resistance. Another example is a coating solution, in which the grafting of polymers on the surface of the substrate can change the surface characteristics of these substrates to achieve better coating; in addition, in a suspension of metal or metal oxide nanoparticles, the coating ability and stability of these suspensions can be improved by grafting polymers at the surface of these nanoparticles. Other examples are 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 a neutral layer on these surfaces, which allows the block copolymers to orient their domains perpendicular to the substrate surface during self-assembly or directed self-assembly.

[0011] Directed self-assembly of block copolymers is a method for generating smaller and smaller patterned features for manufacturing microelectronic devices in which critical dimensions (CD) of nanoscale features can be achieved. Directed self-assembly methods are desirable for expanding the resolution capabilities of microlithography. In conventional photolithography methods, ultraviolet (UV) radiation can be used to expose through a mask to a photoresist layer coated on a substrate or a layered substrate. Positive or negative photoresists are available, and these can also contain refractory elements such as silicon to achieve dry development of conventional integrated circuit (IC) plasma processing. In positive photoresists, UV radiation through the mask causes a photochemical reaction in the photoresist, so that the exposed area is removed with a developer solution or by conventional IC plasma processing. On the contrary, in negative photoresists, UV radiation through the mask causes the area exposed to the radiation to become 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. When using conventional photolithography exposure processes, the feature size of integrated circuit features is limited. Due to limitations associated with aberrations, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture, it is difficult to achieve further reductions in pattern size with radiation exposure. The demand for large-scale integration has led to a continuous reduction in circuit size and features in devices. In the past, the final resolution of features depended on the wavelength of light used to expose the photoresist, which had its own limitations. Directed assembly techniques, such as graphoepitaxy and chemical epitaxy using block copolymer imaging, are highly desirable techniques for enhancing resolution while reducing CD variations. These techniques can be used to enhance conventional UV lithography or to achieve even higher resolution and CD control in methods using EUV, electron beam, deep UV, or immersion lithography. Directed self-assembling block copolymers contain blocks of etch-resistant copolymer units and blocks of highly etchable copolymer units, which produce areas of very high density patterns when coated, aligned, and etched on a substrate.

[0012] The neutral layer is a layer on the surface of a substrate or treated substrate that has no affinity for any of the block segments of the block copolymers used in the directed self-assembly. In the graphoepitaxy method of directed self-assembly of block copolymers, neutral layers are available because they allow the proper arrangement or orientation of the block polymer segments for directed self-assembly, which results in the proper arrangement of the etch-resistant block polymer segments and the highly etchable block polymer segments relative to the substrate. For example, in a surface containing lines and space features defined by conventional radiation lithography, the neutral layer allows the block segments to be oriented so that the block segments are oriented perpendicular to the surface of the substrate, which is ideal for both pattern rectification and pattern multiplication, depending on the length of the block segments in the block copolymers as related to the length between the lines defined by conventional photolithography. If the substrate interacts too strongly with one of these block segments, it will cause it to be laid flat on the surface to maximize the surface of the contact between the segments and the substrate; such a surface will disturb the desired vertical alignment, which can be used to achieve pattern rectification or pattern multiplication based on features created by conventional photolithography. Modifying selected small areas or pinning the substrate to interact strongly with one block of the block copolymer and leaving the rest of the surface coated with a neutral layer can be used to force the domains of the block copolymer to align in a desired direction and is the basis of pinned chemical epitaxy or graphoepitaxy for pattern multiplication.

[0013] There is a need for novel materials that can form a grafted polymer layer 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 by simple spin coating, followed by post-coating baking to achieve chemical bonding in the absence of activating components (such as acidic compounds, thermal acid generators, photoacid generators, thermal free radical generators, photochemical free radical generators, basic additives, thermal base generators, or photobase generators) for promoting the grafting reaction on the substrate. The presence of such thermally or photochemically reactive additive compounds is undesirable because of the small size and reactivity of these compounds, which may cause them to diffuse from the grafted film into other layers, causing undesirable reactions, such as corrosion. Another need is a grafted material in which the graftable polymer does not contain overly reactive grafting sites that may adversely affect the shelf life of the grafted solution in an organic solvent, such as a spin coating solvent. There is also a need for novel grafting materials, which can be selectively grafted to a specific type of substrate by changing the grafting baking. In this way, the surface properties of these materials, such as coating ability and corrosion resistance, can be changed by a simple spin coating process without the use of plasma deposition or electrochemical grafting, and in the case of a novel selective grafting process using the novel material of the present invention, in one step, only one type of material is coated on a substrate containing a morphology or chemical pattern, in which different materials are present on a substrate. There is also a need for novel neutral layer compositions, which remain neutral to the self-assembling block copolymer when forming a layer and are not damaged by the processing steps of the directed self-assembly technology, and can further enhance the lithographic performance of the directed self-assembly material and process, especially reduce the number of processing steps and provide better pattern resolution with good lithographic performance. There is also a need for a coatable pinning material for a small area metal or metal oxide substrate coated with a neutral layer (e.g., in a chemical epitaxial method) in other ways, so as to force the domain to be oriented vertically to the neutral layer substrate to force the domain to align in the desired direction. There is also a need for polar and non-polar brush compositions that will selectively form on only one type of material on a substrate containing a pattern of a different material to create a pinned area. Summary of the invention

[0014] One aspect of the disclosed subject matter relates to a polymer containing a grafted end group having at least two heteroatoms. Specifically, the polymer of structure (A) comprises 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 3pis C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but wherein if the repeating unit in the polymer chain (R) is (IIp), then R 3p can only be selected from C-1 to C-8 alkyl groups, and further, wherein if in the polymer chain (R) the repeating unit has the structure (Ip), then R 3p Only moieties selected from structures (IIIp) or (IIIp1) are possible, and the terminal group R 4p is selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, moieties of structure (IVp), moieties of structure (IVp1), or moieties of structure (IVp2). In addition, the terminal group R 3p and R 4p They cannot both be part of structures (IIIp) and (IVp), both be part of structures (IIIp) and (IVp1), or both be part of structures (IIIp) and (IVp2), respectively, but the polymer of structure (A) must contain an end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2).

[0015] In the polymer of structure (A), in the repeating unit of structure (Ip), R m1 is a C-1 to C-8 alkyl group, R 1p is a C-1 to C-8 alkyl group, and n1 is the number of this repeating unit in the polymer chain (R).

[0016] In the polymer of structure (A), in the repeating unit of structure (IIp), R m2 is H or C-1 to C-8 alkyl, R 2p is H or C-1 to C-8 alkyl, and n2 is the number of this repeating unit in the polymer chain (R).

[0017] In addition, in the polymer of structure (A), in structure (IIIp), R1 is a chelating group, which is located at the para position or the meta position and is selected from the dithiophosphinic acid (phosphinothioic) part of structure (Ia), the aminosulfonyl part of structure (Ib), and the phosphonamide part of structure (Ic), wherein *** represents the attachment point of the terminal group part to the polymer of structure (A).

[0018] In addition, in the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 is independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched alkyl, C-3 to C-8 cyclic alkyl, and * represents the point of attachment of this part to the terminal moiety of structure (IIIp), but wherein the polymer of structure (A) must contain a terminal moiety selected from structure (IIIp), (IVp), (IVp1) or (IVp2).

[0019] In addition, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and the dialkylamino moiety -N(R9)(R 10 ), and * represents the point of attachment of this moiety to the terminal moiety of the structure of (IIIp),

[0020] Furthermore, 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, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy, and * represents the point of attachment of this moiety to the terminal portion of the structure of (IIIp),

[0021] In addition, in structure (IIIp), R2 is selected from the group consisting of H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl of structure (Ib) and the phosphonamide of structure (Ic), and R 15 is a C-1 to C-8 alkyl group, and R e1 and R e2 independently selected from H, C-1 to C-8 alkyl and C-1 to C-8 alkoxy,

[0022] Furthermore, in the polymer of structure (A), in structure (IIIp1), R e1 and R e2 are independently selected from H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy, and R 15 is a C-1 to C-8 alkyl group, and *** represents the point of attachment of the terminal moiety to the polymer of structure (A).

[0023] Furthermore, in the polymer of structure (A), in structure (IVp), R 12 is H or C-1 to C-4 alkyl,

[0024] R 11 is a dithiophosphinic acid moiety of structure (IIa), *** represents the point of attachment of the terminal moiety to the polymer of structure (A), L1 is a linking moiety selected from the group consisting of a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the moiety R 11 L1 in the structure (IVp) is attached to the carbonyloxy group, and R 17 is selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties. In structure (IIa), * represents the point of attachment of the dithiophosphinic acid moiety to structure (IVp), R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0025] In addition, in the polymer of structure (A), in structure (IVp1), L is a connecting portion, which is a direct valence bond or a connecting group selected from C-1 to C-8 straight chain alkylene, C-3 to C-8 branched alkylene and C-5 to C-8 cyclic alkylene, alkyleneoxyaryl portion (*-alkylene-O-aryl-**) and alkylenearyl portion (*-alkylene-aryl-**), wherein ** represents the attachment point of the L connecting portion to the phosphorus in structure (IVp1), and * represents where L is attached to the polymer of structure (A), and Rs and Rs1 are individually selected from C-1 to C-8 alkoxy or C-1 to C-8 alkyl, and in addition, *** represents the attachment point of the terminal portion to the polymer of structure (A).

[0026] In addition, in the polymer of structure (A), in structure (IVp2), R1 is a chelating group, which is located at the para position or the meta position and is selected from the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl portion of structure (Ib) and the phosphonamide portion of structure (Ic), and R2 is selected from the group consisting of: H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight-chain alkyl, C-3 to C-8 branched alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight-chain alkoxy, C-3 to C-8 branched alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl portion of structure (Ib) and the phosphonamide of structure (Ic), R 18 Selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, and wherein *** represents the point of attachment of the terminal moiety to the polymer of structure (A).

[0027] In addition, the polymer of structure (A) has an M ranging from about 4000 to about 7000. n and have a polydispersity ranging from 1 to about 1.15.

[0028]

[0029]

[0030] Another aspect of the present invention relates to a composition of the polymer of structure (A) in an organic spin coating solvent.

[0031] Other aspects of the invention include methods of forming a pinned layer using the composition and chemical epitaxial methods using the pinning in the directed self-assembly of an overlying block copolymer, and subsequent methods of etching the directed self-assembled block polymer layer into a substrate.

[0032] Yet another aspect of the present invention is a novel compound of structure (I) and its use in the preparation of a polymer, wherein R1 is a chelating group located at the meta or para position and is selected from the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl moiety of structure (Ib), and the phosphonamide moiety of structure (Ic), wherein * represents the attachment point of these moieties to the compound of structure (I).

[0033] In the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0034] In the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and the dialkylamino moiety -N(R9)(R 10 ).

[0035] 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, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, or C-3 to C-8 cyclic alkoxy.

[0036] In addition, in the novel compound of structure (I), R2 is a substituent located at the meta or para position, which is selected from the group consisting of: H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl group of structure (Ib) and the phosphinamide of structure (Ic).

[0037]

[0038] Yet another aspect of the present invention is a novel compound of structure (II) and its use in the preparation of a polymer, wherein R 11 is the dithiophosphinic acid portion of structure (IIa), wherein * represents the point of attachment of the portion to the compound of structure (II), R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0039] In addition, in the compound, L1 is a linking moiety selected from the group consisting of a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the part R 11 L1 in the compound (II) is attached to the carbonyloxy group, and R 12 is H or C-1 to C-4 alkyl.

[0040]

[0041] Details

[0042] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not limitations on the subject matter claimed. In this application, unless otherwise specifically stated, the use of the singular includes the plural, the word "a / an" means "at least one", and the use of "or" means "and / or". In addition, the use of the term "including" and other forms such as "includes" and "included" is not restrictive. In addition, unless otherwise specifically stated, terms such as "element" or "component" include both elements and components containing one unit and elements or components containing more than one unit. As used herein, unless otherwise specified, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0043] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are hereby expressly incorporated herein by reference in their entirety for any purpose. If one or more of the incorporated literature references and similar materials define a term in a manner that contradicts the definition of the term in this application, the present application shall prevail.

[0044] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be straight chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.) or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.) polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties can be substituted or unsubstituted as described below. Unless otherwise specified, the term "alkyl" refers to such a moiety having C-1 to C-8 carbons. It should be understood that for structural reasons, straight chain alkyls start with C-1, while branched chain alkyls and cycloalkyls start with C-3 and polycyclic alkyls start with C-5. In addition, it should be further understood that, unless otherwise specified, moieties derived from the alkyls described below, such as alkoxy (alkoxy), have the same carbon number range. The same criteria apply to C-1 to C-4 alkyls. If the length of the alkyl group is specified as described above, the above-mentioned definition of the alkyl group still includes all types of alkyl moieties as described above relative to it, and structural considerations about the minimum carbon number of a given type of alkyl group still apply.

[0045] Alkyloxy (also known as alkoxy) refers to an alkyl group (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.) attached thereto via an oxy (-O-) moiety. These alkoxy moieties may be substituted or unsubstituted as described below. The criteria for establishing the nature of the alkyl group in a C-1 to C-8 alkoxy or C-1 to C-4 alkoxy are the same as previously described for the alkyl moiety.

[0046] Halo or halogen refers to a halogen, F, Cl, Br or I, attached to an organic moiety through a bond.

[0047] Haloalkyl refers to a linear, cyclic or branched saturated alkyl as defined above, wherein if more than one halo moiety is present, at least one of the hydrogens has been replaced by a halogen selected from the group of F, Cl, Br, I or a mixture of these. Fluoroalkyl is a specific subgroup of these moieties.

[0048] The term "alkylene" refers to a hydrocarbon group that can be straight chain, branched, or cyclic with two or more points of attachment (e.g., two points of attachment: methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, etc.; three points of attachment: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.). Here again, when a possible range of carbons is specified, such as C-1 to C-20, as a non-limiting example, the range covers straight chain alkylene starting with C-1, but only branched chain alkylene, or cycloalkylene starting with C-3 is represented. These alkylene moieties can be substituted or unsubstituted as described below.

[0049] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, biphenyl, triphenyl, etc. These aryl groups may be further substituted with any suitable substituents (e.g., the alkyl, alkoxy, acyl or aryl groups mentioned above).

[0050] Unless otherwise indicated herein, the term "substituted" when referring to aryl, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, fused aromatic ring, arene, heteroarene refers to one of these moieties that also contains one or more substituents selected from the following group: unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkoxyaryl (alkyl-O-aryl-), dialkoxyaryl ((alkyl-O-)2-aryl), haloaryl, alkoxy, alkylaryl, haloalkyl, halo, hydroxy, cyano, nitro, acetyl, alkylcarbonyl, formyl, vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH), and substituents containing vinylenearylene moieties (e.g., Ar (-CH=CH-Ar-)z , wherein z is 1-3). Specific non-limiting examples of substituted aryl and substituted arylvinyl substituents are as follows, wherein Indicates the attachment point:

[0051]

[0052] The polymer of the present invention

[0053] One aspect of the present invention is a polymer of structure (A) comprising two terminal 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 C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but wherein if the repeating unit in the polymer chain (R) is (IIp), then R 3p can only be selected from C-1 to C-8 alkyl groups, and further, wherein if in the polymer chain (R) the repeating unit has the structure (Ip), then R 3p Only moieties of structure (IIIp) or structure (IIIp1) can be selected. 4p is selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, moieties of structure (IVp), moieties of structure (IVp1), or moieties of structure (IVp2). In addition, the terminal group R 3p and R 4p They cannot both be part of structures (IIIp) and (IVp), both be part of structures (IIIp) and (IVp1), or both be part of structures (IIIp) and (IVp2), respectively, but the polymer of structure (A) must contain an end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2).

[0054] In the polymer of structure (A), in the repeating unit of structure (Ip), R m1 is a C-1 to C-8 alkyl group, R 1p is a C-1 to C-8 alkyl group, and n1 is the number of this repeating unit in the polymer chain (R).

[0055] In the polymer of structure (A), in the repeating unit of structure (IIp), Rm2 is H or C-1 to C-8 alkyl, R 2p is H or C-1 to C-8 alkyl, and n2 is the number of this repeating unit in the polymer chain (R).

[0056] In addition, in the polymer of structure (A), in structure (IIIp), R1 is a chelating group, which is located at the para position or the meta position and is selected from the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl portion of structure (Ib), and the phosphonamide portion of structure (Ic), wherein *** represents the attachment point of the terminal group portion to the polymer of structure (A).

[0057] In addition, in the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 are independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, and * represents the point of attachment of the moiety to the terminal portion of the structure of (IIIp).

[0058] In addition, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and the dialkylamino moiety -N(R9)(R 10 ), and * represents the point of attachment of this moiety to the terminal moiety of the structure of (IIIp).

[0059] Furthermore, 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, alkylene aryl, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy, and * represents the point of attachment of this part to the terminal part of the structure of (IIIp).

[0060] In addition, in structure (IIIp), R2 is selected from the group consisting of H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl of structure (Ib) and the phosphonamide of structure (Ic), and R 15 is a C-1 to C-8 alkyl group, and R e1 and R e2 Individually selected from H, C-1 to C-8 alkyl and C-1 to C-8 alkoxy.

[0061] Furthermore, in the polymer of structure (A), in structure (IIIp1), R e1 and R e2 are independently selected from H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy, and R 15 is a C-1 to C-8 alkyl group, and *** represents the point of attachment of the terminal moiety to the polymer of structure (A).

[0062] Furthermore, in the polymer of structure (A), in structure (IVp), R 12 is H or C-1 to C-4 alkyl,

[0063] R 11 is a dithiophosphinic acid moiety of structure (IIa), *** represents the point of attachment of the terminal moiety to the polymer of structure (A), L1 is a linking moiety selected from the group consisting of a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the moiety R 11 L1 in the structure (IVp) is attached to the carbonyloxy group, and R 17Selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties. In structure (IIa), * represents the point of attachment of the dithiophosphinic acid moiety to structure (IVp).

[0064] R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, or C-3 to C-8 cyclic alkyl.

[0065] In addition, in the polymer of structure (A), in structure (IVp1), L is a direct bond or a linking group selected from C-1 to C-8 straight chain alkylene, C-3 to C-8 branched alkylene and C-5 to C-8 cyclic alkylene, alkyleneoxyaryl moiety (*-alkylene-O-aryl-**) and alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the attachment point of the L linking moiety to the phosphorus in structure (IVp1), and * represents where L is attached to the polymer of structure (A), and Rs and Rs1 are individually selected from C-1 to C-8 alkoxy or C-1 to C-8 alkyl, and in addition, *** represents the attachment point of the terminal moiety to the polymer of structure (A).

[0066] In addition, in the polymer of structure (A), in structure (IVp2), R1 is a chelating group, which is located at the para position or the meta position and is selected from the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl portion of structure (Ib) and the phosphonamide portion of structure (Ic), and R2 is selected from the group consisting of: H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight-chain alkyl, C-3 to C-8 branched alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight-chain alkoxy, C-3 to C-8 branched alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl portion of structure (Ib) and the phosphonamide of structure (Ic), R 18 Selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, and wherein *** represents the point of attachment of the terminal moiety to the polymer of structure (A).

[0067] In addition, the polymer of structure (A) has an M ranging from about 4000 to about 7000. n and have a polydispersity ranging from 1 to about 1.15.

[0068]

[0069]

[0070] In one aspect of the polymers of the invention described herein, when the terminal group R 4p When it is not any of the chelating moieties (IVp), (IVp1) or (IVp2), it is H. In another aspect of this embodiment, R 4p is C-1 to C-8 alkyl. In another aspect of this embodiment, R 4p is C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 4p is a C-1 to C-8 trialkylsilyl group ((alkyl)3Si-). In another aspect of this embodiment, R 4p is a C-1 to C-8 dialkylsilyl group ((alkyl)2HSi-). In another aspect of this embodiment, R 4p is a C-1 to C-8 monoalkylsilyl group ((alkyl)H2Si-). In another aspect of this embodiment, R 4pis silane (H3Si-). In another aspect of this embodiment, R 4p is the benzyl moiety.

[0071] In one aspect of the polymer of the invention, when the chelating moiety (IVp) is present, R 17 is H. In another aspect of this embodiment, R 17 is C-1 to C-8 alkyl. In another aspect of this embodiment, in another aspect of this embodiment, R 17 is C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 17 is a C-1 to C-8 trialkylsilyl group ((alkyl)3Si-). In another aspect of this embodiment, R 17 is a C-1 to C-8 dialkylsilyl group ((alkyl)2HSi-). In another aspect of this embodiment, R 17 is a C-1 to C-8 monoalkylsilyl group ((alkyl)H2Si-). In another aspect of this embodiment, R 17 is silane (H3Si-). In another aspect of this embodiment, R 17 is the benzyl moiety.

[0072] In one aspect of the polymer of the invention, when the chelating moiety (IVp2) is present, R 18 is H. In another aspect of this embodiment, R 18 is C-1 to C-8 alkyl. In another aspect of this embodiment, R 18 is C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 18 is a C-1 to C-8 trialkylsilyl group ((alkyl)3Si-). In another aspect of this embodiment, R 18 is a C-1 to C-8 dialkylsilyl group ((alkyl)2HSi-). In another aspect of this embodiment, R 18 is a C-1 to C-8 monoalkylsilyl group ((alkyl)H2Si-). In another aspect of this embodiment, R 18 is silane (H3Si-). In another aspect of this embodiment, R 18 is the benzyl moiety.

[0073] In one aspect of the polymer of the present invention of structure (A), it has a more specific structure (A-1).

[0074]

[0075] In one aspect of the polymer of the present invention of structure (A-1), it has structure (A-2). In one aspect of this embodiment, Rm1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R2 is H.

[0076]

[0077] In another aspect of the polymer of the present invention of structure (A-1) or (A-2), it has structure (A-2a). In another embodiment of this structure, it has structure (A-2b). In one aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 alkoxy or C-1 to C-4 alkyl. In another aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 alkoxy. In another aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 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 embodiment of this structure, it has structure (A-2c). In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R2 is H.

[0078]

[0079] In another aspect of the polymer of the invention of 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 embodiment of this structure, it has structure (A-2f). In one aspect of these embodiments, R5 and R6 are independently selected from C-1 to C-4 alkyl. In another aspect of these embodiments, R5 and R6 are independently selected from C-1 to C-2 alkyl. In one aspect of these embodiments, R5 and R6 are methyl. In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R2 is H.

[0080]

[0081] In another aspect of the polymer of the present invention of structure (A-1) or (A-2), it has structure (A-2g). In another embodiment of this structure, it has structure (A-2h). In yet another aspect of this embodiment, it has structure (A-2i). In one aspect of these embodiments, R9 and R 10In another aspect of these embodiments, R9 and R 10 In one aspect of these embodiments, R9 and R 10 In one aspect of these embodiments, wherein R9 and R 10 R is independently selected from C-1 to C-4 alkyl, R8 is selected from C-1 to C-4 alkyl or aryl; in one aspect of this embodiment, R8 is C-1 to C-2 alkyl; in another aspect of this embodiment, the aryl is phenyl. In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R2 is H.

[0082]

[0083] In another aspect of the polymer of the present invention of structure (A-1) or (A-2), it has structure (A-3). In one aspect of the polymer, L1 is a direct valence bond. In another aspect of the polymer, L1 is a C-2 to C-8 alkylene moiety. In another aspect of the polymer, wherein L1 is an arylene moiety (-aryl-). In yet another aspect of the polymer, L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). 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 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 In another aspect of these embodiments, R 13 and R 14 In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are H. In another aspect of these embodiments, R17 is H. In another aspect of these embodiments, R 12 It's H.

[0084]

[0085] In another aspect of the polymer of structure (A-3), wherein L1 is a C-2 to C-8 alkylene moiety having structure (A-3a) or structure (A-3b), wherein and n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 is selected from C-1 to C-4 alkoxy and R 14 In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 It's H.

[0086]

[0087] In another aspect of the polymer of structure (A-3), it has structure (A-3c) or (A-3d), wherein L1 is an alkylene aryl moiety (*-alkylene-aryl-**), wherein n' is an integer ranging from 0 to 7. In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14In another aspect of these embodiments, R 13 is selected from C-1 to C-4 alkoxy and R 14 In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 It's H.

[0088]

[0089] In another aspect of the polymer of the present invention 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 C-2 to C-8 alkylene moiety. In another aspect of this embodiment, L is an arylene moiety (-aryl-). In yet another aspect of this embodiment, L is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In yet another aspect of this embodiment, L is an alkylenearyl moiety (*-alkylene-aryl-**). In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 All are H.

[0090]

[0091] In another aspect of the polymer of the present invention of structure (A-4), it has structure (A-4a) or structure (A-4b), wherein n' is an integer ranging from 0 to 7. In another aspect of this embodiment, it has structure (A-4b). In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkoxy. In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 All are H.

[0092]

[0093]

[0094] In another aspect of the polymer of the present invention of structure (A-4), it has structure (A-4c) or structure (A-4d), wherein n' is an integer ranging from 0 to 7. In another aspect of this embodiment, it has structure (A-4d). In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkoxy. In one aspect of these embodiments, R m1 In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 All are H.

[0095]

[0096]

[0097] In one aspect of the polymer of the present invention of structure (A), it has a more specific structure (B-1), wherein R 3p It is a C-1 to C-8 alkyl group.

[0098]

[0099] In another aspect of the polymer of the present invention of structure (B-1), it has structure (B-1a), wherein R 3p is C-1 to C-8 alkyl. 3p is a C-1 to C-8 alkyl group, and L1 is a direct bond. 3p is a C-1 to C-8 alkyl group, and L1 is a C-2 to C-8 alkylene group. In another aspect of this embodiment, R 3p is a C-1 to C-8 alkyl group, and L1 is an arylene moiety (-aryl-). In another aspect of this embodiment, R 3p is a C-1 to C-8 alkyl group, and L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13and R 14 In another aspect of these embodiments, R 13 is selected from C-1 to C-4 alkoxy and R 14 In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p It's H.

[0100]

[0101] In one aspect of the polymer of the present invention of structure (B-1), it has structure (B-1b) or (B-1c), wherein R 3p is C-1 to C-8 alkyl and n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of these embodiments, R 13 is selected from C-1 to C-4 alkoxy and R 14 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 It's H.

[0102] In another aspect of these embodiments, R 12 It's H.

[0103]

[0104]

[0105] In one aspect of the polymer of the present invention of structure (B-1), it has a more specific structure (B-1d) or (B-1e), wherein R 3p is C-1 to C-8 alkyl and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, R 13 and R 14In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of these embodiments, R 13 is selected from C-1 to C-4 alkoxy and R 14 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 It's H.

[0106]

[0107]

[0108] In another aspect of the polymer of the present invention of structure (B-1), it has structure (B-2). In one aspect of this embodiment, L is a direct valence bond. In another aspect of this embodiment, L is a C-2 to C-8 alkylene moiety. In another aspect of this embodiment, wherein L is an arylene moiety (-aryl-). In another aspect of this embodiment, is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In another aspect of this embodiment, wherein Rs and Rs1 are individually selected from C-1 to C-4 alkyl. In another aspect of this embodiment, Rs and Rs1 are individually selected from C-1 to C-4 alkoxy. In yet another embodiment, Rs and Rs1 are methyl. In another aspect of this embodiment, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p It's H.

[0109]

[0110] In aspects of the polymers of the invention of structure (B-2), wherein L is a direct bond and which has structure (B-2aa), another aspect of this embodiment is wherein Rs and Rs1 are independently selected from C-1 to C-4 alkyl. In another aspect of this embodiment, Rs and Rs1 are independently selected from C-1 to C-4 alkoxy. In yet another embodiment, Rs and Rs1 are methyl. In another aspect of this embodiment, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p It's H.

[0111]

[0112] In another aspect of the polymer of structure (B-2), it has structure (B-2a) or structure (B-2b), wherein R 15 is C-1 to C-8 alkyl, and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkoxy. In yet another embodiment, Rs and Rs1 are methyl. In another aspect, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p It's H.

[0113]

[0114] In another aspect of the polymer of structure (B-2), it has structure (B-2c) or structure (B-2d), wherein R 15 is C-1 to C-8 alkyl, and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C-1 to C-4 alkoxy. In yet another embodiment, Rs and Rs1 are methyl. In another aspect, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p It's H.

[0115]

[0116] In another aspect of the polymer of the present invention of structure (B-1), it has structure (B-3). In one aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 alkoxy or C-1 to C-4 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 It's H.

[0117]

[0118] In another 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 C-1 to C-4 alkoxy or C-1 to C-4 alkyl. In another aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 alkoxy. In another aspect of these embodiments, R3 and R4 are independently selected from C-1 to C-4 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 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 It's H.

[0119]

[0120]

[0121] 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 C-1 to C-4 alkyl. In another aspect of these embodiments, R5 and R6 are independently selected from C-1 to C-2 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 It's H.

[0122]

[0123]

[0124] 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, R9 and R 10 In another aspect of these embodiments, R9 and R 10 In one aspect of these embodiments, R9 and R 10 In one aspect of these embodiments, wherein R9 and R 10 R is independently selected from C-1 to C-4 alkyl, R8 is selected from C-1 to C-4 alkyl or aryl; in one aspect of this embodiment, R8 is C-1 to C-2 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 It's H.

[0125]

[0126] Compositions of the present invention

[0127] Another aspect of the present invention is a composition of any of the polymers of the present invention having structure (A) described herein and an organic spin-coating solvent.

[0128] Another aspect of the present invention is a composition of any of the polymers of the present invention having structure (A-1) described herein and an organic spin-coating solvent.

[0129] Another aspect of the invention is a composition comprising any of the polymers of the invention having any of structures (A-2), (A-2a), (A-2b), (A-2c), (A-2d), (A-2e), (A-2f), (A-2g), (A-2h), or (A-2i) described herein and an organic spin coating 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 consists of any of the above polymer structures and an organic spin-coating solvent.

[0130] Another aspect of the invention is a composition comprising any of the polymers of the invention having any of structures (A-3), (A-3a), (A-3b), (A-3c), or (A-3d) described herein and an organic spin-coating 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 of the polymer structures described in this embodiment and an organic spin-coating solvent.

[0131] Another aspect of the invention is a composition comprising any of the polymers of the invention having any of structures (A-4), (A-4a), (A-4b), (A-4c), or (A-4d) described herein and an organic spin-coating 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 of the polymer structures described in this embodiment and an organic spin-coating solvent.

[0132] Another aspect of the invention is a composition comprising any of the polymers of the invention described herein having any 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 of the polymer structures described in this embodiment and an organic spin coating solvent.

[0133] Another aspect of the invention is a composition comprising any of the polymers of the invention described herein having any 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 of the polymer structures described in this embodiment and an organic spin coating solvent.

[0134] Another aspect of the invention is a composition comprising any of the polymers of the invention described herein having any 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 of the polymer structures described in this embodiment and an organic spin coating solvent.

[0135] In the above embodiments of the novel composition, the organic spin-coating solvent is a solvent that can dissolve the novel polymer and any other additional optional components as indicated above. The organic spin-coating solvent can be a single solvent or a mixture of solvents. Suitable solvents are organic solvents that can include, 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 oxalate 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; ketoesters such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylates 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; ketoether derivatives such as diacetone alcohol methyl ether; ketoalcohol derivatives such as acetone alcohol or diacetone alcohol; ketals or acetals, such as 1,3 dioxolane and diethoxypropane; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, anisole and mixtures thereof.

[0136] In addition to the polymer and the solvent, the novel composition may also contain surfactants as additives to facilitate coating.

[0137] Another aspect of the invention is a novel composition, wherein the novel polymer accounts for about 0.1wt.% to about 10wt.% of the total weight of the composition (including the organic spin-coating solvent). On the other hand, it accounts for about 0.1wt.% to about 2wt.%. In yet another embodiment, it accounts for about 0.5wt.% to about 1.5wt.%. In yet another embodiment, it accounts for about 0.75wt.% to about 1.5wt.%. In yet another embodiment, it accounts for about 1.0wt.%. Methods of using the compositions of the invention.

[0138] Another aspect of the present invention is a method of selectively forming a pinning layer brush on a substrate comprising both a metallic surface region and a non-metallic surface region, comprising the steps of;

[0139] i) coating a composition comprising any one of the polymers having structure (A) or its substructures on the substrate to form a film,

[0140] 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,

[0141] iii) washing the baked film with a solvent to remove the ungrafted polymer and form a pinning layer brush only on the metal surface area of ​​the substrate.

[0142] In one aspect of this embodiment, the metal 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-metal surface region is selected from the group consisting of Si, silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiON) and an organic dielectric substrate.

[0143] Another aspect of the present invention is a method comprising the steps of:

[0144] ia) coating a composition comprising a polymer having structure (A), or any of its substructures, on a substrate comprising both a metallic surface region and a non-metallic surface region to form a film,

[0145] 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,

[0146] iiia) washing the baked film with a solvent to remove ungrafted polymer to form a grafted substrate wherein the pinning layer brushes are present only on the metal surface region of the substrate,

[0147] iva) coating the grafted substrate with a neutral layer composition to form a neutral layer coating,

[0148] va) curing the neutral layer coating,

[0149] via) washing away the uncured neutral layer with a solvent, leaving a neutral oriented brush in the non-metallic region, and forming a chemical epitaxial oriented layer on the substrate,

[0150] viia) coating the chemical epitaxy orientation layer with a block copolymer solution to form a block copolymer coating,

[0151] viiia) annealing the coating of the block copolymer to form an oriented self-assembled film of the block copolymer on the chemical epitaxy oriented layer.

[0152] In one aspect of the method, in the substrate, the metal surface region is tungsten and the non-metal surface region is silicon or silicon oxide. In another aspect of this, the block copolymer is a block copolymer consisting of styrene repeating units and alkyl acrylic repeating units. In another aspect of this embodiment, the block copolymer is an AB diblock copolymer of alkyl acrylic repeating units and styrene repeating units, or an ABA triblock copolymer of alkyl acrylic repeating units and styrene repeating units.

[0153] Compounds of the present invention

[0154] Another aspect of the present invention are novel compounds which are useful in the synthesis of the polymers of the present invention of structure (A) and substructures thereof as described herein.

[0155] One embodiment of these novel compounds are those having structure (I), wherein R1 is a chelating group located at the meta or para position selected from the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl moiety of structure (Ib), the phosphonamide moiety of structure (Ic), wherein * represents the point of attachment of these moieties to the compound of structure (I).

[0156] In addition, in the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0157] In addition, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and dialkylamino moiety -N(R9)(R 10 ).

[0158] Furthermore, 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, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy. In one aspect of this embodiment, R8 is aryl, and in a more specific aspect of this embodiment is phenyl. In one aspect of this embodiment, R8 is alkylene aryl. In one aspect of this embodiment, R8 is C-2 to C-8 alkyleneoxy alkyl. In one aspect of this embodiment, R8 is C-2 to C-8 haloalkyl. In one aspect of this embodiment, R8 is C-1 to C-8 straight chain alkyl. In one aspect of this embodiment, R8 is C-3 to C-8 branched chain alkyl. In one aspect of this embodiment, R8 is C-3 to C-8 cyclic alkyl. In one aspect of this embodiment, R8 is C-1 to C-8 straight chain alkoxy. In one aspect of this embodiment, R8 is C-3 to C-8 branched alkoxy. In one aspect of this embodiment, R8 is or C-3 to C-8 cyclic alkoxy.

[0159] In addition, in the compound of structure (I), R2 is a substituent located at the meta or para position, which is selected from the group consisting of: H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid portion of structure (Ia), the aminosulfonyl of structure (Ib) and the phosphinamide of structure (Ic).

[0160] Specifically, when both R1 and R2 are the phosphonamide moieties of structure (Ic), R8 can be individually selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkylene oxide alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy. In one aspect of this embodiment, R8 is aryl, and in a more specific aspect of this embodiment is phenyl. In one aspect of this embodiment, R8 is alkylene aryl. In one aspect of this embodiment, R8 is C-2 to C-8 alkylene oxide alkyl. In one aspect of this embodiment, R8 is C-2 to C-8 haloalkyl. In one aspect of this embodiment, R8 is C-1 to C-8 straight chain alkyl. In one aspect of this embodiment, R8 is a C-3 to C-8 branched alkyl. In one aspect of this embodiment, R8 is a C-3 to C-8 cyclic alkyl. In one aspect of this embodiment, R8 is a C-1 to C-8 straight chain alkoxy. In one aspect of this embodiment, R8 is a C-3 to C-8 branched alkoxy.

[0161] In one aspect of this embodiment, R8 is or C-3 to C-8 cyclic alkoxy.

[0162]

[0163] In another embodiment of the compound of structure (I), it has the more specific structure (I-1).

[0164]

[0165] In another embodiment of the compound of structure (I), it has the more specific structure (I-2).

[0166]

[0167] In more specific embodiments of compounds of structures (I), (I-1) or (I-2), R1 is the chelating group as the dithiophosphinic acid portion of structure (Ia). In more specific embodiments of compounds of structures (I), (I-1) or (I-2), R1 is the chelating group as the aminosulfonyl portion of structure (Ib). In more specific embodiments of compounds of structures (I), (I-1) or (I-2), R1 is the phosphonamide portion 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 alkylene aryl. In another aspect of these embodiments, R2 is C-2 to C-8 alkyleneoxyalkyl. In another aspect of these embodiments, R2 is C-2 to C-8 haloalkyl. In another aspect of these embodiments, R2 is C-1 to C-8 straight chain alkyl. In another aspect of these embodiments, R2 is C-3 to C-8 branched chain alkyl. In another aspect of these embodiments, R2 is a C-3 to C-8 cyclic alkyl. In another aspect of these embodiments, R2 is a C-1 to C-8 straight chain alkoxy. In another aspect of these embodiments, R2 is a C-3 to C-8 branched alkoxy. In another aspect of these embodiments, R2 is a C-3 to C-8 cyclic alkoxy. In another aspect of these embodiments, R2 is a dithiophosphinic 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).

[0168] One embodiment of these novel compounds are those having structure (II) wherein R 11 is the dithiophosphinic acid portion of structure (IIa), wherein * represents the point of attachment of the portion to the compound of structure (II), R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0169] In addition, in these compounds of structure (II), L1 is a linking moiety selected from the group consisting of a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the part R 11 L1 in the compound (II) is attached to the carbonyloxy group.

[0170] Furthermore, in these compounds of structure (II), R 12 is H or C-1 to C-4 alkyl.

[0171]

[0172] In a more specific embodiment of the compound of structure (II) above, R 13 is a C-1 to C-8 straight chain alkoxy group. In another aspect of these embodiments, R 13 is a C-3 to C-8 branched alkoxy group. In another aspect of these embodiments, R 13 It is a C-3 to C-8 cyclic alkoxy group.

[0173] In a more specific embodiment of the compound of structure (II) above, R 14 In another aspect of these embodiments, R 14 In another aspect of these embodiments, R 14 is C-2 to C-8 alkyleneoxyalkyl. In another aspect of these embodiments, R 14 is C-2 to C-8 haloalkyl. In another aspect of these embodiments, R 14 is a C-1 to C-8 straight chain alkyl. In another aspect of these embodiments, R 14 is a C-3 to C-8 branched alkyl group. In another aspect of these embodiments, R 14 is a C-3 to C-8 cyclic alkyl. In another aspect of these embodiments, R 14 is a C-1 to C-8 straight chain alkoxy group. In another aspect of these embodiments, R 14 is a C-3 to C-8 branched alkoxy group. In another aspect of these embodiments, R 14 is a C-3 to C-8 cyclic alkoxy group. In another aspect of these embodiments, R 14 is a dialkylamino moiety, -N(R9)(R 10 ).

[0174] In another more specific embodiment, R13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl.

[0175] In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 is selected from C-1 to C-4 alkoxy and R 14 Selected from C-1 to C-4 alkyl.

[0176] In a more specific embodiment of the compound of the above structure (II), R9 is a C-1 to C-8 straight chain alkyl. In another aspect of these embodiments, R9 is a C-3 to C-8 branched chain alkyl. In another aspect of these embodiments, R9 is a C-3 to C-8 cyclic alkyl.

[0177] In more specific embodiments of the compounds of structure (II) above, L1 is a direct valence bond. In another aspect of these embodiments, L1 is a C-2 to C-8 alkylene moiety. In another aspect of these embodiments, L1 is an arylene moiety (-aryl-). In more specific embodiments of these embodiments, L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

[0178] In more specific embodiments of the compound of structure (II) above, it has structure (IIc) or structure (IIc1), wherein n is 1 to 7. In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 is selected from C-1 to C-4 alkoxy and R 14 Selected from C-1 to C-4 alkyl.

[0179]

[0180] In more specific embodiments of the compound of structure (II) above, it has structure (IIb) or structure (IIb1), wherein n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 and R 14 In another aspect of this embodiment, R 13 is selected from C-1 to C-4 alkoxy and R 14 Selected from C-1 to C-4 alkyl.

[0181]

[0182] In a more specific embodiment of the compound of structure (II) above, it has structure (IIb2), wherein R 13a and R 14a and are individually selected from C-1 to C-4 alkyl groups.

[0183] DETAILED DESCRIPTION

[0184] Example

[0185] Reference will now be made to more specific embodiments of the present disclosure and to experimental results that provide support for these embodiments.The following examples are given to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0186] It will be apparent to those skilled in the art that various modifications and variations may be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, it is intended that the disclosed subject matter, including the description provided by the following embodiments, covers modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0187] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is to be understood that the disclosure is made by way of example only and that those skilled in the art may resort to numerous variations in the conditions and sequence of steps without departing from the spirit and scope of the disclosed and claimed subject matter.

[0188] Chemicals

[0189] Unless otherwise stated, all chemicals were purchased from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g., Techniques in High-Vacuum Anionic Polymerization" By David Uhrig and Jimmy Mays and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0190] Phenyl acrylate derivatives were synthesized by esterification of acryloyl chloride with corresponding hydroxy compounds under alkaline conditions, and DPE derivatives were synthesized by alkoxylation of DPE-(m)-CH2Br (1-(bromomethyl)-3-(1-phenylvinyl)benzene) with corresponding hydroxy compounds under alkaline conditions.

[0191] All synthesis experiments were performed under N2 atmosphere. Photolithography experiments were performed as described herein. The molecular weight of the copolymers was measured using a gel permeation chromatograph. The gel permeation chromatograph was equipped with and μ-ultrastyragel column.

[0192] Lithography experiments were performed using a TEL Clean ACT8 track. SEM images were taken with an Applied Materials NanoSEM_3D scanning electron microscope at 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm).

[0193] Etching experiments were performed on self-assembled monolayer block copolymers of methyl methacrylate and styrene using standard isotropic oxygen etching conditions.

[0194] Gel permeation chromatography was equipped with styrene-DVB gels connected in series, and The HPLC-MS / MS was carried out on a porous column (PSS (polymer standard services), Germany) and THF at 1 ml / min was used as the mobile phase. Polystyrene standards (18 samples) with Mn ranging from 1,000 g / mol to 200,000 g / mol (PSS, Germany) were used to construct calibration curves for determining the molecular weight and polydistribution index (PDI) of the synthesized polymers. A Bruker 400 MHz NMR unit was used for molecular characterization.

[0195] Recorded in CDCl3 using a Bruker Advanced III 400 MHz spectrometer 1 H NMR spectrum.

[0196] Coating studies were performed using dielectric blankets as well as metal coupons. The films were baked at the desired temperature and time and rinsed with excess material. The grafted brushes were studied using water contact angle, FT and XPS.

[0197] The polymer brushes were coated on blanket metal or dielectric wafers using 230°C / 5 min bake conditions and excess material was rinsed off with an organic solvent, and the substrates were analyzed using WCA, FT, and XPS.

[0198] experiment:

[0199] Preparation of polymer formulations:

[0200] The polymers described herein were dissolved separately in PGMEA to form 1wt.% solutions. These solutions were filtered separately using nylon filters (Entegris, Billerica, Ma). These solutions were coated on both metal (Cu, W) and SiO2 wafers at 1500rpm, and then the wafers were baked at 230°C for 5min. After baking, the wafers were rinsed with PGMEA for 2min to remove any ungrafted polymer from the wafers, which were then dried by spinning "1,500rpm" and then baked at 110°C for 1min. Water contact angles, XPS were then measured to understand the grafting efficiency and the results are shown in Table 1. Subsequently, polymer formulations containing a second brush of hydroxyl-terminated PS-OH or PMMA-OH were prepared in PGMEA at 1wt.% solid. Then, after filtering with a 0.25-micron nylon filter, the solution was spin-coated onto a pre-brushed metal and SiO2 substrate. After baking at various temperatures and times, the double-brushed substrates were rinsed to remove the unreacted second brush. Then, the dual-brush treated substrates were examined for cross-grafting by water contact angle (WCA) and X-ray photoelectron spectroscopy (XPS) to judge the efficiency of the first brush and the selectivity to the metal substrate.

[0201] Example 1 Synthesis of dimethylphosphinethioate-terminated polystyrene

[0202] Anionic polymerization is carried out in a nitrogen-dried 250mL round-bottomed flask equipped with a magnetic stirring bar, a diaphragm adapter that can be connected to a vacuum or nitrogen atmosphere and a rubber diaphragm for reagent addition via a syringe or cannula. Anhydrous cyclohexane 100mL is transferred to a flask using a cannula under nitrogen. Purified styrene monomer 20mL (18g) is added to the cyclohexane solution. The reaction mixture is degassed and filled with nitrogen.

[0203]

[0204] Scheme 1: Synthesis of thiophosphine-terminated polystyrene

[0205] Under rapid stirring, the required amount of initiator sec-butyl lithium in hexane (1.3 M) was added to the monomer solution. Immediately, an orange color of the carbanion was formed, indicating that the polystyryl lithium proliferated with a slight increase in the reaction temperature. The reaction was kept stirring at 35°C-45°C for 2h. Then, purified dimethylthiophosphonyl chloride (distilled over CaH2) was transferred via a cannula to the active polystyryl lithium anion solution. The color of the reaction slowly disappeared over 5 minutes. The reaction mixture was diluted with THF (2×) and then precipitated into an excess (5×) of isopropanol: water (80:20) mixture. The polymer was filtered and dried under vacuum at 80°C for 18h. Yield: 17.2 g (96%), M n , GPC=6,600g / mol, PDI=1.05, 31 P NMR shows a signal at 44ppm, confirming the presence of end groups with -P=S. Solutions of the polymer in PGMEA (1wt.%) spin-coated onto tungsten and silicon coupons show 90° on W and 52° on silicon coupons after baking (200°C / 15min / N2) and rinsing (2min, dynamic), respectively. This confirms the selectivity of the polymer for W. XPS studies show that the elemental ratios of C / W and C / Si are 25.84 and 0.43, respectively.

[0206] Example 2. Synthesis of polymethyl methacrylate terminated with diethyl thiophosphonate

[0207] In the first step, diethyl phosphonothioate DPE derivative was prepared by thiolation of MTAG-10. Diethyl phosphonate-terminated PMMA was synthesized using an initiator prepared from diethyl phosphonothioate DPE derivative and sec-BuLi. The reaction was carried out in tetrahydrofuran at -78°C.

[0208]

[0209] Scheme 2.1: Synthesis of DPE derivative (diethyl thiophosphonate DPE)

[0210] Step 1: Synthesis of diethyl thiophosphonate DPE

[0211] Diethylphosphonate DPE (MTAG-10) (29.0 g, 91.67 mmol) and Lawesson's reagent (18.7 g, 404.471 mmol) were weighed into a two-necked round bottom flask with a reflux condenser and a rubber septum attached. 250 mL of anhydrous toluene was transferred by cannula. The flask was kept in an oil bath and the temperature was raised to 120° C. The reaction was allowed to run overnight (although 2-4 hours is sufficient). Toluene was removed on a rotary evaporator. The brown-red liquid was loaded on a silica column and separated using a mixture of hexane:ethyl acetate in a 70:30 ratio. Excess Lawesson's reagent and its byproducts eluted very close to the desired product. The desired DPE derivative ((4-(1-phenylvinyl)phenyl)phosphonothioic acid O,O-diethyl ester [DPE-PS(OEt)2) was obtained as a pale yellow liquid. Lawesson's reagent and MTAG-26 have a very foul odor typical of thiol compounds. Yield: 20 g, % yield 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

[0212] Step 2: Synthesis of PMMA terminated with diethylthiophosphonate

[0213]

[0214] Scheme 2.2: Polymethyl methacrylate terminated with diethyl thiophosphonate

[0215] O,O-diethyl (4-(1-phenylvinyl)phenyl)phosphinothioate [DPE-PS(OEt)2] (1.72 g, 5 mmol) was dissolved in 6 ml toluene titrated with hexyl lithium and added to an ampoule. 28 mL of methyl methacrylate was added to a separate ampoule and degassed under dynamic vacuum to 25 mL (23.3 g, 23.3 mmol) of methyl methacrylate. The ampoule was attached to the side arm of a reactor containing lithium chloride (2.2 g, 41 mmol) and a magnetic stirring bar. The reactor was evacuated under vacuum and charged with nitrogen. Tetrahydrofuran (300 mL) was added via a cannula and the mixture was stirred and cooled to -78 °C, in which case the mixture was titrated with sBuLi until the yellow color persisted. The mixture was warmed to room temperature, in which case the yellow color dissipated. The mixture was cooled to -78 °C and a DPE-P(S)(OEt)2) solution was added. sBuLi (4.0 mL, 1.17 M in cyclohexane, 4.68 mmol) was then slowly added to produce a red mixture. Methyl methacrylate was added dropwise over 6 minutes, at which point the red color turned to colorless. The mixture was stirred for an additional 12 minutes, at which point 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times the polymer solution), filtered, and dried at 40 °C for 1 h. 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 , 4,460 g / mole Mw, 1.046 PDI. 1 H NMR MW 6,000 g / mol. 1 HNMR and 31 P NMR analysis confirmed the presence of terminal functional groups.

[0216] Example 3 Synthesis of diethyl thiophosphonate-terminated polystyrene:

[0217]

[0218] Scheme 3: Diethylthiophosphonate-terminated polystyrene

[0219] (2.0g, 3.322mmol) diethyl thiophosphonate DPE is dissolved in 6ml toluene, titrated with 1,1-diphenyl-3-methylpentyl lithium (prepared by the reaction of sec-butyl lithium and DPE), and added to an ampoule. 28mL of styrene is added to a separate ampoule and degassed to 25mL (24.543g, 23.65mmol) of styrene under dynamic vacuum. The ampoule is attached to the side arm of a reactor equipped with lithium chloride (2.2g, 41mmol) and a magnetic stirring bar. The reactor is evacuated under vacuum and nitrogen is loaded. Tetrahydrofuran (300mL) is added via a cannula and the mixture is stirred and cooled to -78°C, in which case the mixture is titrated with sBuLi until the yellow color lasts. The mixture is warmed to room temperature, in which case the yellow color dissipates. The mixture was cooled to -78 °C and sBuLi (4.0 mL, 1.17 M in cyclohexane, 4.68 mmol) was added to produce a pale yellow mixture. Styrene was added dropwise over 10 minutes, at which point an orange color was formed. The mixture was stirred for another 5 minutes, at which point a DPE-P(S)(OEt)2) solution was added. The red solution was stirred for a few minutes and the reaction was terminated with 1 mL of degassed methanol. The polymer was recovered by precipitation in an excess of isopropanol (7 times the polymer solution), filtered, and dried at 40 °C for 1 h. Redissolved in ethyl acetate and washed with Milli-Q water, and precipitated in an excess of isopropanol. Filtered and dried under vacuum to give a white powder (24 g, 92% yield). GPC: 3,900 g / mol M n , 4,800 g / mole Mw, 1.14 PDI. 1 H NMR MW 4,700 g / mol. 1 HNMR and 31 P NMR analysis confirmed the presence of terminal functional groups.

[0220] Example 4 Synthesis of Ethyldimethylphosphonamide-Terminated Polymethyl Methacrylate

[0221] 4.1 Synthesis of 1-phenyl-1'-[4-ethyl(dimethylphosphonamido)]-phenylethylene

[0222]

[0223] Scheme 4.1: Synthesis of 1-phenyl-1'-[4-ethyl(dimethylphosphonamido)]-phenylethylene

[0224] 4-bromobenzophenone (25g, 95.7mmol) and THF were stirred together and cooled to 0°C. n-Butyl lithium (71.38mL, 114.9mmol) was added, followed by methyl triphenylphosphonium bromide (41g, 114.9mmol). The mixture was warmed to room temperature. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% aqueous HCl and NaCl aqueous solutions and dried over MgSO4. MgSO4 was filtered out and the filtrate was concentrated in vacuo. 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 eluent, and then concentrated to give 4-bromo-1,1'-diphenylethylene (18g, % yield 72%) as a colorless oil

[0225] 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 warmed to room temperature for 30 minutes. The slurry was filtered and the filtrate was concentrated in vacuo. The residue was redissolved in dichloromethane and ground with ether. The mixture was filtered and concentrated, then repeated to remove salts. This gave chloroethyl (dimethylphosphonamido) (2.3 g, 95% yield) as a sticky solid.

[0226] Step-2: 4-bromo-1,1'-diphenylethylene (1 g, 3.86 mmol) generated by (a) was dissolved in tetrahydrofuran and cooled to -78°C. nBuLi (2.4 mL, 3.86 mmol, 1.6 M in hexane) was added and stirred for 30 minutes. In a separate flask, chloroethyl (dimethylphosphinamide) (0.6 g, 3.86 mmol) generated by (b) was slurried in THF and cooled to -78°C. The previously generated 4-lithium-1,1'-diphenylethylene was added through a 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. MgSO4 was filtered out, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as eluent. The product fractions were concentrated to give 1-phenyl-1'-[4-ethyl(dimethylphosphinamido)]-phenylethylene (0.7 g, yield 60%) as a pale yellow oil 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.

[0227]

[0228] Scheme 4.2: Ethyldimethylphosphonamide-terminated polymethyl methacrylate

[0229] 4.2 Synthesis of PMMA-ethyl (dimethylphosphonamide) end-capping:

[0230] 1-phenyl-1'-(4-ethyldimethylphosphonamido)phenylethylene [DPE-P(O)(Et)(NMe2)](1.43g, 5mmol) in 6ml of dry toluene is added to ampoule.Methyl methacrylate (20.7g, 207mmol) is added to a separate ampoule and freeze-thawed 3 times to degas.The ampoule is attached to the side arm of a reactor equipped with lithium chloride (1.75g, 41mmol) and a magnetic stirring bar.The reactor is evacuated under vacuum and nitrogen is loaded.Tetrahydrofuran (210mL) is added via a cannula and the mixture is stirred and cooled to -78°C, in which case the mixture is titrated with sBuLi until yellow continues.The mixture is warmed to room temperature, in which case the yellow dissipates.The mixture is once again cooled to -78°C and DPE-P(O)(Et)(NMe2) solution is added.SBuLi (1.2mL) is added dropwise to titrate the mixture until yellow continues. sBuLi (2.96 mL, 1.4 M in cyclohexane, 4 mmol) was then slowly added to produce a red mixture. Methyl methacrylate was rapidly added dropwise to the mixture over 2 minutes, at which point the red color turned colorless. The mixture was stirred for an additional 30 minutes, at which point 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times the polymer solution), filtered, and dried under vacuum at 40 °C for 12 h to give a white powder (21 g, 97% yield). GPC: 4,195 g / mol M n , 4,460 g / mole Mw, 1.06 PDI.

[0231] Example 5. Synthesis of polymethyl methacrylate terminated with phenyl dimethylphosphonamide

[0232]

[0233] Scheme 5.1: Synthesis of 1-phenyl-1'-[4-phenyl(dimethylphosphinamido)]-phenylethylene

[0234] 5.1 Synthesis of 1-phenyl-1'-[4-phenyl(dimethylphosphonamido)]-phenylethylene:

[0235] Step-1: 4-bromobenzophenone (25 g, 95.7 mmol) and THF were stirred together and cooled to 0 ° C. n-Butyl lithium (71.38 mL, 114.9 mmol) was added, followed by methyltriphenylphosphonium bromide (41 g, 114.9 mmol). The mixture was warmed to room temperature. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% HCl aqueous solution and NaCl aqueous solution and dried over MgSO4. MgSO4 was filtered out and the filtrate was concentrated in vacuo. 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 eluent, and then concentrated to give 4-bromo-1,1'-diphenylethylene (20 g, 80% yield) as a colorless oil

[0236] 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 warmed 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 and then repeated to remove the salts. This gave chlorophenyl(dimethylphosphonamide) as a sticky solid (12 g, 80% yield)

[0237] Step-3: 4-Bromo-1,1'-diphenylethylene (3 g, 11.6 mmol) generated by 5.1 was dissolved in tetrahydrofuran and cooled to -78°C. nBuLi (8.7 mL, 13.9 mmol, 1.6 M in hexane) was added and stirred for 30 minutes. In a separate flask, chlorophenyl (dimethylphosphamide) (3.4 g, 16.7 mmol) generated by (b) was slurried in THF and cooled to -78°C. The previously generated 4-lithium-1,1'-diphenylethylene was added through a 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. MgSO4 was filtered out, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as eluent. The product fractions were concentrated to give 1-phenyl-1'-[4-phenyl(dimethylphosphinamido)]-phenylethylene as a light 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.

[0238]

[0239] Scheme 5.2: Phenylphosphonamide-terminated polymethyl methacrylate

[0240] 5.2: Synthesis of polymethyl methacrylate terminated with phenyl dimethylphosphonamide:

[0241] 1-phenyl-1'-(4-phenyldimethylphosphonamido)phenylethylene [DPE-P(O)(Ph)(NMe2)](1.58g, 5mmol) in 6ml of dry toluene is added in ampoule.Methyl methacrylate (20.68g, 207mmol) is added in a separate ampoule and freeze-thawed 3 times to degas.Ampoule is attached to the side arm of the reactor equipped with lithium chloride (1.75g, 41mmol) and magnetic stirring bar.The reactor is evacuated under vacuum and nitrogen is loaded.Through cannula, tetrahydrofuran (210mL) is added and the mixture is stirred and cooled to -78°C, in which case the mixture is titrated with sBuLi, until yellow continues.The mixture is warmed to room temperature, in which case the yellow dissipates.The mixture is once again cooled to -78°C and DPE-P(O)(Ph)(NMe2) solution is added. sBuLi (1.2 mL) was added dropwise to titrate the mixture until the yellow color persisted. sBuLi (3 mL, 1.4 M in cyclohexane, 4 mmol) was then slowly added to produce a red mixture. Methyl methacrylate was quickly added dropwise to the mixture over 2 minutes, at which point the red color turned colorless. The mixture was stirred for another 30 minutes, at which point 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in an excess of hexane (7 times that of the polymer solution), filtered, and dried under vacuum at 40 °C for 12 h to give a white powder (21 g, 99% yield). GPC: 5,602 g / mol M n , 6,158 g / mole Mw, 1.10 PDI.

[0242] Example 6. Synthesis of dimethylsulfonamide-terminated polymethyl methacrylate:

[0243] 6.1 Synthesis of 1-phenyl-1'-[4-(dimethylsulfonyl)]-phenylethylene:

[0244] Step-1: Acetophenone (3.31mL, 28.4mmol) is dissolved in tetrahydrofuran and cooled to -78°C. nBuLi (12.6mL, 20.2mmol, 1.6M in hexane) is added, stirred for 30 minutes, 4-bromobenzene dimethyl sulfonamide (4.85g, 18.4mmol) is added, and the mixture is stirred for 30 minutes, then warmed to room temperature for 1 hour. The mixture is diluted with ethyl acetate, washed with water, and dried over MgSO4. MgSO4 is filtered out, and the filtrate is concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as eluent. The product fraction is concentrated to obtain 1-phenyl-1-[4-(dimethylsulfonamido)]-phenylethyl-1-ol (2.7g, 48% yield) as a white solid.

[0245]

[0246] Scheme 6.1: Synthesis of 1-phenyl-1'-[4-(dimethylsulfonamido)]-phenylethylene

[0247] Step-2: 1-phenyl-1-[4-(dimethylsulfonyl)]-phenylethane-1-ol (2.7 g, xmmol) and p-toluenesulfonic acid monohydrate (catalyst) generated by (a) were slurried in toluene and heated to 70°C for 3 hours. The mixture was diluted with ethyl acetate and washed with water, and dried over MgSO4. MgSO4 was filtered out, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as eluent. The product fraction was concentrated to obtain 1-phenyl-1'-[4-(dimethylsulfonyl)]-phenylethylene (2.6 g, 99% yield) as a light yellow oil. 1 HNMR, 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

[0248] 6:2: PMMA-brush synthesis:

[0249]

[0250] Scheme 6.2: Dimethylsulfonamide-terminated polymethyl methacrylate

[0251] 1-phenyl-1'-[4-(dimethylsulfonamido)]-phenylethylene [DPE-SO2(NMe2)] (1.02g, 3.6mmol) in 3ml of dry toluene is added to an ampoule. Methyl methacrylate (15.8g, 157mmol) is added to a separate ampoule and freeze-thawed 3 times to degas. The ampoule is attached to the side arm of a reactor equipped with lithium chloride (0.4g, 10mmol) and a magnetic stirring bar. The reactor is evacuated under vacuum and nitrogen is loaded. Tetrahydrofuran (200mL) is added via a cannula and the mixture is stirred and cooled to -78°C, in which case the mixture is titrated with sBuLi until the yellow color lasts. The mixture is warmed to room temperature, in which case the yellow color dissipates. The mixture is once again cooled to -78°C and DPE-SO2(NMe2) solution is added. sBuLi (1.2mL) is added dropwise to titrate the mixture until the yellow color lasts. sBuLi (2.1 mL, 1.4 M in cyclohexane, 3 mmol) was then slowly added to produce a red mixture. Methyl methacrylate was rapidly added dropwise to the mixture over 2 minutes, at which point the red color turned colorless. The mixture was stirred for an additional 30 minutes, at which point 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times the polymer solution), filtered, and dried under vacuum at 40 °C for 12 h to give a white powder (15 g, 95% yield). GPC: 5,773 g / mol M n , 5,946 g / mole Mw, 1.03 PDI.

[0252] Preparation of polymer formulations:

[0253] The polymers described herein were dissolved separately in PGMEA to form 1wt.% solutions. These solutions were filtered separately using nylon filters (Entegris, Billerica, Ma). These solutions were coated on both metal (Cu, W) and SiO2 wafers at 1500rpm, and then the wafers were baked at 230°C for 5min. After baking, the wafers were rinsed with PGMEA for 2min to remove any ungrafted polymer from the wafers, which were then dried by spinning "1,500rpm" and then baked at 110°C for 1min. Water contact angles, XPS were then measured to understand the grafting efficiency and the results are shown in Table 1. Subsequently, polymer formulations containing a second brush of hydroxyl-terminated PS-OH or PMMA-OH were prepared in PGMEA at 1wt.% solid. Then, after filtering with a 0.25-micron nylon filter, the solution was spin-coated onto a pre-brushed metal and SiO2 substrate. After baking at various temperatures and times, the double-brushed substrates were rinsed to remove the unreacted second brush. Then, the dual-brush treated substrates were examined by WCA and XPS for cross-grafting to judge the efficiency of the first brush and the selectivity to the metal substrate.

[0254] Brush coating:

[0255] The polymer brushes were coated on blanket metal or dielectric wafers using 230°C / 5 min bake conditions and excess material was rinsed off with an organic solvent, and the substrates were analyzed using WCA, FT, and XPS.

[0256] Table 1 shows data for selective grafting of metals with different materials, which show high carbon ratios to the substrate and appropriately high contact angles, depending on the polarity of the grafted polymer on the metal. The polymers were coated as 1% solutions in PGMEA and baked at 230°C / 5 min, then rinsed with PGMEA solvent for 2 minutes. All polymers used in these tests had an M of approximately 5,000 g / mol. n .

[0257] Table 1.

[0258]

[0259]

[0260] Preparation of polymer formulations:

[0261] The polymers described herein were dissolved separately in PGMEA to form 1wt.% solutions. These solutions were filtered separately using nylon filters (Entegris, Billerica, Ma). These solutions were coated on both metal (Cu, W) and SiO2 wafers at 1500rpm, and then the wafers were baked at 230°C for 5min. After baking, the wafers were rinsed with PGMEA for 2min to remove any ungrafted polymer from the wafers, which were then dried by spinning "1,500rpm" and then baked at 110°C for 1min. Water contact angles, XPS were then measured to understand the grafting efficiency and the results are shown in Table 1. Subsequently, polymer formulations containing a second brush of hydroxyl-terminated PS-OH or PMMA-OH were prepared in PGMEA at 1wt.% solid. Then, after filtering with a 0.25-micron nylon filter, the solution was spin-coated onto a pre-brushed metal and SiO2 substrate. After baking at various temperatures and times, the double-brushed substrates were rinsed to remove the unreacted second brush. Then, the dual-brush treated substrates were examined by WCA and XPS for cross-grafting to judge the efficiency of the first brush and the selectivity to the metal substrate.

Claims

1. A polymer of structure (A) comprising two terminal 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 the anionic initiator 3p is C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but wherein if the repeating unit in the polymer chain (R) is (IIp), then R 3p can only be selected from C-1 to C-8 alkyl, and further, wherein if in the polymer chain (R) the repeating unit has structure (Ip), then R 3p can only be selected from moieties of structure (IIIp) or structure (IIIp1), End group R 4p is a moiety selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, moieties of structure (IVp), moieties of structure (IVp1) or moieties of structure (IVp2), and in addition, the terminal group R 3p and R 4p It cannot be a part of both structures (IIIp) and (IVp), a part of both structures (IIIp) and (IVp1), or a part of both structures (IIIp) and (IVp2), but the polymer of structure (A) must contain a terminal moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2), In the repeating unit of the structure (Ip), R m1 is a C-1 to C-8 alkyl group, R 1p is a C-1 to C-8 alkyl group, and n1 is the number of this repeating unit in the polymer chain (R); In the repeating unit of structure (IIp), R m2 is H or C-1 to C-8 alkyl, R 2p is H or C-1 to C-8 alkyl, n2 is the number of this repeating unit in the polymer chain (R); and In structure (IIIp), R1 is a chelating group located at the para or meta position and is selected from the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl moiety of structure (Ib), and the phosphonamide moiety of structure (Ic), wherein *** represents the attachment point of the terminal moiety to the polymer of structure (A), wherein In the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 is independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, and * represents the point of attachment of the moiety to the terminal moiety of the structure of (IIIp), In the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and the dialkylamino moiety -N(R9)(R 10 ), and * represents the point of attachment of this moiety to the terminal moiety of the structure of (IIIp), In the phosphonamide moiety of structure (Ic), R7 is the dialkylamino moiety -N(R9)(R 10 ), and R8 is selected from aryl, alkylene aryl, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy, and * represents the point of attachment of the moiety to the terminal portion of the structure of (IIIp), R2 is selected from the group consisting of H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl of structure (Ib) and the phosphonamide of structure (Ic), and R 15 is a C-1 to C-8 alkyl group, and R e1 and R e2 independently selected from H, C-1 to C-8 alkyl and C-1 to C-8 alkoxy, In structure (IIIp1), R e1 and R e2 are independently selected from H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxyalkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy, and R 15 is a C-1 to C-8 alkyl group, and *** represents the point of attachment of the terminal moiety to the polymer of structure (A), In structure (IVp), R 12 is H or C-1 to C-4 alkyl, R 11 is the dithiophosphinic acid portion of structure (IIa), wherein * represents the point of attachment of the dithiophosphinic acid portion to structure (IVp), wherein R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, L1 is a linking moiety selected from the following: a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the moiety R wherein 11 L1 in the structure (IVp) is attached to the carbonyloxy group, R 17 is selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, and *** represents the point of attachment of the terminal moiety to the polymer of structure (A), In structure (IVp1), L is a direct bond or a linking group selected from C-1 to C-8 straight chain alkylene, C-3 to C-8 branched chain alkylene and C-5 to C-8 cyclic alkylene, alkyleneoxyaryl moiety (*-alkylene-O-aryl-**) and alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L linking moiety to the phosphorus in structure (IVp1), and * represents where L is attached to the polymer of structure (A), and Rs and Rs1 are independently selected from C-1 to C-8 alkoxy or C-1 to C-8 alkyl, and wherein *** represents the point of attachment of the terminal moiety to the polymer of structure (A), In structure (IVp2), R1 is a chelating group located at the para position or the meta position and selected from the dithiophosphinic acid moiety of the structure (Ia), the aminosulfonyl moiety of the structure (Ib) and the phosphonamide moiety of the structure (Ic), R2 is selected from the group consisting of H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; dithiophosphinic acid moiety of structure (Ia), aminosulfonyl of structure (Ib) and phosphonamide of structure (Ic), R 18 is selected from the group consisting of H, C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(=O)-), C-1 to C-8 trialkylsilyl ((alkyl)3Si-), C-1 to C-8 dialkylsilyl ((alkyl)2HSi-), C-1 to C-8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-) and benzyl moieties, and wherein *** represents the point of attachment of the terminal moiety to the polymer of structure (A), In addition, the polymer of structure (A) has an M ranging from about 4000 to about 7000. n , and having a polydispersity ranging from 1 to about 1.15; 2. The polymer according to claim 1, having structure (A-1), 3. The polymer according to claim 1 or 2, having structure (A-2), 4. The polymer according to any one of claims 1 to 3, having structure (A-2a) 5. The polymer according to any one of claims 1 to 4, having structure (A-2b) 6. The polymer according to any one of claims 1 to 4, having structure (A-2c), 7. The polymer according to any one of claims 1 to 3, having structure (A-2d), 8. The polymer according to any one of claims 1 to 3, having structure (A-2e) 9. The polymer according to any one of claims 1 to 3 and 8, having structure (A-2f), 10. The polymer according to any one of claims 1 to 3, having structure (A-2g), 11. The polymer of any one of claims 1 to 3 and 10, and having structure (A-2h), 12. The polymer according to any one of claims 1 to 3 and 10, having structure (A-2i), 13. The polymer according to any one of claims 1 to 2, having structure (A-3) 14. The polymer according to any one of claims 1 to 2 and 13, wherein L1 is a direct bond.

15. The polymer according to any one of claims 1 to 2 and 13, wherein L1 is a C-2 to C-8 alkylene moiety.

16. The polymer according to any one of claims 1 to 2 and 13, wherein L1 is an arylene moiety (-aryl-).

17. The polymer according to any one of claims 1 to 2 and 13, wherein L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

18. The polymer according to any one of claims 1 to 2, having structure (A-3a), wherein: R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n is an integer ranging from 1 to 7, 19. The polymer according to any one of claims 1 to 2 and 18, having structure (A-3b), wherein R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n is an integer ranging from 1 to 7, 20. The polymer according to any one of claims 1 to 2, having structure (A-3c), wherein: R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7, 21. The polymer of any one of claims 1 to 2 and 20, having structure (A-3d), wherein: R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7, 22. The polymer according to any one of claims 1 to 2, having structure (A-4), 23. The polymer of any one of claims 1 to 2 and 22, wherein L is a direct bond.

24. The polymer of any one of claims 1 to 2 and 22, wherein L is a C-2 to C-8 alkylene moiety.

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

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

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

28. The polymer of any one of claims 1 to 2 and 22, having structure (A-4a), wherein: n' is an integer ranging from 0 to 7, 29. The polymer of any one of claims 1, 2, 22 and 28 having structure (A-4b) and n' is an integer ranging from 0 to 7, 30. The polymer of claim 1 or 2, having structure (A-4c), wherein: n' is an integer ranging from 0 to 7, 31. The polymer of any one of claims 1 to 2, 22 and 30 having structure (A-4d), wherein: R s and R s1 are independently selected from C-1 to C-8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7, 32. The polymer of claim 1 having structure (B-1), wherein: R 3p is a C-1 to C-8 alkyl group, 33. The polymer according to claim 1 or 32, having structure (B-1a), wherein: R 3p is a C-1 to C-8 alkyl group, 34. The polymer of any one of claims 1, 32 and 33, wherein R 3p is a C-1 to C-8 alkyl group, and L1 is a direct bond.

35. The polymer of any one of claims 1, 32 and 33, wherein R 3p is a C-1 to C-8 alkyl group, and L1 is a C-2 to C-8 alkylene moiety.

36. The polymer of any one of claims 1, 32 and 33, wherein R 3p is a C-1 to C-8 alkyl group, and L1 is an arylene moiety (-aryl-).

37. The polymer of any one of claims 1, 32 and 33, wherein R 3p is a C-1 to C-8 alkyl group, and L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

38. The polymer of any one of claims 1, 32 and 33, having structure (B-1b), wherein: R 3p is a C-1 to C-8 alkyl group, and R 13 and R 14 are individually selected from C-1 to C-4 alkoxy groups, and n is an integer ranging from 1 to 7, 39. The polymer of any one of claims 1, 32, 33 and 38, having structure (B-1c), wherein: R 3p is a C-1 to C-8 alkyl group, and R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n is an integer ranging from 1 to 7, 40. The polymer of any one of claims 1, 32 and 33, having structure (B-1d), wherein: R 3p is a C-1 to C-8 alkyl group, wherein R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7, 41. The polymer of any one of claims 1, 32, 33 and 40 having structure (B-1e), wherein: R 3p is a C-1 to C-8 alkyl group, wherein R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7, 42. The polymer of claim 1 or 32, having structure (B-2), 43. The polymer of any one of claims 1, 32 and 42, wherein L is a direct bond.

44. The polymer of any one of claims 1, 32 and 42, wherein L is a C-2 to C-8 alkylene moiety.

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

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

47. The polymer of any one of claims 1, 33 and 42, having structure (B-2a), wherein: Rs and Rs1 are independently selected from C-1 to C-4 alkoxy groups, R 15 is a C-1 to C-8 alkyl group, and n' is an integer ranging from 0 to 7, 48. The polymer of any one of claims 1, 33, 42 and 47 having structure (B-2b), wherein: Rs and Rs1 are independently selected from C-1 to C-8 alkyl or alkoxy groups, R 15 is a C-1 to C-8 alkyl group, and n' is an integer ranging from 0 to 7, 49. The polymer of any one of claims 1, 33 and 42, having structure (B-2c), wherein: Rs and Rs1 are independently selected from C-1 to C-8 alkyl or alkoxy groups, R 15 is a C-1 to C-8 alkyl group, and n' is an integer ranging from 0 to 7, 50. The polymer of any one of claims 1 to 2, 45 and 49 having structure (B-2d), wherein Rs and Rs1 are independently selected from C-1 to C-8 alkyl or alkoxy groups, R 15 is a C-1 to C-8 alkyl group, and n' is an integer ranging from 0 to 7, 51. The polymer of claim 1 or 32, having structure (B-3), 52. The polymer of any one of claims 1 and 51, having structure (B-3a) 53. The polymer of any one of claims 1, 51 and 52, having structure (B-3b) 54. The polymer of any one of claims 1, 51 and 52, having structure (B-3c), 55. The polymer of claim 1 or 51 having structure (B-3d), 56. The polymer of any one of claims 1, 51 and 55, having structure (B-3e) 57. The polymer of any one of claims 1, 51 and 55, having structure (B-3f), 58. The polymer of claim 1 or 51 having structure (B-3g), 59. The polymer of any one of claims 1, 51 and 58, and having structure (B-3h), 60. The polymer of any one of claims 1, 51 and 58, having structure (B-3i), 61. A composition comprising a polymer as claimed in claims 1 to 60 and an organic spin coating solvent.

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

63. A composition comprising a polymer as claimed in any one of claims 3 to 12 and an organic spin coating solvent.

64. A composition comprising a polymer as claimed in any one of claims 13 to 21 and an organic spin coating solvent.

65. A composition comprising a polymer as claimed in any one of claims 22 to 31 and an organic spin coating solvent.

66. A composition comprising the polymer of claim 32 and an organic spin coating solvent.

67. A composition comprising a polymer as claimed in any one of claims 33 to 41 and an organic spin coating solvent.

68. A composition comprising a polymer as claimed in any one of claims 42 to 50 and an organic spin coating solvent.

69. A composition comprising a polymer as claimed in any one of claims 51 to 60 and an organic spin coating solvent.

70. A method for selectively forming a pinning layer brush on a substrate comprising both a metallic surface region and a non-metallic surface region, comprising the steps of: i) coating the composition according to any one of claims 61 to 69 on 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 the ungrafted polymer and form a pinning layer brush only on the metal surface area of ​​the substrate.

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

72. A method comprising the following steps: ia) applying the composition according to any one of claims 51 to 58 on a substrate comprising both a metallic surface region and a non-metallic surface region 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 to form a grafted substrate wherein the pinning layer brushes are present only on the metal surface region 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) washing away the uncured neutral layer with a solvent, leaving a neutral oriented brush in the non-metallic region, and forming a chemical epitaxial oriented layer on the substrate, viia) coating the chemical epitaxy orientation layer with a block copolymer solution to form a block copolymer coating, viiia) annealing the coating of the block copolymer to form an oriented self-assembled film of the block copolymer on the chemical epitaxy oriented layer.

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

74. The method of claim 72 or 73, wherein: The block copolymer is a block copolymer composed of styrene repeating units and alkyl acrylic acid repeating units.

75. The method of any one of claims 72 to 74, wherein: The block copolymer is an AB diblock copolymer of an alkyl acrylic acid repeating unit and a styrene repeating unit, or an ABA triblock copolymer of an alkyl acrylic acid repeating unit and a styrene repeating unit.

76. A compound of structure (I), wherein R1 is a chelating group located at the meta or para position and is selected from the dithiophosphinic acid moiety of structure (Ia), the aminosulfonyl moiety of structure (Ib), and the phosphonamide moiety of structure (Ic), wherein * represents the attachment point of these moieties to the compound of structure (I), wherein In the dithiophosphinic acid portion of structure (Ia), R3 and R4 are independently aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy; and the dialkylamino portion -N(R9)(R 10 ), where R9 and R 10 independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, In the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl and the dialkylamino moiety -N(R9)(R 10 ), 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, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy or C-3 to C-8 cyclic alkoxy, R2 is a substituent located at the meta or para position selected from the group consisting of: H, aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; dithiophosphinic acid moiety of structure (Ia), aminosulfonyl of structure (Ib) and phosphonamide of structure (Ic) 77. The compound of claim 76, wherein The compound has structure (I-1), 78. The compound of claim 76, wherein The compound has structure (I-2), 79. The compound of claim 76, wherein R1 in the chelating group is a dithiophosphinic acid moiety of structure (Ia).

80. The compound of claim 76, wherein R1 in the chelating group is the aminosulfonyl moiety of structure (Ib).

81. The compound of claim 76, wherein R1 in the chelating group is a phosphonamide moiety of structure (Ic).

82. A compound as described in any one of claims 76 to 81, wherein R2 is H.

83. A compound as described in any one of claims 76 to 81, wherein R2 is an aryl group.

84. A compound as described in any one of claims 76 to 81, wherein R2 is an alkylene aryl group.

85. A compound as described in any one of claims 76 to 81, wherein R2 is a C-2 to C-8 alkyleneoxyalkyl group.

86. A compound as described in any one of claims 76 to 81, wherein R2 is a C-2 to C-8 haloalkyl group.

87. A compound as described in any one of claims 76 to 81, wherein R2 is a C-1 to C-8 straight chain alkyl group.

88. A compound as described in any one of claims 76 to 81, wherein R2 is a C-3 to C-8 branched chain alkyl group.

89. A compound as described in any one of claims 76 to 81, wherein R2 is a C-3 to C-8 cyclic alkyl group.

90. A compound as described in any one of claims 76 to 81, wherein R2 is a C-1 to C-8 straight chain alkoxy group.

91. A compound as described in any one of claims 76 to 81, wherein R2 is a C-3 to C-8 branched alkoxy group.

92. A compound as described in any one of claims 76 to 81, wherein R2 is a C-3 to C-8 cyclic alkoxy group.

93. A compound as described in any one of claims 76 to 81, wherein R2 is the dithiophosphinic acid moiety of structure (Ia).

94. A compound as described in any one of claims 76 to 81, wherein R2 is the aminosulfonyl moiety of structure (Ib).

95. A compound as described in any one of claims 76 to 81, wherein R2 is the phosphonamide moiety of structure (Ic).

96. A compound of structure (II), wherein R 11 is the dithiophosphinic acid moiety of structure (IIa), wherein * represents the point of attachment of the moiety to the compound of structure (II), wherein R 13 and R 14 independently selected from the group consisting of aryl, alkylene aryl, C-2 to C-8 alkyleneoxy alkyl, C-2 to C-8 haloalkyl, C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl, C-1 to C-8 straight chain alkoxy, C-3 to C-8 branched chain alkoxy, C-3 to C-8 cyclic alkoxy; and dialkylamino moiety -N(R9)(R 10 ), where R9 and R 10 Independently selected from C-1 to C-8 straight chain alkyl, C-3 to C-8 branched chain alkyl, C-3 to C-8 cyclic alkyl; L1 is a linking moiety selected from the following: a direct bond, a C-2 to C-8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** represents the point of attachment of the L1 organic linking moiety to the phosphorus in structure (IIa), and * represents the moiety R wherein 11 L1 in the compound (II) is attached to the carbonyloxy group, R 12 is H or C-1 to C-4 alkyl, 97. The compound of claim 96, wherein R 13 It is a C-1 to C-8 straight chain alkoxy group.

98. The compound of claim 96, wherein R 13 It is a C-3 to C-8 branched chain alkoxy group.

99. The compound of claim 96, wherein R 13 It is a C-3 to C-8 cyclic alkoxy group.

100. A compound as described in any one of claims 96 to 99, wherein R 14 It is an aromatic group.

101. A compound as described in any one of claims 96 to 99, wherein R 14 It is an alkylene aryl group.

102. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-2 to C-8 alkyleneoxyalkyl group.

103. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-2 to C-8 haloalkyl group.

104. A compound as described in any one of claims 95 to 99, wherein R 14 It is a C-1 to C-8 straight chain alkyl group.

105. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-3 to C-8 branched chain alkyl group.

106. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-3 to C-8 cyclic alkyl group.

107. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-1 to C-8 straight chain alkoxy group.

108. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-3 to C-8 branched chain alkoxy group.

109. A compound as described in any one of claims 96 to 99, wherein R 14 It is a C-3 to C-8 cyclic alkoxy group.

110. A compound as described in any one of claims 96 to 99, wherein R 14 is the dialkylamino moiety -N(R9)(R 10 ).

111. The compound of claim 110, wherein R9 is a C-1 to C-8 straight chain alkyl group.

112. The compound of claim 110, wherein R9 is a C-3 to C-8 branched chain alkyl group.

113. The compound of claim 110, wherein R9 is a C-3 to C-8 cyclic alkyl group.

114. A compound as described in any one of claims 96 to 113, wherein L1 is a direct bond.

115. A compound as described in any one of claims 96 to 113, wherein L1 is a C-2 to C-8 alkylene moiety.

116. A compound as described in any one of claims 96 to 113, wherein L1 is an arylene moiety (-aryl-).

117. A compound as described in any one of claims 96 to 113, wherein L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

118. The compound of claim 117 having structure (IIc), wherein: n is 1 to 7, 119. The compound of claim 117 or 118 having structure (IIc1), wherein R 13 and R 14 are independently selected from C-1 to C-8 alkyl or alkoxy, and n is an integer from 1 to 7, 120. A compound as described in any one of claims 117 to 119 having structure (IIa1), wherein R 13 and R 14 are independently selected from C-1 to C-4 alkyl or alkoxy, and n is an integer ranging from 1 to 7, 121. A compound as described in any one of claims 96 to 113, wherein L1 is an alkylene aryl moiety (*-alkylene-aryl-**).

122. The compound of claim 121 having structure (IIb), wherein n is an integer ranging from 1 to 7, 123. The compound of claim 121 or 122 having structure (IIb1), 124. A compound as described in any one of claims 121 to 123 having structure (IIb2), wherein, R 13a and R 14a independently selected from C-1 to C-4 alkyl, 125. Use of a compound according to any one of claims 76 to 124 in the preparation of a polymer.

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