Selectively self-assembled monolayers via spin-coating for use in DSA

Abstract

The present invention relates to compounds of formula (I) in which A is a core moiety selected from structures (Ia), (Ib), (Ic) and (Id) attached via a direct valence bond or a divalent linking group as X; m is the number of linear alkylene moieties of chain length n, each of which has a terminal B reactive moiety; and further, * indicates a possible point of attachment of the linear alkylene moiety in each structure; B is selected from -OH, -CH=CH, -O-(P=O)(OR), -O-(P=O)(OR)R. s , -N3 and -SH, where n is in the range of 8 to 12. The invention also relates to compositions comprising these compounds, the use of these compositions to form self-assembled monolayers (SAMs), their use in DSA processing as neutral or derivative layers that can be selectively removed from metal substrates, and remover solutions that achieve this selective removal. TIFF2024533218000064.tif72170

Description

[Technical field]

[0001] The present invention relates to compounds and compositions comprising these compounds capable of forming self-assembled monolayers on substrates. These self-assembled monolayers can act as neutral hydrophobic or hydrophilic pinning layers in the directed self-assembly of block copolymers and are useful in the manufacture of electronic devices. [Background technology]

[0002] Self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the manufacture of microelectronic devices, which can achieve critical dimensions (CD) of features on the nanoscale order. Self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques for repeating features such as arrays of contact holes or posts. In conventional lithography approaches, ultraviolet (UV) radiation can be used to expose through a mask onto a photoresist layer coated on a substrate or layered substrate. Positive or negative photoresists are useful, and they can also contain refractory elements such as silicon to allow dry development using conventional integrated circuit (IC) plasma processing techniques. In positive photoresists, UV radiation passing through the mask causes a photochemical reaction in the photoresist that renders the exposed areas removable with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through the mask renders the exposed areas less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features such as gates, vias, or interconnects are then etched into the substrate or layered substrate, and the remaining photoresist is removed. With conventional lithographic exposure processes, there is a limit to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve using radiation exposure due to limitations related to aberrations, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture. Due to the need for large scale integration, device circuit dimensions and features have been continually reduced. In the past, the final resolution of features has depended on the wavelength of light used to expose the photoresist, which is itself limited. Directed (also known as guided) self-assembly (DSA) techniques such as graphoepitaxy and chemoepitaxy using block copolymer imaging with patterned regions on the substrate are highly desirable techniques used to improve resolution while reducing CD variation.These techniques can be used to augment conventional UV lithography techniques or to enable higher resolution and CD control in approaches using EUV, e-beam, deep UV or immersion lithography. Directed self-assembling block copolymers contain blocks of etch-resistant and easily etched copolymer units that, when coated, aligned and etched on a substrate, provide areas of very dense patterns.

[0003] In guided or unguided self-assembly of block copolymer films on patterned or unpatterned substrate regions, respectively, the self-assembly process of the block copolymer layer typically occurs during annealing of the film over a neutral layer. The neutral layer on the semiconductor substrate may be an unpatterned neutral layer, or in chemoepitaxy or graphoepitaxy, the neutral layer may contain graphoepitaxy or chemoepitaxy guided features, respectively (formed via UV lithography techniques as described above). While the block copolymer film is annealed, the underlying neutral layer induces nanophase separation of the block copolymer domains. One example is the formation of phase-separated domains that are lamellae or cylinders perpendicular to the underlying neutral layer surface. These nanophase-separated block copolymer domains form pre-patterns (e.g., lines and spaces L / S) that can be transferred into the substrate via an etching process (e.g., plasma etching). In graphoepitaxy or chemoepitaxy, these guiding figures can affect both pattern modification and pattern multiplication. In the case of unpatterned neutral layers, this produces, for example, repeating arrays of L / S or CH. For example, in conventional block copolymers such as poly(styrene-b-methyl methacrylate) (P(Sb-MMA)), where both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermal annealing the block copolymer onto a layer of non-preferential or neutral material that is grafted or crosslinked at the polymer-substrate interface.

[0004] In the graphoepitaxy-induced self-assembly method, block copolymers self-assemble on substrates that have been pre-patterned using conventional lithography (ultraviolet, deep UV, e-beam, extreme ultraviolet (EUV) exposure sources) to form repeating topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-induced self-assembly array, block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the pre-patterned lines to enhance pattern resolution by dividing the spaces in the trenches between the topographical lines into finer patterns. For example, diblock or triblock copolymers capable of microphase separation, including carbon-rich blocks (e.g., styrene or containing some other element such as Si, Ge, Ti) that are resistant to plasma etching, and blocks that are highly etchable or removable by plasma, can provide high-resolution pattern definition. An example of a highly etchable block may include a monomer that is oxygen-rich and free of refractory elements, yet capable of forming a highly etchable block, such as methyl methacrylate. The plasma etching gases used in the etching process that defines the self-assembled pattern are typically those used in processes used in the manufacture of integrated circuits (ICs). In this manner, very fine patterns can be created in typical IC substrates compared to those that can be defined by conventional lithography techniques, thus achieving pattern multiplication. Similarly, graphoepitaxy can be used to create more dense features such as contact holes. In graphoepitaxy, a suitable block copolymer aligns itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography to form a denser array of regions of etchable and etch-resistant domains, which when etched, provides a denser array of contact holes. As a result, graphoepitaxy can provide both pattern modification and pattern multiplication.

[0005] In chemical epitaxy or pinned chemical epitaxy, block copolymers self-assemble on surfaces with induced geometries that are regions of differing chemical affinity, but without or significant topography on which to base the induced self-assembly process (in other words, non-induced topography). For example, the surface of a substrate can be patterned using conventional lithography (e.g., UV, deep UV, e-beam, EUV) to produce a line-and-space (L / S) pattern of surfaces with differing chemical affinities in which exposed regions, where the surface chemistry has been modified by radiation, alternate with unexposed regions that show no chemical change. These regions do not provide topographical differences, but rather surface chemical differences or pinning that guide the self-assembly of block copolymer segments. Specifically, the directed self-assembly of block copolymers with block segments containing etch-resistant repeat units (e.g., styrene repeat units) and fast-etching repeat units (e.g., methyl methacrylate repeat units) allows for precise placement of the etch-resistant and fast-etching block segments on a pattern. This technique allows for precise placement of these block copolymers and subsequent pattern transfer to a substrate after plasma or wet etching processing. Chemical epitaxy has the advantage that this can be fine-tuned by changing chemical differences to help improve line edge roughness and CD control, allowing for modification of the pattern. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern modified using chemoepitaxy.

[0006] These neutral layers are layers on the substrate or surfaces of the treated substrate that have no affinity for any of the block segments of the block copolymers used for directed self-assembly. Neutral layers are useful in graphoepitaxy methods of directed self-assembly of block copolymers because they allow for the proper placement or orientation of the block polymer segments for directed self-assembly, which results in the proper placement of the etch-resistant and highly etchable block polymer segments relative to the substrate. For example, in a surface containing line-and-space features defined by conventional radiation lithography, the neutral layer allows for the orientation of the block segments such that they are oriented perpendicular to the surface of the substrate, which is an ideal orientation for both pattern modification and pattern multiplication depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, the segment will lie flat on the surface, maximizing the contact area between the segment and the substrate; such a surface would disrupt the desired vertical alignment that can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modifying or pinning selected small regions of the substrate to make them interact strongly with one block of the block copolymer, while leaving the rest of the surface coated with a neutral layer, can be useful to align the domains of the block copolymer in a desired direction, and this is the basis of pinned chemoepitaxy or graphoepitaxy used for pattern multiplication. The pinned regions can be hydrophilic, with a relatively large affinity for polar block copolymer segments, such as, for example, polymethylmethacrylate block segments in a block copolymer of styrene and methylmethacrylate, or alternatively, hydrophobic, with a relatively large affinity for, for example, polystyrene block segments in a block copolymer of styrene and methylmethacrylate.

[0007] Area-selective deposition of organic or inorganic materials is an important process in the IC industry that requires limited selectivity to either metal or dielectric via guided or non-guided assembly processes. One such application is the passivation of dielectric or metal surfaces on a predefined patterned substrate for area-selective deposition of metal oxides via atomic layer deposition. This application requires selective grafting of organic materials such as self-assembled monolayers (SAMs) or chain-end functional polymers (brushes) for subsequent introduction of a deposition or assembly process that allows passivation of the selective areas underside. There is a strong industrial need for simple methods such as spin-coating organic materials that can show selectivity to specific areas in chip fabrication lithography processes for ALD or DSA. The commonly used methods of SAM deposition are solution or immersion and gas-phase methods. Both of these methods have their own advantages and disadvantages. The chemistry and processing of the SAM precursor limits its selective deposition via spin-coating.

[0008] There is a need for new materials that can easily form self-assembled monolayers (SAMs) with a high density of moieties that can impart neutral or pinning properties on semiconductor substrates (e.g., Si, GaAs, etc.), metal substrates (e.g., Cu, W, Mo, Al, Zr, Ti, Hf, Au, etc.), and metal oxide substrates (e.g., copper oxide, aluminum oxide, hafnium oxide, zirconium oxide, titanium oxide, etc.) via a simple spin coat and subsequent post-coat bake that results in the formation of a SAM. Such self-assembled monolayers would have a much higher density and uniformity of moieties that can impart neutral or pinning properties than conventional polymer brush layers or cross-linked and / or grafted MAT materials. Additionally, MAT materials, such as DSA-derived, are much thicker than SAM materials, which can lead to residue issues during DSA processing, and further, MAT materials may also contain other additives, such as radical generators, thermal acid generators, or other additives that can contaminate the substrates used in DSA. A MAT layer in this context is a crosslinked layer that can be used as a DSA neutral or pinning layer that is insoluble with respect to any layers coated on top of it.

[0009] There is also a need for such SAM neutral layers that can be easily selectively cleaved from metal substrates, further improving the lithographic performance of directed self-assembly materials and processes by reducing the number of steps and providing better pattern resolution with good lithographic performance. [Brief description of the drawings]

[0010] [Figure 1] Schematic structure of a spin-coatable SAM [Diagram 2] Direct flow of chemically modified prepatterns [Diagram 3] Modification of selective cleavage of organic moieties from metal substrates using a remover solution using dielectric first and metal second [Figure 4]Directed self-assembly of block copolymers (PS-b-PMMA) on chemical prepatterns modified with SAMs or polymer brushes with selective pinning strength for PS vs PMMA [Diagram 5] 1H NMR of M-1 [Figure 6] 1H NMR spectrum of undecenyl mesylate [Figure 7] 1H NMR spectrum of undecenyl ether glycerol [Figure 8] 1H NMR spectrum of undecyl tris ether glycerol [Figure 9] 1H NMR spectrum of M-2 [Figure 10] 1H NMR spectrum of M-3 [Figure 11] 1H NMR spectrum of M-4 [Figure 12] 1H NMR spectrum of M-5 [Figure 13] 1H NMR spectrum of M-6 [Figure 14] 1H NMR spectrum of M-7 [Figure 15] 1H NMR spectrum of M-8 [Figure 16] 1H NMR spectrum of M-9 [Figure 17] 1H NMR spectrum of M-10 [Figure 18] 1H NMR spectrum of M-11 [Figure 19] 1H NMR spectrum of M-12 [Figure 20] 1H NMR spectrum of the bromo precursor in Scheme 5 [Figure 21] 1H NMR spectrum of M-13 (thio group) [Figure 22] 1H NMR spectrum of M-14 (azide group) [Diagram 23] 1H NMR spectrum of M-15 (diethylphosphonate group) [Figure 24] 1H NMR spectrum of M-16 with methyl substituents on the aromatic ring [Diagram 25] 1H NMR spectrum of M-17 with methyl ester substituents on the aromatic ring [Figure 26] 1H NMR spectrum of M-18 having a nitro group on the aromatic ring [Figure 27] 1H NMR spectrum of M-19 with dimethyl ester substituents on the aromatic group [Figure 28] 1H NMR spectrum of M-20 having an amino group on the aromatic ring [Figure 29] 1H NMR spectrum of THP-protected M-21 with 1-hexene substituents on the aromatic ring. [Diagram 30] Figure 34: 1H NMR spectrum of M-21 with 1-hexene substituents on the aromatic group [Diagram 31] Figure 35: 1H NMR spectrum of M-22 [Diagram 32] Figure 36: 31P NMR of M-22 [Diagram 33] 1H NMR spectrum of M-23 [Diagram 34] 31P NMR spectrum of M-23 [Diagram 35] 1H NMR spectrum of M-24 [Diagram 36] 31P NMR spectrum of M-24 [Figure 37] 1H NMR spectrum of M-25 [Figure 38] 31P NMR spectrum of M-25 [Figure 39] XRR of SML-8 and SNL-3 [Diagram 40] XRR of SML-6 and comparison material ODTS-Cl3 [Diagram 41] Selective SAM Deposition on Metals (SML-13, SML-14, SML-15) [Diagram 42] Selective removal of metal SAMs (SML-12, SML-7, SML-5 using a solution of dodecylbenzenesulfonic acid (DBSA) in a mixture of PGME:PGMEA (70:30) [Diagram 43]Selective SAM removal using CA detergent (SML-23, SML-16, SML-23) [Diagram 44] Effects of chemical cleaning and heat treatment on Si-SAM (SML-12) [Diagram 45] Effect of temperature on SAM stability on Si (SML-12) [Figure 46] Passivation properties of SAM (SML-4) for ALD of HfOX [Figure 47] SEM morphology of SAMs on metal substrates after DBSA cleaning with 2 wt% dodecylbenzenesulfonic acid in 70:30 PGME:PGMEA [Prior art documents] [Non-patent literature]

[0011] [Non-Patent Document 1] Macromolecules 2019,52,2987-2994 [Non-Patent Document 2] Macromol.Rapid Commun.2018,39,1800479 [Non-Patent Document 3] A.Deiter Shluter et al Synthesis of Polymers,2014,Volume 1,p315 [Non-Patent Document 4] Encyclopedia of Polymer Science and Technology,2014,Vol 7,p.625 Summary of the Invention

[0012] The present invention describes the synthesis and fabrication of spin-coatable SAMs and selective SAM deposition on dielectric and metal surfaces. Structural designs with multi-tether functional groups enable spin-coatability and process conditions allow for the formation of well-defined SAMs. A general description of compounds with various anchoring / reactive groups with either aromatic or aliphatic cores is shown in FIG. 1. By incorporating a single anchor group per chain and more than two chains per molecule, spin-coating provides the desired amount of SAM precursors onto the substrate and baking at relatively high temperatures for a short period of time allows for well-defined self-assembled monolayers with very good packing density. The resulting dielectric SAMs show very good immobilization for atomic layer deposition of hafnium oxide. Modification of the SAM tail groups, i.e. polar vs. non-polar, allows for selective pinning or guiding surfaces for BCP wetting for guiding self-assembly. Anchor groups such as diethyl-phosphonate, thiols, azides, and amines allow for single-step metal-selective SAM deposition. However, metal-selective functional groups such as thiols, phosphonic acids / esters, amines, etc. also show some cross-grafting on the dielectric surface at grafting temperatures >150°C, which is a key step in the spin-coat assembly process. Functional groups typically used for dielectric grafting, such as chlorosilanes, alkoxysilanes, hydroxyls, alkenes, and alkynes, react indiscriminately on dielectric and metal surfaces. Therefore, a process of selective chemical cleavage on the metal regions would provide enhanced dielectric grafting or coating, allowing for subsequent metal grafting or coating.

[0013] The present invention describes novel SAM precursor compounds and novel methods to effect selective chemical cleavage of organic moieties on metal substrates using spin-coatable reagents consisting of organic acids with specific pH between 1 and 4 in organic media including alcohols and ether / ester solvents. Selective area chemical grafting is difficult in dielectric regions using any organic functional group. However, there are specific organic functional groups that can be used to interact with metal surfaces and graft or coat these regions via chemical reactions, either covalently or coordinately. The common organic compounds such as self-assembled monolayers (SAMs) and polymer brushes terminated with various anchoring / reactive groups specific for metal surfaces, e.g., diethyl-phosphonate, thiols, azides and amines, allow metal-selective grafting / deposition in a single step under optimal annealing conditions. These metal-selective functional groups are useful for directed grafting processes as shown in Figure 2.

[0014] One aspect of the invention is a compound of formula (I) in which A is a core moiety selected from structures (Ia), (Ib), (Ic) and (Id) attached through X, which is either a direct valence bond or a divalent linking group; m is the number of linear alkylene moieties of chain length n, where n ranges from 8 to 12, each of said linear alkylene moieties having a terminal B reactive moiety; and further, * indicates possible points of attachment of said linear alkylene moieties in each structure, with structures (Ia) and (Ib) having two or three points of attachment on adjacent carbons (m=2 or 3), structure (Ic) having two points of attachment (m=2), and structure (Id) having three points of attachment (m=3).

[0015] B is selected from -OH, -CH=CH2, -O-(P=O)(OR)2, -O-(P=O)(OR)Rs, N3, and -SH, where R and Rs are independently selected from C1-C8 alkyl.

[0016] R 1a and R 1bare independently selected from H, C1-C4 alkyl, C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl), nitro (NO2), NH2, and CN.

[0017] R 1c , R 1d , R 1e , R 1f and R 1g is independently selected from H, C1-C4 alkyl, C1-C4 alkyloxy, C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl), C3-C6 methylcarbonyloxyalkyl (-CH2-(C=O)-O-alkyl), and CN.

[0018] [ka] Another aspect of the invention relates to compositions containing these compounds and the use of these compositions to form self-assembled monolayers (SAMs) that can be used in DSA processing as either neutral polystyrene or polymethyl methacrylate pinning layers in the directed self-assembly of an overlying block polymer, as well as methods for selectively cleaving these SAMs on metal substrates and remover compositions for effecting this removal. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] It is to be understood that both the general description above and the detailed description below are exemplary and explanatory, and are not intended to be limiting with respect to the invention as claimed. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises" as well as other verb forms such as "includes" is not limiting. Also, the use of terms such as "element" or "component" includes both elements and components that contain one unit, and elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0020] The term C1-C4 alkyl includes methyl and C2-C4 linear alkyl and C3-C4 branched alkyl moieties, examples of which include methyl (-CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2), 2-butyl (-CH(CH3)CH2-CH3), etc. Similarly, a reference to C1-C8 includes methyl, C2-C8 linear alkyl, C3-C8 branched alkyl, C4-C8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), or C5-C8 alkylenecycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0021] The term C2-C5 alkylene includes C2-C5 linear alkylene moieties (eg, ethylene, propylene, etc.) and C3-C5 branched alkylene moieties (eg, -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0022] Diblock and triblock copolymers of styrenic and alkyl 2-methylene alkanoate derived repeat unit moieties useful as components in the compositions of the invention described herein can be prepared by a variety of methods, including anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and living radical polymerization (Macromolecules 2019, 52, 2987-2994 (Non-Patent Document 1); Macromol. Rapid Commun. 2018, 39, 1800479 (Non-Patent Document 2); A. Deiter Shluter et al Synthesis of Polymers, 2014, Volume 1, p315 (Non-Patent Document 3); Encyclopedia of Polymer Science and Technology, 2014, Vol 7, p. 625 (Non-Patent Document 4)).

[0023] The random copolymer poly(styrene-co-methyl methacrylate) is abbreviated as "P(S-co-MMA)" and the oligomeric form of this material is abbreviated as P(S-co-MMA). Similarly, the block copolymer poly(styrene-block-methyl methacrylate) is abbreviated as P(Sb-MMA) while the oligomeric form of this material is abbreviated as oligo(Sb-MMA). The oligomer oligo(styrene-co-p-octylstyrene)-block-(methyl methacrylate-co-di(ethylene glycol) methyl ether methacrylate) uses the same abbreviations to refer to the random block copolymer elements, specifically oligo(S-co-p-OS)-bP(MMA-co-DEGMEMA) [S=styrene, p-OS=para-octylstyrene, MMA=methacrylate, DEGMEMA=di(ethylene glycol) methyl ether methacrylate] to refer to the repeat unit in this block copolymer where the two blocks are random copolymers.

[0024] FOV, in this application, is an abbreviation for field of view for a top-down scanning electron microscope (SEM) in SEM drawings. "L / S" is an abbreviation for line and space lithography drawings.

[0025] PGMEA and PGME are abbreviations for 1-methoxypropan-2-yl acetate and 1-methoxypropan-2-ol, respectively.

[0026] The abbreviation PMMA stands for poly(methyl methacrylate).

[0027] The term PMMA affinity brush refers to a polymer that is polar, has a narrow polydispersity, and has a graft group at one chain end that can be spun from a solution of the polymer and bonded to form a grafted polar brush that has affinity for polar PMMA polymer block segments in block copolymers, such as block copolymers of styrene and methyl methacrylate. An example of such a material is a poly(methyl methacrylate) polymer or other polar alkyl methacrylate that has a reactive end group at one end, such as an alcohol end group (e.g., an alkyl alcohol or benzyl alcohol end group), and has a narrow molecular weight distribution (e.g., from 1 to about 1.1), and that can interact with an IC (integrated circuit) substrate, such as silicon dioxide, to graft the polymer with the reactive end group to the substrate, forming, for example, a surface with attached PMMA polymer brushes.

[0028] Both the general description above and the detailed description below are intended to be illustrative and explanatory, and are not intended to limit the claimed invention. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises" as well as other verb forms such as "includes" is not limiting. Also, the use of terms such as "element" or "component" includes elements and components that contain one unit, as well as elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, whereas the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0029] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials incorporated herein conflicts with that herein, the definition in the present application shall control.

[0030] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be a linear or branched hydrocarbon group (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like) or a cyclic hydrocarbon group (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), a polycyclic hydrocarbon group (e.g., norbornyl, adamantyl, and the like). These alkyl moieties can be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1-C8 carbons. For structural reasons, it is understood that linear alkyls start at C1, while branched alkyls and cyclic alkyls start at C3, and polycyclic alkyls start at C5. Furthermore, it is understood that moieties derived from alkyls described below, such as alkyloxy and perfluoroalkyl, have the same carbon number ranges unless otherwise indicated. If the length of an alkyl group is defined differently than above, the above definition of alkyl still applies in that it encompasses all types of alkyl moieties described above, and the structural considerations regarding the minimum number of carbons for a given type of alkyl group still apply.

[0031] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and similar groups). These alkyloxy moieties may be substituted or unsubstituted as described below.

[0032] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0033] As used herein, the term lactone includes both monolactones (eg, caprolactone) and dilactones (eg, lactide).

[0034] Haloalkyl refers to a saturated linear, cyclic or branched alkyl group, such as those described above, in which at least one of the hydrogens is replaced by a halide selected from the group F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0035] Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which all hydrogens have been replaced by fluorines (eg, trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like).

[0036] One aspect of the invention is a compound of formula (I) where A is a core moiety selected from structures (Ia), (Ib), (Ic) and (Id) attached through X, where X is either a direct valence bond or a divalent linking group, m is the number of linear alkylene moieties of chain length n, where n ranges from 8 to 12, and where said linear alkylene moieties each have a terminal B reactive moiety, and further, * represents a possible point of attachment of said linear alkylene moieties in each structure, where structures (Ia) and (Ib) have two or three points of attachment on adjacent carbons (m=2 or 3), structure (Ic) has two points of attachment (m=2), and structure (Id) has three points of attachment (m=3).

[0037] B is selected from -OH, -CH=CH2, -O-(P=O)(OR)2, -O-(P=O)(OR)Rs, N3, and -SH, where R and Rs are independently selected from C1-C8 alkyl.

[0038] R 1a and R 1b are independently selected from H, C1-C4 alkyl, C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl), nitro (NO2), NH2, and CN.

[0039] R 1c , R 1d , R 1e , R 1f and R 1g is independently selected from H, C1-C4 alkyl, C1-C4 alkyloxy, C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl), C3-C6 methylcarbonyloxyalkyl (-CH2-(C=O)-O-alkyl), and CN.

[0040] [ka] In another aspect of the compounds of the invention of structure (I), X is a direct valence bond.

[0041] In another aspect of the compounds of the invention of structure (I), X is a divalent linking group.

[0042] In one aspect of the compounds of the invention of structure (I), when X is a divalent linking group and the core moiety is (Ia), (Ib), or (Ic), the divalent linking group is selected from the group consisting of oxy (-O-), oxycarbonyl (-O-C(=O)-), carbonyloxy (-C(=O)-O-), carbonyl (-(C=O)-), sulfinyl (-(S(=O))-), and sulfone (-S(=O)-).

[0043] In one aspect of the compounds of the invention of structure (I), when X is a divalent linking group and the core moiety is (Id), the divalent linking group can be oxy (-O-), oxycarbonyl (-OC(=O)-), carbonyloxy (-C(=O)-O-),

[0044] [ka] It is selected from the group consisting of 1,4-phenylene (-Ph-), 1,4-phenyleneoxy (-Ph-O-), 1,4-oxyphenylene (-O-Ph-), carbonyl (-(C=O)-), sulfinyl (-(S(=O))-), sulfone (-S(=O)2-), 1,2-ethene (-CH=CH-), 1,1-ethene (-C(=CH2)-), and methylene (-CH2-).

[0045] In another aspect of the compounds of the invention of structure (I), when X is a divalent linking group and the core moiety is (Ia), (Ib), (Ic), or (Id), the divalent linking group is oxy (-O-). In another aspect of this embodiment, the divalent linking group is oxycarbonyl (-O-C(=O)-). In another aspect of this embodiment, the divalent linking group is carbonyloxy (-C(=O)-O-). In another aspect of this embodiment, the divalent linking group is carbonyl (-(C=O)-). In another aspect of this embodiment, the divalent linking group is sulfinyl (-(S(=O))-). In another aspect of this embodiment, the divalent linking group is sulfone (-S(=O)-).

[0046] In another aspect of the compounds of structure (I), when X is a divalent linking group and the core moiety is (Id), the divalent linking group is

[0047] [ka] In another aspect of this embodiment, the divalent linking group is 1,4-phenylene (-Ph-). In another aspect of this embodiment, the divalent linking group is 1,4-phenyleneoxy (-Ph-O-). In another aspect of this embodiment, the divalent linking group is 1,4-oxyphenylene (-O-Ph-). In another aspect of this embodiment, the divalent linking group is 1,2-ethene (-CH=CH-). In another aspect of this embodiment, the divalent linking group is 1,1-ethene (-C(=CH2)-). In another aspect of this embodiment, the divalent linking group is methylene.

[0048] In one specific aspect of the compounds of the invention above, A has the structure (Ia). In one aspect of this embodiment, structure (Ia) has m=2, and it has the more specific structure (Ia-1), where * indicates the location of the two attachment points; in one more specific aspect of this embodiment, it has the structure (Ia-2).

[0049] In another aspect of this embodiment, compound (I) has m=3 and has structure (Ia), which has three points of attachment at the positions indicated by * in structure (Ia); in a more specific aspect of this embodiment, it has structure (Ia-3), where * indicates the position of the points of attachment. In one aspect of this embodiment, R 1a and R 1b is H. In another embodiment, R 1a and R 1b At least one of R is H. In another aspect, R 1a and R 1b At least one of R is C1-C4 alkyl. 1a and R 1b At least one of R is C1-C4 alkyloxy. 1a and R 1b At least one of R is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). 1a and R 1b At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1a and R 1b In yet another aspect of this embodiment, at least one of R 1a and R 1b In yet another aspect of this embodiment, at least one of R 1a and R 1b In another aspect of this embodiment, at least one of R 1a and R 1bare both the same substituent as previously described. In another aspect of this embodiment, R 1a and R 1b are both different substituents as described above. In another aspect of this embodiment, R 1a and R 1b are not both H, but are the same substituent. In another aspect of this embodiment, R 1a and R 1b are not both H and are different substituents.

[0050] [ka] In one specific aspect of the compounds of the invention of structure (I) described herein, A has structure (Ib). In one aspect of this embodiment, the compound of structure (I) has m=2 and structure (Ib) has the more specific structure (Ib-1), where * indicates the location of the two attachment points; in another aspect of this embodiment, it has the more specific structure (Ib-2), where * indicates the location of the two attachment points. In one aspect of this embodiment, R 1c and R 1d At least one of R is H. In another aspect, R 1c and R 1d At least one of R is C1-C4 alkyl. 1c and R 1d At least one of R is C1-C4 alkyloxy. 1c and R 1d At least one of R is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). 1c and R 1d At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1dIn yet another aspect of this embodiment, at least one of R 1c and R 1d In another aspect of this embodiment, at least one of R 1c and R 1d are both the same substituent as previously described. In another aspect of this embodiment, R 1c and R 1d are different substituents as described above. In one particular embodiment, R 1c and R 1d Both are H.

[0051] In another aspect of the compound of the invention of structure (I) where m=2 and A has structure (Ib), it has the more specific structure (Ib-1), where * indicates the location of the two attachment points; in another aspect of this embodiment, it has the more specific structure (Ib-2), where * indicates the location of the two attachment points. In one aspect of this embodiment, R 1c and R 1d At least one of R is H. In another aspect, R 1c and R 1d At least one of R is C1-C4 alkyl. 1c and R 1d At least one of R is C1-C4 alkyloxy. 1c and R 1d At least one of R is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). 1c and R 1d At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1d In yet another aspect of this embodiment, at least one of R1c and R 1d In another aspect of this embodiment, at least one of R 1c and R 1d are both the same substituent as previously described. In another aspect of this embodiment, R 1c and R 1d are different substituents as described above. In one particular embodiment, R 1c and R 1d Both are H.

[0052] In another aspect of the compound of the invention of structure (I), m=3 and A has the structure (Ib), where * indicates the location of three attachment points; in another aspect of this embodiment, it has the more specific structure (Ib-3), where * indicates the location of three attachment points. In one aspect of this embodiment, R 1c and R 1d At least one of R is H. In another aspect, R 1c and R 1d At least one of R is C1-C4 alkyl. 1c and R 1d At least one of R is C1-C4 alkyloxy. 1c and R 1d At least one of R is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). 1c and R 1d At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1d In another aspect of this embodiment, at least one of R1c and R 1d are both the same substituent as previously described. In another aspect of this embodiment, R 1c and R 1d are different substituents as described above. In one particular embodiment, R 1c and R 1d Both are H.

[0053] In another aspect of the compound of the invention of structure (I), m=3 and A has the structure (Ib), where * indicates the location of the three attachment points; in another aspect of this embodiment, it has the more specific structure (Ib-4), where * indicates the location of the three attachment points. In one aspect of this embodiment, R 1c and R 1d At least one of R is H. In another aspect, R 1c and R 1d At least one of R is C1-C4 alkyl. 1c and R 1d At least one of R is C1-C4 alkyloxy. 1c and R 1d At least one of R is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). 1c and R 1d At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1d In yet another aspect of this embodiment, at least one of R 1c and R 1d In another aspect of this embodiment, at least one of R 1c and R 1d are both the same substituent as previously described. In another aspect of this embodiment, R1c and R 1d are different substituents as described above. In one particular embodiment, R 1c and R 1d Both are H.

[0054] [ka] In one specific aspect of the compound of the invention of structure (I), A has the structure (Ic). In one aspect of this embodiment, R 1e and R 1f At least one of R is H. In another aspect of this embodiment, 1e and R 1f At least one of R is C1-C4 alkyl. In one aspect of this embodiment, A has the more specific structure (Ic-1). In another aspect of this embodiment, it has the more specific structure (Ic-2). In yet another aspect of this embodiment, R 1e and R 1f In still another aspect of these embodiments, at least one of R 1e and R 1f At least one of R is a C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). In still another aspect of these embodiments, R 1e and R 1f At least one of R is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). 1e and R 1f At least one of R is NO2. 1e and R 1f At least one of R is NH2. 1e and R 1f In another aspect of this embodiment, at least one of R 1e and R 1fare both the same substituent as described above. In another aspect of this embodiment, they are different substituents as described above. In one specific embodiment, R 1e and R 1f Both are H.

[0055] [ka] In one specific aspect of the compounds (I) of the invention described herein, A has structure (Id). In one aspect of this embodiment, X is a methylene linking group, and A and X together have structure (Id-1), where * indicates the point of attachment of the alkylene moiety. In another aspect of this embodiment, X is a 1,4-phenylene linking group, and A and X together have structure (Id-2), where * indicates the point of attachment of the linear alkylene moiety. In yet another aspect of this embodiment, X is a 1,4-phenyleneoxy (-Ph-O-) linking group, and A and X together have structure (Id-3), where * indicates the point of attachment of the linear alkylene moiety. In yet another aspect of these embodiments, R 1g is C1-C4 alkyloxy. In yet another embodiment of this aspect, R 1g is C2-C5 carbonyloxyalkyl (-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1g is C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl). In yet another aspect of this embodiment, R 1g In yet another embodiment of this aspect, R 1g In yet another aspect of this embodiment, R 1g In yet another aspect of this embodiment, R 1g is H.

[0056] [ka] In one aspect of the embodiment of the compounds of the present invention of structure (I) described herein, n ranges from 9 to 12.

[0057] In one aspect of the embodiment of the compounds of the invention of structure (I) described herein, B is --OH.

[0058] In one aspect of the embodiment of the compounds of the invention of structure (I) described herein, B is -CH=CH2.

[0059] In one aspect of the embodiment of the compounds of the invention of structure (I) described herein, B is -O-(P=O)(OR)2.

[0060] In one aspect of the embodiment of the compounds of the invention of structure (I) described herein, B is -O-(P=O)(OR)R s It is.

[0061] O-(P=O)(OR)2 is at least one substituent R 1a or R 1b In structure (Ib), the substituent R 1d or R 1c In structure (Ic), at least one of the substituents R 1f or R 1e or in structure (Id), the substituent R g In one aspect of the embodiment of the compound of the invention of structure (I) described herein, R is ethyl or methyl. In one aspect of this embodiment, R is ethyl. In another aspect of this embodiment, R is methyl.

[0062] -O-(P=O)(OR)Rs is at least one substituent R 1a or R 1b In structure (Ib), the substituent R 1d or R 1c In structure (Ic), at least one of the substituents R 1f or R 1e or in structure (Id), R gIn one aspect of the embodiment of the compound of the invention of structure (I) described herein, present as: R is ethyl or methyl. In one aspect of this embodiment, R is ethyl. In another aspect of this embodiment, R is methyl. In yet another aspect of this embodiment, R is methyl. In one aspect of this embodiment, R and R are both methyl. In another aspect of this embodiment, R and R are both ethyl.

[0063] In another aspect of the compounds of the invention of structure (I) described herein, B is -N3.

[0064] In another aspect of the compounds of the invention of structure (I) described herein, B is --SH.

[0065] Another aspect of the invention is a compound selected from the group consisting of 11,11',11''-((ethane-1,1,1-triyltris(benzene-4,1-diyl))tris(oxy))tris(undecane-1-ol) (M-1), 11,11',11''-(propane-1,2,3-triyltris(oxy))tris(undecane-1-ol) (M-2), (11,11',11''-(benzene-1,2,3-triyltris(oxy))tris(undecane-1-ol) (M-3), (11,11',11''-(1, 2-phenylenebis(oxy))bis(undecane-1-ol) (M-4), 11,11'-(naphthalene-2,3-diylbis(oxy))bis(undecane-1-ol) (M-5), 11,11'-(naphthalene-1,8-diylbis(oxy))bis(undecane-1-ol) (M-6), 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol) (M-7), 11,11'-((4-(tert-butyl)-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-8) ), 1,2-phenylenebis(oxy))bis(hexadecane-1-ol) (M-9), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-10), 11-(2,6-bis(undeca-10-en-1-yloxy)phenoxy)undecane-1-ol (M-11), 10,10'-(1,2-phenylenebis(oxy))bis(decane-1-ol) (M-12), 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-thiol) (M-13), 1,2-bis((11-azido) doundecyl)oxy)benzene (M-14), tetraethyl ((1,2-phenylenebis(oxy))bis(undecane-11,1-diyl))bis(phosphonate) (M-15), 11,11'-((4-methyl-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-16), methyl 3,4-bis((11-hydroxyundecyl)oxy)benzoate (M-17), 11,11'-((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-18), dimethyl 4,5-Bis((11-hydroxyundecyl)oxy)phthalate (M-19), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-20), (E)-11,11'-((4-(hex-1-en-1-yl)-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-21), tetraethyl(((4-cyano-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phospho nate) (M-22), (tetraethyl (((4-acetyl-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate) (M-23), dimethyl 4,5-bis((11-(diethoxyphosphoryl)undecyl)oxy)phthalate (M-24), and (tetraethyl (((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) (M-25).

[0066] SAM Compositions of the Present Invention Another aspect of the invention is a SAM precursor composition comprising any one of the compounds of the invention described herein and an organic spin-casting solvent, which can be a single solvent or a mixture of at least two solvents.

[0067] In one aspect of this inventive composition, it consists essentially of any one of these compounds and the organic spin-casting solvent. In another aspect of this embodiment, it consists of any one of these compounds and the organic spin-casting solvent. In one aspect of this embodiment, the composition consists of the inventive composition with the proviso that the organic spin-casting solvent is a single solvent. In another aspect, the organic spin-casting solvent is a mixture of at least two solvents.

[0068] PMMA-compatible SAM composition of the present invention Another aspect of the invention is a composition of the invention that forms a polar SAM on a coating on a substrate that has an affinity for a polar block segment in a block copolymer (e.g., a poly(methyl methacrylate (PMMA) block segment), and is a SAM precursor composition comprising an organic spin-casting solvent and one of the following PMMA SAM precursor compounds of the invention: A compound of the present invention selected from: Compounds of the invention comprising structure (Ia), where R 1a and R 1b at least one of R is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C=O)-O-alkyl), nitro(NO2), NH2, and CN, where R that is not one of these substituents 1a or R 1b is either H or C1-C4 alkyl, preferably H. Compounds of the invention comprising structure (Ib), where R 1c or R 1d is a polar substituent independently selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C=O)-O-alkyl), and CN, where R that is not one of these substituents 1c or R 1d is either H or C1-C4 alkyl, preferably H. Compounds of the invention comprising structure (Ic), where R 1e or R 1f is a polar substituent independently selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C=O)-O-alkyl) and CN, where R that is not any of these substituents 1e or R 1fis either H or C1-C4 alkyl, preferably H. Compounds of the invention comprising structure (Id), where R 1g is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH2-(C=O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C=O)-O-alkyl) and CN.

[0069] The PS-affinity SAM composition of the present invention Another aspect of the invention is a composition that forms a non-polar SAM on a coating on a substrate that has an affinity for non-polar block segments in a block copolymer (e.g., polystyrene (PS) block segments), and is a SAM precursor composition comprising an organic spin-casting solvent and one of the following PS SAM precursor compounds of the invention: Compounds of the invention comprising structure (Ia), where R 1a and R 1b At least one of R is a non-polar substituent selected from C1-C4 alkyl, and R that is not one of these non-polar substituents. 1a or R 1b is H. Compounds of the invention comprising structure (Ib), where R 1c or R 1d at least one of R is a non-polar substituent independently selected from C1-C4 alkyl, and R that is not one of these non-polar substituents 1c or R 1d is H. Compounds of the invention comprising structure (Ic), where R 1e or R 1f at least one of R is a non-polar substituent independently selected from C1-C4 alkyl, and R is not one of these non-polar substituents. 1e or R 1f is H. Compounds of the invention comprising structure (Id), where R 1g is a non-polar substituent selected from C1 to C4 alkyl.

[0070] Neutrophilic SAM Composition of the Present Invention Another aspect of the invention is a composition that forms a neutral SAM on a coating on a substrate that has a neutral affinity for the non-polar and polar block segments in a block copolymer (e.g., a polystyrene (PS) block segment and a poly(methyl methacrylate (PMMA)) block segment is a PS-b-PMMA polymer), and is a SAM precursor composition comprising an organic spin-casting solvent and one of the following neutral affinity SAM precursor compounds of the invention: Compounds of the invention comprising structure (Ia), where R 1a and R 1b Both are H. Compounds of the invention comprising structure (Ib), where R 1c and R 1d Both are H. Compounds of the invention comprising structure (Ic), where R 1e and R 1f Both are H. Compounds of the invention comprising structure (Id), where R 1g is H.

[0071] Spin-casting solvents for the SAM compositions of the present invention A suitable solvent for use as an organic spin-casting solvent is any solvent that is used to spin-cast materials such as photoresists, bottom anti-reflective coatings or other types of organic coatings used in lithographic processing of semiconductor materials and that can dissolve the compounds of the present invention. Non-limiting examples. In another aspect of the novel composition, the organic spin-casting solvent is one that can dissolve the compounds of the present invention. The organic spin-casting solvent can be a single solvent or a mixture of solvents.Suitable solvents are organic solvents, for example glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, such as diethyl oxylate and diethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates. esters such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters such as methyl pyruvate or ethyl pyruvate; alkyloxy carboxylates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketone alcohol derivatives such as acetol or diacetone alcohol; ketals or acetals such as 1,3 dioxalane and diethoxypropane; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof. In one aspect of this embodiment, the solvent may be PGMEA or a mixture of PGMEA and PGME. In one aspect of this embodiment, the mixture of PGME and PGMEA is a 70:30 weight:weight mixture.

[0072] In another aspect of these compositions, the compound of the present invention comprises from about 0.5% to about 3.00% by weight of the total weight of the composition, including the organic spin-casting solvent. In another aspect, it comprises from about 0.75% to about 2.75% by weight. In yet another aspect, it comprises from about 1.00% to about 2.5% by weight. In yet another aspect, it comprises from about 1.5% to about 2.25% by weight.

[0073] In another aspect of the composition of the invention, the compound is selected from the group consisting of compounds selected from the following compounds: 11,11',11''-((ethane-1,1,1-triyltris(benzene-4,1-diyl))tris(oxy))tris(undecane-1-ol) (M-1), 11,11',11''-(propane-1,2,3-triyltris(oxy))tris(undecane-1-ol) (M-2), (11,11',11''-(benzene-1,2,3-triyltris(oxy))tris(undecane-1-ol) (M-3), 3), (11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol) (M-4), 11,11'-(naphthalene-2,3-diylbis(oxy))bis(undecane-1-ol) (M-5), 11,11'-(naphthalene-1,8-diylbis(oxy))bis(undecane-1-ol) (M-6), 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol) (M-7), 11,11'-((4-(tert-butyl)-1,2-phenylene)bis(oxy))bis(undecane-1 -ol) (M-8), 1,2-phenylenebis(oxy))bis(hexadecane-1-ol) (M-9), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-10), 11-(2,6-bis(undec-10-en-1-yloxy)phenoxy)undecane-1-ol (M-11), 10,10'-(1,2-phenylenebis(oxy))bis(decan-1-ol) (M-12), 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-thiol) (M-13), 1,2-bis(( 11-azidoundecyl)oxy)benzene (M-14), tetraethyl ((1,2-phenylenebis(oxy))bis(undecane-11,1-diyl))bis(phosphonate) (M-15), 11,11'-((4-methyl-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-16), methyl 3,4-bis((11-hydroxyundecyl)oxy)benzoate (M-17), 11,11'-((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-18), dimethyl 4,5-Bis((11-hydroxyundecyl)oxy)phthalate (M-19), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-20), (E)-11,11'-((4-(hex-1-en-1-yl)-1,2-phenylene)bis(oxy))bis(undecane-1-ol) (M-21), tetraethyl(((4-cyano-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phospho nate) (M-22), (tetraethyl (((4-acetyl-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate) (M-23), dimethyl 4,5-bis((11-(diethoxyphosphoryl)undecyl)oxy)phthalate (M-24), and (tetraethyl (((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) (M-25).

[0074] In all ranges given herein for the different components of the composition, these components are selected so that their sum totals 100% by weight.

[0075] Coating of the PMMA-compatible SAM composition of the present invention and method for forming a PMMA-compatible SAM on a substrate Another aspect of the present invention is a method of coating and forming a PMMA-compatible SAM with any one of the inventive PMMA-compatible SAM compositions described herein, comprising the steps of: i) coating a substrate with the polarophilic (also known as PMMA-philic) SAM composition described above; ii) baking at a temperature ranging from about 150° C. to about 200° C.; iii) washing with an organic spin-casting solvent to form a PMMA-compatible SAM; The method comprises:

[0076] The PMMA-compatible SAM has an affinity for PMMA block segments in a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA).

[0077] PMMA SAMs of the invention Another aspect of the invention is a PMMA-compatible SAM formed on a substrate by a method comprising steps i)-iii).

[0078] Coating of the PS-Affinity SAM Composition of the Present Invention and Method for Forming a PS-Affinity SAM on a Substrate Another aspect of the invention is a method of coating with a non-polar affinity SAM (also known as PS block segment affinity) composition, comprising the steps of: ia) coating a substrate with the PS-affining SAM composition of the present invention described herein; iia) baking at a temperature ranging from about 150° C. to about 200° C.; iiia) washing with an organic spin-casting solvent to form a self-assembled monolayer having affinity for the PS block segment of a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA); The method comprises:

[0079] PS SAMs of the invention Another aspect of the invention is a PS-compatible SAM formed on a substrate by a method comprising steps ia) to iiia).

[0080] Coating of the Neutrophilic SAM Composition of the Present Invention and Method for Forming a Neutrophilic SAM on a Substrate Another aspect of the invention is a method of coating with a neutral affinity SAM (in other words, no affinity for either the PMMA or PS block segments in a PS-b-PMMA block copolymer) composition, comprising the steps of: ib) coating a substrate with the neutrophilic SAM composition of the present invention described herein; iib) baking at a temperature ranging from about 150° C. to about 200° C.; iiib) washing with an organic spin-casting solvent to form a self-assembled monolayer having a neutral affinity for the block segments of a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA); The method comprises:

[0081] PS SAMs of the invention Another aspect of the invention is a neutophilic SAM formed on a substrate by a method comprising steps ib) through iiib).

[0082] Method for selective deposition of PMMA-philic and PS-philic self-assembled monolayers of the present invention when used in a chemo-epitaxy DSA process flow Another aspect of the present invention is a method for selective deposition of a self-assembled monolayer followed by directed self-assembly of a block copolymer, comprising the steps of: ic) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iic) coating said substrate with a PMMA-compatible brush polymer or a PMMA-compatible SAM composition of the invention as described herein; iiic) baking at a temperature ranging from about 150°C to about 200°C; ivc) washing with an organic spin-casting solvent to produce a substrate with PMMA-compatible brushes or PMMA-compatible self-assembled monolayers bound only to the metal lines; vc) coating with the neutrophilic SAM composition of the present invention described herein; vic) baking at a temperature ranging from about 150° C. to about 200° C.; viic) washing with an organic spin-casting solvent to produce a substrate in which the PMMA brushes are still attached to the metal lines, but the neutral affinity self-assembled monolayer is also attached to the non-metal lines; viiic) coating the substrate formed in step viic) with a block copolymer solution; vivc) annealing the block copolymer coating to form a directed self-assembled block copolymer L / S pattern; The method comprises:

[0083] Method for selective deposition of PMMA-philic and PS-philic self-assembled monolayers of the present invention when used in a chemo-epitaxy DSA process flow Another aspect of the present invention is a method for selective removal of a self-assembled monolayer and directed self-assembly of a polymer, comprising the steps of: id) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iid) coating with the PS-affining SAM composition of the invention described herein; iiid) baking at a temperature ranging from about 150° C. to about 200° C.; ivd) washing with an organic spin-casting solvent to produce a substrate having a PS-compatible self-assembled monolayer bound over the entire substrate, on both the metal and non-metal lines; vd) selectively removing the PS-affined self-assembled monolayer by treating with a removal solution, the removal solution comprising: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents with water and a pK of about 2.9 to about 5 a Tricarboxylic acids having a pK of about 3 to about 5 aand an acid component selected from a dicarboxylic acid having the formula: · Alcohol-based and glycol-based spin-casting solvents, and removal solutions consisting of dithiols, and · Removal solution consisting of alcohol-based and glycol-based spin-cast solvents and amines, The steps are selected from the group consisting of: vid) optionally baking at a temperature ranging from about 100° C. to about 200° C.; viid) washing with an organic spin-casting solvent to produce a substrate having only a PS-compatible self-assembled monolayer on the non-metallic lines over the entire substrate; viiid) coating with the neutrophilic SAM composition of the present invention described herein; ixd) baking at a temperature ranging from about 150° C. to about 200° C.; xd) washing with an organic spin-casting solvent to produce a substrate having a neutral affinity self-assembled monolayer attached to the metal lines and a PS affinity self-assembled monolayer attached to the non-metal lines; xd) coating the substrate formed in step ixd) with a solution of a block copolymer having polar and non-polar block segments; xid) annealing the block copolymer coating to form a directed self-assembled block copolymer L / S pattern; The method comprises:

[0084] A method for selective removal of PMMA-compatible self-assembled monolayers when used in a chemo-epitaxy DSA process flow Another aspect of the invention is a method for coating a PMMA-compatible SAM composition onto a chemo-epitaxy array of metal and non-metal lines and selectively removing the deposited SAM on the metal lines, comprising the steps of: ie) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iie) coating the substrate with the inventive PMMA-compatible SAM composition described herein; iiie) baking at a temperature ranging from about 150° C. to about 200° C.; ive) washing with an organic spin-casting solvent to form a PMMA-compatible self-assembled monolayer on both the metal and non-metal lines; ve) selectively removing the PMMA-compatible self-assembled monolayer from the metal lines by treatment with a removal solution, said removal solution comprising: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents with water and a pK of about 2.9 to about 5 a Tricarboxylic acids having a pK of about 3 to about 5 a and an acid component selected from a dicarboxylic acid having the formula: · Alcohol-based and glycol-based spin-casting solvents, and removal solutions consisting of dithiols, and · Removal solution consisting of alcohol-based and glycol-based spin-cast solvents and amines, The steps are selected from the group consisting of: vie) optionally baking at a temperature ranging from about 100°C to about 200°C; viie) treatment with an organic spin-casting solvent to remove the cleaved SAM, thereby producing a substrate with a PMMA-compatible self-assembled monolayer bound only to the non-metallic lines; The method comprises:

[0085] A method for selective removal of PS-affined self-assembled monolayers Another aspect of the invention is a method for coating a chemo-epitaxy array of metal and non-metal lines with a PS-compatible SAM composition and selectively removing the deposited SAM on the metal lines, comprising the steps of: if) forming a chemo-epitaxy array of metal and non-metal lines on the substrate using lithographic processing; iif) coating the substrate with the PS-affining SAM composition of the present invention described herein; iiif) baking at a temperature ranging from about 150° C. to about 200° C.; ivf) washing with an organic spin-casting solvent to form a PS-compatible self-assembled monolayer on both the metal and non-metal lines; vf) selectively removing the PS-affined self-assembled monolayer from the metal lines by treatment with a removal solution, said removal solution comprising: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents with water and a pK of about 2.9 to about 5 a Tricarboxylic acids having a pK of about 3 to about 5 a and an acid component selected from a dicarboxylic acid having the formula: · Alcohol-based and glycol-based spin-casting solvents, and removal solutions consisting of dithiols, and · Removal solution consisting of alcohol-based and glycol-based spin-cast solvents and amines, The steps are selected from the group consisting of: vif) optionally baking at a temperature ranging from about 100° C. to about 200° C.; viif) removing the cleaved PS-affine self-assembled monolayer from the metal lines by treatment with an organic spin-casting solvent to produce a substrate in which the PS-affine self-assembled monolayer is only bonded to the non-metallic lines; The method comprises:

[0086] Method for selective removal of neutrophil self-assembled monolayers - Patent Application 20070229633 Another aspect of the invention is a method for coating a chemo-epitaxy line of metal and non-metal lines with a neutral affinity SAM composition and selectively removing the deposited SAM on the metal lines, comprising the steps of: ig) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iig) coating a substrate with the neutrophilic SAM composition of the present invention described herein; iiig) baking at a temperature ranging from about 150° C. to about 200° C.; ivg) washing with an organic spin-casting solvent to form a neutrophilic self-assembled monolayer on both the metal and non-metal lines; vg) selectively removing the neutrophil self-assembled monolayer from the metal lines by treatment with a removal solution, said removal solution comprising: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents with water and a pK of about 2.9 to about 5 a Tricarboxylic acids having a pK of about 3 to about 5 a and an acid component selected from a dicarboxylic acid having the formula: · Alcohol-based and glycol-based spin-casting solvents, and removal solutions consisting of dithiols, and · Removal solution consisting of alcohol-based and glycol-based spin-cast solvents and amines, The steps are selected from the group consisting of: vig) optionally baking at a temperature ranging from about 100° C. to about 200° C.; viig) treating with an organic spin-casting solvent to remove the cleaved neutophilic self-assembled monolayer from the metal lines, thereby producing a substrate in which the neutophilic self-assembled monolayer is bonded only to the non-metallic lines; The method comprises:

[0087] Solvent for the method In the above method of the invention, a suitable solvent is any organic spin-casting solvent that does not harm the substrate itself or the patterned metal and non-metal lines that may be present on said substrate. For some SAM formulations, it is preferred to use an alcohol-based glycol-based spin-casting solvent (e.g., PGME, or a mixture of PGME and PGMEA). The cleaning solution used to remove residual unbound SAM precursor from the patterned substrate may be an organic spin-casting solvent as described herein.

[0088] Removal solution In order to selectively remove the SAMs of the invention from metal patterns on a substrate while not cleaving the SAMs attached to non-metal patterns on the substrate, such as silicon oxide, several different types of remover solutions have been used in the methods of the invention described herein, including: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an arylsulfonic acid substituted with an alkyl, preferably a C8-C14 alkyl, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents with pK ranging from about 2.9 to about 5 a a tricarboxylic acid (preferably citric acid) having a pK of about 3 to about 5; a or an alkyl substituted aryl sulfonic acid (preferably dodecylbenzene sulfonic acid), and optionally water, having a pH of about 3 to about 5; · Alcohol-based and glycol-based spin-casting solvents, and removal solutions consisting of dithiols, and · A removal solution consisting of alcohol-based, glycol-based spin-cast solvents and amines.

[0089] These removal solutions useful for selectively removing the SAM from the metal pattern are described in more detail below: An aqueous remover solution of glycine, hydrogen peroxide and a secondary acid component.

[0090] One type of removal solution, having a pH of about 3 to about 5, is composed of water, glycine, hydrogen peroxide, and a co-acid component selected from a tricarboxylic acid, a dicarboxylic acid, or a C8-C14 alkyl substituted aryl sulfonic acid.

[0091] In one aspect of the removal solution, it comprises from about 3 to about 7% hydrogen peroxide by weight. In another aspect of this embodiment, it comprises from about 4 to about 6% by weight. In yet another aspect of this embodiment, it comprises about 5% by weight.

[0092] In another aspect of the removal solution, it contains from about 7 to about 12% glycine by weight. In another aspect of this embodiment, it contains from about 8 to about 11% glycine by weight. In yet another aspect of this embodiment, it contains from about 9 to about 10.5% glycine by weight. In yet another aspect, it contains about 9.8% glycine by weight.

[0093] In another aspect of this stripping solution, it comprises from about 0.1 to about 2% by weight of a side acid component selected from a tricarboxylic acid, a dicarboxylic acid. In one aspect of this embodiment, the side acid component is selected from a dicarboxylic acid or a tricarboxylic acid having a pKa of from about 1.3 to about 5, respectively. In another aspect of this embodiment, the dicarboxylic acid is succinic acid, glutaric acid, adipic acid, malonic acid, or oxalic acid; in another aspect of this embodiment, it is oxalic acid or adipic acid. In another aspect of this embodiment, the tricarboxylic acid is selected from citric acid, isocitric acid, and 1,2,3-propanetricarboxylic acid; in another aspect of this embodiment, it is citric acid. In another aspect of this embodiment, the acid is citric acid.

[0094] In another embodiment of this removal solution, it comprises from about 0.1 to about 2 wt. % of a C8-C14 alkyl substituted aryl sulfonic acid; in another aspect of this embodiment, the acid is dodecylbenzene sulfonic acid.

[0095] The solution may also optionally contain about 40 to about 60 wt.% of an alcohol-based, glycol-based spin-cast solvent that is a 60:30 to 80:20 weight / weight mixture of hydroxy- and alkyloxy-functionalized alkylene moieties and both alkylcarboxyloxy- and alkyloxy-functionalized alkylene moieties. In one specific aspect of this embodiment, this is a mixture of PGMEA and PGME. In another more specific embodiment, this is about a 70:30 mixture of PGME and PGMEA. In all ranges described herein for the different components of the removal solution, these components are selected such that their sum equals 100 wt.%.

[0096] A removal solution comprising an alcohol-based, glycol-based spin-cast solvent and an acid component selected from tricarboxylic acids, dicarboxylic acids, and alkyl-substituted arylsulfonic acids. The remover solution, having a pH of about 3 to about 5, comprises about 70 to about 90 wt. % of an alcohol-based, glycol-based spin-cast solvent that is a 60:30 to 80:20 weight / weight mixture of hydroxy- and alkyloxy-functionalized alkylene moieties and both alkylcarboxyloxy- and alkyloxy-functionalized alkylene moieties. In one specific aspect of this embodiment, it is a mixture of PGME and PGMEA. In another more specific embodiment, it is about a 70:30 weight:weight mixture of PGME and PGMEA. In one aspect of this removal solution, it contains about 10 to about 30 wt. % water. In another removal solution, it contains about 1 to about 2 wt. % water and a pK of about 2.9 to about 5. a In another aspect of this embodiment, the tricarboxylic acid is selected from citric acid, isocitric acid, and 1,2,3-propanetricarboxylic acid; in another aspect of this embodiment, it is citric acid. In another aspect, the acid is citric acid. In another aspect of this removal solution, it is from about 1 to about 2% by weight of a tricarboxylic acid having a pK between about 3 and about 5. a In another aspect of this embodiment, the dicarboxylic acid is succinic acid, glutaric acid, or adipic acid. In another aspect of this embodiment, the stripping solution comprises from about 1 to about 2 weight percent of a C8-C14 alkyl substituted aryl sulfonic acid; in another aspect of this embodiment, the acid is dodecylbenzene sulfonic acid. In all ranges described herein for the different components of this stripping solution, these components are selected such that their sum equals 100 weight percent.

[0097] Removal solution consisting of alcohol-based, glycol-based spin-cast solvent and dithiols In one aspect of the removal solution, it comprises about 98 to about 99 wt. % of an alcohol-based, glycol-based spin-cast solvent that is a 60 / 30 to 80 / 20 wt. / wt. mixture of hydroxy- and alkyloxy-functionalized alkylene moieties and both alkylcarboxyloxy- and alkyloxy-functionalized alkylene moieties. In one specific aspect of this embodiment, it is a mixture of PGME and PGMEA. In another more specific embodiment, it is about a 70:30 mixture of PGME and PGMEA. In one aspect of the removal solution, it comprises about 1 to about 2 wt. % of C3-C6 alkanedithiols. In another aspect of this embodiment, it comprises butanedithiol selected from propanedithiol, butanedithiol, and pentanedithiol. In all ranges described herein for the different components of the removal solution, these components are selected such that their sum equals 100 wt. %.

[0098] Removal solution consisting of alcohol-based, glycol-based spin-cast solvents and amines In one aspect of the removal solution, it comprises about 98 to about 99 wt. % of an alcohol-based, glycol-based spin-cast solvent that is a 60 / 30 to 80 / 20 wt. / wt. mixture of hydroxy- and alkyloxy-functionalized alkylene moieties and alkylcarboxyoxy- and alkyloxy-functionalized alkylene moieties. In one specific aspect of this embodiment, it is a mixture of PGMEA and PGME. In another more specific embodiment, it is about a 70:30 mixture of PGME and PGMEA. In one aspect of the removal solution, it comprises about 1 to about 2 wt. % of a C2-C4 trialkylamine. In another aspect of this embodiment, it comprises amines selected from the group consisting of triethylamine, tripropylamine, and tributylamine. In all ranges described herein for the different components of the removal solution, these components are selected such that their sum equals 100 wt. %.

[0099] Washing solvent to remove cleaved SAM The method for selectively removing the SAM described herein requires treatment with a remover solution followed by rinsing with an organic spin-casting solvent. EXAMPLES

[0100] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich (3050 Spruce Street, St. Louis, MO 63103).

[0101] All synthesis experiments were carried out in a N2 atmosphere. Lithography experiments were carried out as described herein. The molecular weight of the copolymer was measured using gel permeation chromatography. 3 Å, 10 5 Å and 10 6 Gel permeation chromatography with an Åμ-Ultrastyragel column.

[0102] Lithography experiments were performed using a TEL Clean ACT8 track. SEM images were taken using an Applied Materials NanoSEM 3D. Scanning electron micrographs are shown at either 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm).

[0103] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembled film block copolymers of methyl methacrylate and styrene.

[0104] Unless otherwise specified, molecular weight determination (also known as M n Polydispersity) is 100Å, 500Å, 10 3 Å, 10 5 Å and 10 6 The analysis was carried out by gel permeation chromatography equipped with an Åμ-Ultrastyragel column (PSS Inc., Germany) using THF solvent as the eluent. Polystyrene polymer standards were used for calibration.

[0105] 11 H NMR spectra were recorded in CDCL3 solvent on a Bruker Advanced III 400 MHz spectrometer.

[0106] The molecular weight of the copolymers was determined using gel permeation chromatography. Chemicals were obtained from Sigma-Aldrich Corporation (St. Louis, MO) unless otherwise stated.

[0107] Lithography experiments were performed using a TEL Clean ACT8 track. SEM images were taken using an Applied Materials NanoSEM 3D. Scanning electron micrographs are shown at either 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm with 1, 2 and 5 FOV).

[0108] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembled film block copolymers of methyl methacrylate and styrene.

[0109] Unless otherwise specified, molecular weight determination (also known as M n Polydispersity) is 100Å, 500Å, 10 3 Å, 10 5 Å and 10 6 The analysis was carried out by gel permeation chromatography equipped with an Åμ-Ultrastyragel column (PSS Inc., Germany) using THF solvent as the eluent. Polystyrene polymer standards were used for calibration.

[0110] Synthesis of test polymer materials Polymer synthesis example 1: Synthesis of PS-co-PMMA neutral layer material A 250 ml flask equipped with a temperature controller, heating jacket and magnetic stirrer was set up. 26.04 grams (0.25 moles) of styrene, 24.03 grams (0.24 moles) of methyl methacrylate, 1.42 grams (0.10 moles) of glycidyl methacrylate, 0.41 grams (0.0025 moles) of azobisisobutyronitrile (AIBN) initiator and 100 grams of anisole were added to the flask. The stirrer was turned on and set to about 400 rpm. The reaction solution was then degassed by vigorously bubbling nitrogen through the solution at room temperature for about 30 minutes. After degassing for 30 minutes, the heating jacket was turned on and the temperature controller was set to 70° C. and the stirred reaction mixture was maintained at this temperature for 20 hours. After this time, the heating jacket was turned off and the reaction solution was allowed to cool to about 40° C. The reaction mixture was then poured into 1.5 L of isopropanol and stirred by mechanical stirring during the addition. During the addition, the polymer precipitated. The precipitated polymer was collected by filtration. The collected polymer was dried in a vacuum oven at 40° C. About 36 grams of polymer was obtained. The dried polymer was dissolved in 300 g of THF and then filtered through a 0.2 μm nylon filter. The filtered solution was then precipitated again in a stirred solution of 1.5 L of methanol, the precipitated polymer was collected and dried under vacuum at 40° C. as before. In this way, 26 grams (50% yield) of polymer was obtained after drying. The polymer had a Mw of about 36k and a polydispersity (PDI) of 1.5.

[0111] Polymer synthesis example 2: Synthesis of P(Sb-MMA)(78K-b-39K) Styrene and methyl methacrylate monomers were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquid was transferred into the reactor under N2 via the ampoules or using a stainless steel cannula. 700 mL of anhydrous tetrahydrofuran was added into a dry 1 L round-bottom reactor equipped with a side arm for connecting the ampoules, a magnetic stir bar, and a nitrogen / vacuum three-way septum adapter. The temperature of the reactor was lowered to -78°C using a dry ice-acetone bath. Then, after titrating the impurities, 0.2 mL (1.4 M solution) of sec-butyl lithium was added to the reactor. Then, 20 g (0.192 moles) of styrene was added from the ampoules into the reactor with rapid stirring. The reaction solution changed its color to yellow-orange, and the reaction was stirred for 30 minutes. Then, 0.06 g (0.0003 mol) of 1,1'-diphenylethylene (DPE) in 2.5 mL of anhydrous toluene was added to the reactor via the ampoule. The orange color of the reaction mixture changed to a dark brick red color, suggesting that the styryllithium active centers were converted to delocalized DPE-adducted carbanions. After 2 minutes of stirring, a small amount (2 mL) of the reaction mixture was taken for PS block molecular weight analysis. Methyl methacrylate (9.98 g, 0.0998 mol) was then added via the ampoule. The reaction was quenched after 30 minutes with 1 mL of degassed methanol. The block copolymer was recovered by precipitation into excess isopropanol (five times the volume of the polymer solution) containing 10% water, filtered, and dried under vacuum at 55° C. for 12 hours to give 28 g of P(Sb-MMA) consisting of 66 mol % polystyrene blocks and 34 mol % polymethyl methacrylate blocks (94% yield).

[0112] 100Å, 500Å, 10 3 Å, 10 5 Å and 10 6 Gel permeation chromatography with an Åμ-Ultrastyragel column was performed against PS calibration standards. The first P(SDPE) block was n (GPC) = 64,622 g / mol and M w / M nThe diblock copolymer molecular weight obtained from GPC was shown to have M n,PS-b-PMMA = 107,150 g / mol and M w / M n =1.01.

[0113] Polymer synthesis example 3: Synthesis of P(Sb-MMA)(45k-b-51k) P(Sb-MMA)(45K-b-51K) was synthesized using the same procedure as described in Example 2. n The amount of initiator and monomer were varied to achieve the desired composition of PS and PMMA blocks. Briefly, 20 g (0.192 mol) of styrene was polymerized with 0.32 mL (1.4 M solution) of sec-butyllithium. Then, 0.095 g (0.0005 mol) of 1,1'-diphenylethylene (DPE) in 2.5 mL of anhydrous toluene was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark brick red color, suggesting that the styryllithium active centers were converted to delocalized DPE-adducted carbanions. After 2 min of stirring, a small amount (2 mL) of the reaction mixture was taken for PS block molecular weight analysis. Then, methyl methacrylate (22.85 g, 0.23 mol) was added via an ampoule. The reaction was quenched after 30 min with 1 mL of degassed methanol. The block copolymer was recovered by precipitation into excess isopropanol (five times the volume of the polymer solution) containing 10% water, filtered, and dried under vacuum at 55° C. for 12 hours to give 40 g of P(Sb-MMA) consisting of 46.9 mol % polystyrene blocks and 53.1 mol % polymethyl methacrylate blocks (94% yield).

[0114] 100Å, 500Å, 10 3 Å, 10 5 Å and 10 6 Gel permeation chromatography with an Åμ-Ultrastyragel column was performed against PS calibration standards. The first P(SDPE) block was n (GPC) = 45,048 g / mol and M w / M nThe diblock copolymer molecular weight obtained from GPC was shown to have M n,PS-b-PMMA = 88,348 g / mol, and M w / M n =1.02.

[0115] Synthesis of novel SAM precursor molecules for testing Section A: This section describes the synthesis of multihydroxyalkyl SAMs. Synthesis of SAM precursor: Generally, all multiple hydroxyl SAM precursors were prepared using Williamson etherification reactions of multihydroxy aromatic or aliphatic cores with the corresponding bromo-alkyl-alcohols or bromo-alkyl-olefins. The reaction with aromatic cores is a single step, whereas the reaction with aliphatic core glycerols involves a multi-step synthesis. The molecules are referred to as Mx, where M refers to the multi-tether and x refers to the number. 1) Protocol 1: The starting aromatic diol was reacted with alpha-bromo-alkyl-omega alcohol (hydroxy functional molecule) in 2-butanone at reflux under basic conditions. The solid compound was purified via recrystallization from 2-butanone. 2) Protocol 2: The starting aromatic diol was reacted with an alpha bromo alkyl diethyl phosphonate (a diethyl phosphonate functional molecule) under basic conditions in 2-butanone at reflux. 3) Protocol 3: Diethylphosphonate functional groups were prepared using a two-step strategy. In the first step, the starting hydroxyl-functional molecules were converted to bromo derivatives, which were then reacted with excess triethylphosphite. After removal of the excess triethylphosphite, the desired compounds were obtained. 4) Protocol 4: This protocol involves a multi-step synthesis or conversion of olefins to alcohols using protected hydroxyl derivatives.

[0116] Synthesis of (M-1): Scheme 1 shows the general synthetic route leading to M-1. 9.2 g of 4,4',4''-(ethane-1,1,1-trityl)triphenol (0.03 mol), 28.2 g (0.112) of 11-bromoundecan-1-ol, 28 g (0.202 mol) of potassium carbonate, and 3 g of potassium iodide (0.0018 mol) and 500 mL of methyl ethyl ketone were added to a round bottom flask equipped with a magnetic stir bar, a condenser and a nitrogen blanket and stirred at a temperature of 90°C for 24 hours. The reaction mixture was passed through a short silica bed, rotary evaporated and subjected to column chromatography using 100% ethyl acetate as the mobile phase. Upon removal of the ethyl acetate, a yellowish viscous liquid was obtained (18.0 g of M-1, yield 73.5). This compound was purified using column chromatography using a 570:30 mixture of ethyl acetate and hexane as the eluent. Figure 5 shows the elution of this material (M-1). 1 H NMR is shown.

[0117] [ka] Synthesis of M-2 Scheme 2 shows the overall synthetic route used to prepare M-2, consisting of steps I through IV below.

[0118] Step I: In a three-necked round bottom flask equipped with a magnetic stir bar, condenser, dropping funnel and nitrogen blanket, triethylamine, 10-undecenol and 500 mL of dichloromethane (DCM) were added and 108 g of mesyl chloride was transferred to the dropping funnel. After cooling the round bottom flask using an ice bath, mesyl chloride was added dropwise while maintaining the temperature below 10° C. Stirred at low temperature for 1 hour and then at room temperature for several hours. After aqueous workup and removal of dichloromethane, 210 g of mesyl protected 10-undecenol was obtained. Figure 6 shows the structure of the product, i.e. undec-10-en-1-yl methanesulfonate (undecenyl methanesulfonate). 1 H NMR is shown.

[0119] Step II: In a three-neck round-bottom flask equipped with a dropping funnel, a Dean-Stark condenser, and a thermometer, under a nitrogen blanket, were added 96 g of powdered KOH, 92.3 g of Solketal((2,2-dimethyl-1,3-dioxolan-4-yl)methanol, and 600 mL of toluene. The flask was heated to 150 °C using a hot plate. At this temperature, the toluene began to condense in the Dean-Stark apparatus. After stirring the viscous solution for 30 min (no water removal was visually observed), 110 g of Undecenyl mesylate was added over 20 minutes and an immediate reaction was observed (rapid condensation of toluene). After 30 minutes the reaction mixture became unstirrable, after which the reaction mixture was cooled to room temperature and transferred to a separatory flask, neutralized with concentrated hydrochloric acid, and 400 mL of heptane was added. The organic layer was washed with brine and 500 mL of distilled water (DIW). The organic layer was dried over sodium sulfate, filtered, and evaporated on a rotary evaporator to give 114 g of a pale yellow brownish liquid. This liquid was dissolved in methanol and concentrated to give Amberlyst. TM The ketal group was deprotected using 1:1 ethyl acetate and heptane for 3 hours with 15. The pure product was isolated by column chromatography using 1:1 ethyl acetate and heptane. The yield was 58 g of 3-(undec-10-en-1-yloxy)propane-1,2-diol (undecenyl ether glycerin). 1 The H NMR is shown in Figure 6.

[0120] Step III: In a three-necked round bottom flask equipped with a dropping funnel, a Dean-Stark condenser, and a thermometer, 90.7 g of powdered KOH, 26.4 g of the Step II product (undecenyl ether glycerin), and 630 mL of toluene were added under a nitrogen blanket. The reaction mixture was heated at 150 °C using a metal hot plate until toluene began to condense in the Dean-Stark apparatus. After stirring the resulting viscous solution for 30 minutes (no visible removal of water was observed), 56 g of undecenyl mesylate was added over 20 minutes, and an immediate reaction (instant condensation of toluene) was observed. After 30 minutes, the reaction mixture was cooled to room temperature and transferred to a separatory flask and neutralized with concentrated hydrochloric acid. The mixture was extracted with 400 mL of heptane. The resulting organic layer was washed with brine and 500 mL of DIW. The organic layer was dried over sodium sulfate, filtered, and evaporated on a rotary evaporator to give a light yellow brownish liquid (yield=54 g). The crude intermediate was passed through a silica column and eluted with heptane to give 45 g of the desired product 11-((1,3-bis(undec-10-en-1-yloxy)propan-2-yl)oxy)undec-1-ene (undecyl tris-ether glycerol). 1 The H NMR is shown in Figure 7.

[0121] Step IV: 40 g of the product from Step III and 250 mL of THF were added to a two-neck round bottom flask equipped with a condenser and nitrogen blanket, rubber septum inlet. At room temperature, 100 mL of BH3-THF (1M) was added quickly. Immediate gelation was observed, and the flask was then heated to 80° C. on a hot plate for 30 minutes. 70 mL of hydrogen peroxide was then added to dissolve in the gel, and after 5 minutes, 13 g of KOH dissolved in 70 mL of water was added, and the flask was heated for an additional 30 minutes. The resulting water / THF layer separated in the flask, and the entire mixture was added to 400 mL of DIW containing HCl to neutralize the KOH. A sticky white paste-like product was obtained. This was dissolved in DCM, and the aqueous layer was separated and dried over sodium sulfate, and the DCM was removed to give a white semi-solid (yield=37 g). The product shows multiple TLC spots and contains a mixture of pure trishydroxy derivative and unreacted olefin groups. Purification was performed using hot heptane. The mixed olefin / hydroxyl-containing compound is soluble in heptane and the trishydroxy compound is insoluble in heptane. (Yield 19 g, % hydroxy functionality = ca. 92%). Figure 8 shows the 1H NMR spectrum of the product.

[0122] [ka]

[0123] [ka] Synthesis of M-3 Scheme 3 shows the synthetic route used to prepare M-3, which was carried out as follows: The following reagents were added to a three-necked round bottom flask equipped with a N2 inlet, condenser and temperature probe: 0.2024 moles of 11-bromo-1-undecanol, 0.0713 moles of pyrogallol, 0.4573 moles of potassium carbonate, 0.030 moles of potassium iodide, and 250 mL of acetone. The flask was heated until the acetone started to reflux and was maintained at reflux temperature for 72 hours. The reaction mixture was then cooled to room temperature, filtered, and washed with about 500 mL of excess acetone. The acetone was rotary evaporated to give a yellowish crude solid. (TLC showed three spots, indicating the absence of starting pyrogallol). The tris ether M-3 was recovered by recrystallization from hot acetonitrile. The yield was 29.6 g. FIG. 10 shows the structure of this material M-3 (11,11',11''-(benzene-1,2,3-triyltris(oxy))tris(undecane-1-ol). 1 The H NMR spectrum is shown.

[0124] [ka] Synthesis of M-4 Scheme 4 shows the synthetic route used to prepare M-4 as follows. The following reagents were added to a three-necked round bottom flask equipped with a N2 inlet, condenser, and temperature probe: 8.25 g (0.075 mol) of 1,2 dihydroxybenzene, 38.9 g (0.155 mol) of 11-bromo-1-undecanol, 100 g (0.723 mol) of potassium carbonate, 9 g (0.0542 mol) of potassium iodide, and 420 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 48 hours. The hot solution was filtered through a short silica column and washed with about 200 mL of excess MEK. The solution was kept at -20°C overnight to crystallize and the white solid was isolated by filtration. Yield = 26.0 g (76.5%). FIG. 11 shows the structure of this material M-4 (11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol). 1 The H NMR spectrum is shown.

[0125] [ka] Synthesis of M-5 Structure (M-5) shows the structure of this material, which was prepared as follows: A three-necked round-bottom flask equipped with a N2 inlet, condenser, and temperature probe was charged with all the following reagents: 27.6 g (0.1722 mol) of 2,3-dihydroxynaphthalene, 96.2 g (0.3829 mol) of 11-bromo-1-undecanol, 190.6 g (1.3799 mol) of potassium carbonate, 19.9 g (0.1198 mol) of potassium iodide, and 1500 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 72 hours. The hot solution was filtered through a short silica column and washed with about 300 mL of excess MEK. The solution was kept at -20°C overnight to crystallize and a white solid was isolated by filtration (yield 65 g, 75.4%). Structure (M-5) (11,11'-(naphthalene-2,3-diylbis(oxy))bis(undecane-1-ol)) and FIG. 1 See the H NMR spectrum.

[0126] [ka] Synthesis of M-6 The structure of M-6 is shown in Structure (M-6), which was prepared as follows: To a three-necked round bottom flask equipped with a N2 inlet, condenser, and temperature probe was added all the following reagents: 5.6 g (0.0.03796 mol) 1,8-dihydroxynaphthalene, 22.3 g (0.08871 mol) 11-bromo 1-undecanol, 55.7 g (0.400 mol) potassium carbonate, 6.8 g (0.0496 mol) potassium iodide, and 400 mL methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 24 hours. The hot solution was filtered through a short silica column and washed with about 100 mL excess MEK. The solution was kept at -20°C overnight to crystallize and a white solid was isolated by filtration yield 15 g (85.7%). FIG. 13 shows the structure of M-6 (11,11'-(naphthalene-1,8-diylbis(oxy))bis(undecane-1-ol)). 1 H NMR is shown.

[0127] [ka] Synthesis of M-7 The structure of M-7 is shown in Structure (M-7). It was prepared using Grignard cross-coupling of 1,2-dibromobenzene and 11-bromo-undecyl alcohol THP ether (2-((11-bromoundecyl)oxy)tetrahydro-2H-pyran) in the presence of Pd catalyst as follows. First, the Grignard agent was prepared from 11-bromo-undecyl THP and magnesium in THF, which was added to a mixture of 1,2-dibromobenzene and Ni catalyst [1,2-bis(diphenylphosphino)ethane]dichloronickel(II) at room temperature. The mixture was refluxed for 24 hours, cooled to room temperature, neutralized with dilute hydrochloric acid, and extracted into heptane. After removing the solvent, the resulting yellowish liquid was hydrolyzed with concentrated hydrochloric acid in methanol under reflux. After cooling to room temperature, the mixture was precipitated in DIW, the solid was filtered and washed with acetone to give M-7 (11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol) as a white solid. Figure 14 shows the structure of M-7. 1 The H NMR spectrum is shown.

[0128] [ka] Synthesis of M-8: The structure of M-8 is shown in Structure (M-8). A three-necked round bottom flask equipped with an N2 inlet, condenser, and temperature probe was charged with 15.7 g (0.09625 mol) of 4-tert-butylcatechol, 50.4 g (0.1990 mol) of 11-bromo-1-undecanol, 159.6 (1.152 mol) of potassium carbonate, 13.8 g (0.083 mol) of potassium iodide, and 800 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 14 hours. The hot solution was filtered through a short silica column and washed with approximately 100 mL of excess MEK. The solution was kept at -20°C overnight to crystallize and the white solid was isolated by filtration. Yield: 28.8 g (60.0%) of M-8 (11,11'-((4-(tert-butyl)-1,2-phenylene)bis(oxy))bis(undecane-1-ol)). 1 H NMR is shown.

[0129] [ka] Synthesis of M-9 The structure of M-9 is shown in Structure (M-9). A three-necked round-bottom flask equipped with an N2 inlet, condenser, and temperature probe was charged with all the following reagents: 1.0 g (0.00908 mol) of catechol, 6.0 g (0.01867 mol) of 16-bromo-1-hexadecanol, 15.0 g (0.1082 mol) of potassium carbonate, 1.50 g (0.00904 mol) of potassium iodide, and 100 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 32 hours. The hot solution was filtered through a short silica column and washed with about 100 mL of excess MEK. The solution was kept at -20°C overnight to crystallize and the white solid was isolated by filtration. Yield: 4.2 g (78.3%) of M-9 (16,16'-(1,2-phenylenebis(oxy))bis(hexanedecan-1-ol). Figure 16 shows the reaction of M-9. 1 The H NMR spectrum is shown.

[0130] [ka] Synthesis of M-10 The structure of M-10 is shown in Structure (M-10). A three-necked round-bottom flask equipped with an N2 inlet, condenser, and temperature probe was charged with all the following reagents: 12.5 (0.09250 mol) sino-catechol, 50.4 (0.1990 mol) 11-bromo-1-undecanol, 110.0 (0.796 mol) potassium carbonate, 9.2 g (0.0554 mol) potassium iodide, and 750 mL methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 20 hours. The hot solution was filtered through a short silica column and washed with about 500 mL excess MEK. The solution was kept at -20°C overnight to crystallize and the white solid was isolated by filtration. Yield: 36 g (81.8%) of M-10 (3,4-bis((11-hydroxyundecyl)oxy)benzonitrile). 1 The H NMR spectrum is shown.

[0131] [ka] Synthesis of M-11 The structure of M-11 is shown in Structure (M-11). A three-necked round-bottom flask equipped with a N2 inlet, condenser, and temperature probe was charged with 20.5 g (0.1586 mol) of pyrogallol, 35.5 (0.1522 mol) of 11-bromo-1-undecene, 71.7 (0.5188 mol) of potassium carbonate, 7.0 g (0.0421 mol) of potassium iodide, and 800 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux, and the reaction mixture was maintained at reflux temperature for 30 hours. The hot solution was filtered through a short silica column and washed with about 500 mL of excess MEK. The solvent was evaporated on a rotary evaporator to give a brownish liquid (about 30 g) containing both the mono- and di-ethers. The mono- and di-ethers were separated by column chromatography using an eluent containing 10% ethyl acetate and 90% heptane. The yield was 1.6 g of mono-ether and 27.7 g of di-ether. The di-ether was subjected to etherification with 11-bromo-1-undecanol. A three-necked round-bottom flask equipped with a N2 inlet, a condenser, and a temperature probe was charged with 24.7 g (0.0555 mol) of pyrogallol di-ether, 13.5 (0.1522 mol) of 11-bromo-1-undecanol, 40.0 (0.28943 mol) of potassium carbonate, 4.5 g (0.0271 mol) of potassium iodide, and 400 mL of methyl ethyl ketone (MEK). The flask was heated until the MEK started to reflux and was maintained at reflux temperature for 48 hours. The hot solution was filtered through a short silica column and washed with about 500 mL of excess MEK. The solvent was removed on a rotary evaporator to give a brownish liquid (about 30 g) containing both the mono- and di-ethers. The mono- and di-ethers were separated by column chromatography using an eluent of 10% ethyl acetate:90% heptane. The yield was 31 g of M-11 (11-(2,6-bis(undec-10-en-1-yloxy)phenoxy)undecane-1-ol). Figure 18 shows the elution of M-11. 1 The H NMR spectrum is shown.

[0132] [ka] Synthesis of M-12 The structure of M-12 is shown in Structure (M-12). A three-necked round bottom flask equipped with a N2 inlet, condenser and temperature probe was charged with 10.0 (0.0908 mol) catechol, 50.0 (0.2108 mol) 10-bromo-1-decanol, 92.0 (0.06654 mol) potassium carbonate, 12 g (0.07228 mol) potassium iodide and 1000 mL methyl ethyl ketone (MEK). The flask was heated until the MEK began to reflux and maintained at reflux temperature for 48 hours. The hot solution was filtered through a short silica column and washed with about 500 mL excess MEK. The solution was kept at -20°C overnight to crystallize and the white solid was isolated by filtration. Yield: 30.7 g (80.0%) of M-12 (10,10'-(1,2-phenylenebis(oxy))bis(decan-1-ol). Figure 18 shows the structure of M-12. 1 The H NMR spectrum is shown.

[0133] [ka] Synthesis of M-13, M-14 and M-15 M-13, M-14, and M-15 were synthesized using the synthetic route shown in Scheme 5. In the first step, 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-ol) was converted to the bromide. This bromide was then converted to either the diethyl phosphonate (M-13) (tetraethyl((1,2-phenylenebis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) (yield >90%), the sulfide (M-15) (11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-thiol)) (yield >90%), or the azide (M-14) (1,2-bis((11-azidoundecyl)oxy)benzene) (yield >90%) according to Scheme 3. Figures 20, 21, 22 and 23 show the H NMR spectra of the bromide precursors in Scheme 5, 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-thiol) (M-13), 1,2-bis((11-azidoundecyl)oxy)benzene (M-14) and tetraethyl((1,2-phenylenebis(oxy))bis(undecane-11,1-diyl))bis(phosphonate) (M-15), respectively.

[0134] [ka] Synthesis of M-16 The structure of M-16 (11,11'-((4-methyl-1,2-phenylene)bis(oxy))bis(undecane-1-ol)) is shown in Scheme 6. Protocol 1 was used here to prepare this material in 70% yield. Figure 24 shows the structure of M-16. 1 The H NMR spectrum is shown.

[0135] [ka] M-17: The structure of (methyl 3,4-bis((11-hydroxyundecyl)oxy)benzoate) is shown in Scheme 7. It was synthesized in 65% yield using Protocol 1. Figure 25 shows the structure of M-17. 1 The H NMR spectrum is shown.

[0136] [ka] The structure of M-18 (11,11'-((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-1-ol)) is shown in Scheme 8. It was synthesized in 70% yield using Protocol 1. Figure 26 shows the structure of M-18. 1 The H NMR spectrum is shown.

[0137] [ka] The structure of M-19 (dimethyl 4,5-bis((11-hydroxyundecyl)oxy)phthalate) is shown in Scheme 9. It was synthesized in 60% yield using Protocol 1. Figure 27 shows the structure of M-19. 1 The H NMR spectrum is shown.

[0138] [ka] The structure of M-20 (3,4-bis((11-hydroxyundecyl)oxy)benzonitrile) is shown in Scheme 10. It was synthesized in 80% yield by this procedure using reduction of the nitro group with tin chloride in ethanol. Figure 28 shows the structure of M-20. 1 The H NMR spectrum is shown.

[0139] [ka] Synthesis of M-21: The synthesis of M-21 ((E)-11,11'-((4-(hex-1-en-1-yl)-1,2-phenylene)bis(oxy))bis(undecane-1-ol)) was carried out in a three-step protocol from dihydroxybenzaldehyde as starting material and alpha-bromo-alkylhydroxyl group protected with tetrahydropyran by Protocol 3 shown in Scheme 11. This step was followed by Wittig reaction with butyltriphenylphenyl bromide salt and subsequent hydrolysis of THP group with Amberlyst®-15 to give M-21 in 40% yield. Figure 29 shows the cleavage of THP-protected M-21. 1 1 H NMR spectrum of M-21. 1 The H NMR spectrum is shown.

[0140] [ka] Synthesis of M-22 The synthesis of M-22 (tetraethyl(((4-cyano-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) was carried out according to Protocol 2 shown in FIG. 12 to give M-22 in >95% yield. FIG. 31 and FIG. 32 show the synthesis of M-22, respectively. 1 H NMR spectrum and 31 The P NMR spectrum is shown.

[0141] [ka] Synthesis of M-23 Scheme 13 shows a synthetic route for the preparation of M-23 (tetraethyl(((4-acetyl-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) in >95% yield. Figures 33 and 34 show the synthesis of M-23, respectively. 1 H and 31 The P NMR spectrum is shown.

[0142] [ka] Synthesis of M-24: M-23 (dimethyl 4,5-bis((11-(diethoxyphosphoryl)undecyl)oxy)phthalate) was synthesized using Protocol-2. Scheme 14 shows the synthetic route to prepare M-23 (dimethyl 4,5-bis((11-(diethoxyphosphoryl)undecyl)oxy)phthalate) in >95% yield. Figures 35 and 36 show the synthesis of M-24, respectively. 1 H and 31 The P NMR spectrum is shown.

[0143] [ka] Synthesis of M-25: M-25 (tetraethyl(((4-nitro-1,2-phenylene)bis(oxy))bis(undecane-11,1-diyl))bis(phosphonate)) was synthesized using Protocol-2 as shown in Scheme 15 and obtained in >95% yield. Figure 37 shows the H NMR spectrum of M-25.

[0144] [ka] Section B: Materials Processing This section describes the processing of compounds of the invention to form self-assembled monolayers (SAMs) on SiOx substrates and testing the interactions of these SAMs.

[0145] X-ray photoelectron spectroscopy (XPS) measurement These were performed using a Thermo Fisher K-Alpha. Experiments were performed using a pass energy of 50 eV, a step size of 0.100 eV, a dwell time of 50 ms, and 10 scans per element.

[0146] Water contact angle (WCA) measurement These were performed at room temperature using a Cruz Dynamic Contact Angle Measurement Tool. A 4 microliter drop of denoised water was used. Reported values ​​are the average of measurements of 5 to 6 spots per 1 x 1 inch coupon.

[0147] Preparation of PS-b-PMMA BCP solution for SAM testing Polymer Synthesis Example 3 was dissolved in 70 / 30 PMMEA to produce a 0.4 wt % solution which was filtered using 0.2 μm PTFE.

[0148] Si / SiOx wafer The 6-inch and 8-inch wafers were obtained from Silicon Valley Microelectronics (SVM).

[0149] X-ray reflectance (XRR) measurement These measurements were carried out at the Technical University of Darmstadt, Germany.

[0150] Ellipsometry Ellipsometry film thickness measurements were performed using a JAWoollam. SAM FT was measured using a single layer model with an RI of 1.45 for the organic phase.

[0151] Selective Wetting of Block Copolymers SAM precursors with the prefix "M-" were individually dissolved in PGMEA to prepare formulations denoted by the prefix "SML-", and SAM assemblies were formed by spin-coating 1% PGMEA SML solutions at 2000-300 RPM, followed by baking at 125-200 °C for 5-30 min in nitrogen or air. After baking, the excess SAM precursor was removed by washing with PGMEA and blown dry before being used for further analysis. The thickness of the SAM was measured using ellipsometry. Tables 1 and 2 summarize the properties of the self-assembled monolayers formed by some of these SAM precursors on Si / SiO2 wafers, and also report the self-assembly behavior of a representative block copolymer (PS-b-PMMA) containing both polar and non-polar block segments after annealing (Table 1). Table 1 shows the results of selected wetting experiments in WCA, % carbon atoms. The SAM materials of the present invention with variable tail groups and hydroxyl anchor groups were coated onto blanket Si / SiOx wafers as described herein to form self-assembled layers on the Si / SiOx wafers, the WCA was measured, and XPS measurements of the atomic % of carbon were performed to confirm that self-assembled layers formed on the substrates as reported in Table 1. Each Si / SiOx substrate with these different SAM coatings was then individually coated with BCP (PS-b-PMMA) solution to obtain a 50 nm (1Lo) thick BCP coating. The BCP coating was then annealed at 250° C. for 20 minutes, and the surface morphology of the block copolymer film was examined by SEM, and the water contact angle of the block copolymer was measured as described in Table 1. As shown in Table 1, the non-polar tail group preferentially wetted the PS block of BCP, and the polar tail group wetted the PMMA block of BCP. Here, SEM morphology examination of the block copolymer film shows that both the polar and non-polar tail groups give a flat morphology.This suggests a preference for either the polar PMMA block segment or the non-polar PS block segment of this block copolymer, since either the non-polar PS block segment or the polar PMMA block segment interacts strongly with the non-polar or polar SAM, respectively, resulting in the block copolymer segments being parallel to the SAM layer. In the case of the short alkyl tail group, methyl, especially the H tail group, it was observed that the block copolymer formed a fingerprint pattern when annealed. The formation of the fingerprint pattern suggests that the block copolymer segments did not show a preference for either SAM substrate, but were oriented perpendicular to the substrate. Table 1 confirms that the preferential wetting of BCP was obtained through the appropriate selection of the tail group. Therefore, when the prepattern was modified with either the non-polar or polar SAM, this allowed for the parallel alignment of either the non-polar PS polymer block segment or the polar PMMA block segment of PS-b-PMMA, respectively, resulting in the flat shape observed by SEM. Conversely, when SAMs resulting from precursors with H or methyl as tails were used, the polar or non-polar polymer block segments of PS-b-PMMA did not show strong affinity and were oriented perpendicular to the SAM surface, resulting in the formation of fingerprint patterns as observed by SEM. Therefore, polar and non-polar SAMs substituted with polar or non-polar tail groups, respectively, can be used in chemoepitaxy DSA processes when patterned to form pinned polar or non-polar pinned regions, respectively, on the patterned substrate. Additionally, SAM materials with H tail groups were used as neutral layers in DSA lithography processing such as chemoepitaxy. In some cases, methyl-tailed SAM materials that showed partial neutral layer formation in our tests may also be useful as neutral layers on other substrates, where they may exhibit the properties of a completely neutral layer.

[0152] [Table 1]

[0153] [Table 2]

[0154] 39 and 40 show the XRR curves measured for a few selected SML molecules (SML-8, SML-3 and SML-6) and for octadecyltrichlorosilane (ODTS-Cl3) as a comparative material. The calculated values ​​obtained from these XRR curves are shown in Table 3. As can be seen in the table, the 2 The value of the number of molecules per 1000 depends on the number of alkyl chains in the SAM molecule. These electron density values ​​indicated very good close packing of the SAM molecules on the substrate surface.

[0155] [Table 3]

[0156] Selective SAM assembly and passivation properties on dielectric surfaces. At high temperatures (>150°C), SAMs with hydroxyl head groups were observed to react on silanol Si surfaces and on native metal oxides. To obtain dielectric-selective SAMs, selective removal of SAMs from metal lines was necessary. Metal-OC- bonds are weaker than -Si-OC- bonds and are susceptible to both acidic and basic reagents. Furthermore, the thermal stability of these metal-OC- bonds is much lower than Si-O-alkyl bonds. Therefore, to selectively deposit dielectric-SAMs, metal SAMs were removed using formulations containing organic acids, glycine as oxidizer and chelator (Figure 41, Tables 5, 6, 7 and 8), organic bases (Table 10), and dithiol solutions (2 wt% butanedithiol in 70:30 PGME:PGMEA) (Table 9), and thermal cleavage (Table 9). All of the above methods showed negligible effect on SAMs on SiOx (Figures 41-44). Additionally, removal solutions containing citric acid and 70 / 30 PGME / PGMEA were also tested. These solutions also did not remove SAMs with Si-O-alkyl bonds. Therefore, the dielectric SAMs on the SiOx substrates remained stable. After selectively depositing the SAM on the dielectric, its passivation properties were analyzed against atomic layer deposition of hafnium oxide. Selective deposition of 7-8 nm HfOx on W vs SiOx was achieved (Figure 45). The data tabulated in Tables 5-8 showed that these different remover solutions selectively removed the SAM from the metal surface but had no effect on the SAM on the SiOx surface. 1) Table 5 shows that the glycine / hydrogen peroxide composition removed the SAM from the metal surface but had no effect on the SiOx SAM. 2) Table 6 shows the XPS data for the SAM on SiOx vs SAM on metal, with negligible C atomic % indicating that DBSA selectively removed the SAM from the metal surface. 3) Table 7 shows the effect of DBSA on metal surfaces by X-SEM, which indicates that the FT of the metal layer is not affected by DBSA cleaning. 4) Table 8 shows XPS data showing the removal of the SAM from the metal surface as evidenced by negligible atomic % C on the metal and no change of the SAM on SiOx.

[0157] Selective SAM Assembly on Metal Surfaces: Formulations SML-13, SML-14 and SML-15 were prepared by dissolving M-13, M-14 and M-15 in PGMEA at 1 wt% concentration, respectively. Spin-coated at RPM1500, baked at 170°C / 5min and washed with excess PGMEA to remove unreacted SAM precursor. SAMs were analyzed by measuring water contact angle (Table 4) and XPS normalized C atom% (Figure 40). Selective deposition on tungsten and copper vs. dielectric silanols was obtained by preferential reaction of metal / metal oxide with dithiol, azide and diethylphosphonate functional groups.

[0158] Selective SAM Removal on Metal Surfaces: The water contact angle information in Table 4 shows that self-assembled monolayers were deposited on W, Cu and Si using SML-13, SML-14 and SML-15.

[0159] Table 4 shows the composition and pH of glycine removal solutions in water, including oxidizers and stabilizers, used to selectively remove metal SAMs in the presence of non-metal SAMs formed with SML-12.

[0160] Table 6 shows the removal effect of a 2 wt % dodecylbenzene DBSA solution in PGME:PGMEA 70:30 on SAMs formed from SML-13, SML-14, and SML-15 on various substrates using XPS data. The data showed that the solution was effective in removing these SAMs from both Cu and W, and that the removal was selective, as the high carbon counts on the SAMs formed on the Si samples indicated that the SAMs were not cleaved on this non-metallic substrate.

[0161] Table 7 shows the SEM morphology of the SAM on the metal substrate after DBSA cleaning with 2 wt % dodecylbenzenesulfonic acid in 70:30 PGME:PGMEA, followed by a 2 min rinse with PGMEA and N2 blow dry, indicating that the acid is mild and removes only the SAM without leaching the metal layer.

[0162] Table 8 shows the effect of a stripping solution of 2 wt% dodecylbenzene (DBSA) in PGME:PGMEA 70:30 on the removal of SAMs formed from SML-12 and SML-5 on W, Cu, and Si using thickness, XPS, and water contact angle data. This shows that in the case of SAMs on Cu and W, the SAM is selectively removed from these metals but retained on Si, and that the acid solution is mild and only removes the SAM without leaching or corroding the metal layer. In this experiment, a 2 minute clean with the stripper was followed by a 2 minute PGMEA and N2 blow dry.

[0163] Table 5 shows the performance of a citric acid-based remover formulation containing 1 wt% citric acid in a 50:50 wt:wt solution of water and 70:30 PGME:PGMEA. This solution was used to clean the SAM for 2 minutes, followed by a 2 minute PGMEA rinse and N2 blow dry. The data shows that the SAM was selectively removed from the metal substrate while remaining intact on the Si.

[0164] Table 10 shows the effect that butanedithiol has on SAM (M-12) removal. The solution was a 1 wt% solution in 70:30 PGME:PGMEA. The SAM substrate was washed with this solution for 2 minutes and then further annealed at a higher temperature. The change in WCA and XPS carbon atom % on the metal surface vs. SiOx indicates that the SAM was selectively removed from the metal surface.

[0165] Table 11 shows the effect of the base triethylamine on SAM (M-12) removal. The solution was a 1 wt% solution in 70:30 PGME:PGMEA. The SAM substrate was washed with this solution for 2 minutes and then washed with PGME:PGMEA 70:30 for 2 minutes. The change in WCA and XPS carbon atom % on the metal surface vs. SiOx indicates that the SAM was selectively removed from the metal surface.

[0166] Table 12 shows the effect of heat treatment to effect selective removal of SAMs from metallic Cu and W compared to SAMs on Si. The data showed that thermal annealing at relatively high temperatures selectively cleaved the SAM bonds to the metal surface and were washed away with a PGME:PGMEA 70:30 mixture.

[0167] These solutions had a pH range of about 3 to about 5.

[0168] Citric acid solution in EBR70 / 30 (70 / 30 PGME / PGMEA) Example of the above: 50% Citric Acid (aqueous) / EBR70 / 30 (50:50 ratio) for 2 min, PGMEA for 2 min, N2 blow dry (Table 9).

[0169] [Table 4]

[0170] [Table 5]

[0171] [Table 6]

[0172] Table 9 (SEM morphology of SAMs on metal substrates after DBSA cleaning with 2 wt % dodecylbenzenesulfonic acid in 70:30 PGME:PGMEA) is shown in FIG.

[0173]

Table 7

[0174]

Table 8

[0175]

Table 9

[0176]

Table 10

[0177]

Table 11

Claims

1. 1. A composition comprising a compound of structure (I) and an organic spin-casting solvent, wherein in said compound of structure (I): A is a core moiety selected from structures (Ia), (Ib), (Ic), and (Id) attached through a direct valence bond or a divalent linking group as X, m is the number of linear alkylene moieties of chain length n, where n ranges from 8 to 12, and each of said linear alkylene moieties has a terminal B reactive moiety, and further, * indicates a possible point of attachment of said linear alkylene moiety in each structure, and structures (Ia) and (Ib) have two or three points of attachment on adjacent carbons (m=2 or 3), structure (Ic) has two points of attachment (m=2), and structure (Id) has three points of attachment (m=3); B is -OH, -CH=CH ２ , -O-(P=O)(OR) ２ , -O-(P=O)(OR)Rs, -N ３ and —SH, wherein R and Rs are independently selected from C1-C8 alkyl; R １ａ and R １ｂ are independently H, C1-C4 alkyl, C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH ２ —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), nitro (NO ２ ), N.H. ２ , and CN; R １ｃ , R １ｄ , R １ｅ , R １ｆ and R １ｇ are independently H, C1-C4 alkyl, C1-C4 alkyloxy, C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), C3-C6 methylcarbonyloxyalkyl (—CH ２ —(C═O)—O-alkyl), and CN; and With respect to the core moieties (Ia), (Ib), and (Ic), the divalent linking group is selected from the group consisting of oxy (—O—), oxycarbonyl (—O—C(═O)—), carbonyloxy (—C(═O)—O—), carbonyl (—(C═O)—), sulfinyl (—(S(═O))—), and sulfone (—S(═O) 2 —); with respect to the core structure (Id), the divalent linking group is selected from the group consisting of oxy (—O—), oxycarbonyl (—O—C(═O)—), carbonyloxy (—C(═O)—O—), 【Chemical 1】 is selected from the group consisting of 1,4-phenylene (-Ph-), 1,4-phenyleneoxy (-Ph-O-), 1,4-oxyphenylene (-O-Ph-), carbonyl (-(C=O)-), sulfinyl (-(S(=O))-), sulfone (-S(=O) 2 -), 1,2-ethene (-CH=CH-), 1,1-ethene (-C(=CH 2 )-), and methylene (-CH 2 -); and the organic spin-casting solvent is selected from the group consisting of glycol ether derivatives, glycol ether ester derivatives, carboxylates, dicarboxylates of dibasic acids, dicarboxylates of glycols, ketone esters, ketone ether derivatives, ketone alcohol derivatives, lactones, amide derivatives, and mixtures thereof; and The compound of formula (I) comprises from about 0.5% to about 3.00% by weight of the composition. The composition. 【Chemistry 2】

2. The composition described in claim 1, wherein the organic spin-casting solvent is selected from the group consisting of glycol ether derivatives, glycol ether ester derivatives, and mixtures thereof.

3. The compound of formula (I) is 11,11',11''-((ethane-1,1,1-triyltris(benzene-4,1-diyl))tris(oxy))tris(undecan-1-ol) (M-1), 11,11',11''-(propane-1,2,3-triyltris(oxy))tris(undecan-1-ol) (M-2), (11,11',11''-(benzene-1,2,3-triyltris(oxy))tris(undecan-1-ol) (M-3), (11,11',11''-(1,2-phenylenebis(oxy))bis(undecane-1 -ol) (M-4), 11,11'-(naphthalene-2,3-diylbis(oxy))bis(undecan-1-ol) (M-5), 11,11'-(naphthalene-1,8-diylbis(oxy))bis(undecan-1-ol) (M-6), 11,11'-(1,2-phenylenebis(oxy))bis(undecan-1-ol) (M-7), 11,11'-((4-(tert-butyl)-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-8), 1,2-phenylenebis(oxy)bis(hexadecan-1 -ol) (M-9), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-10), 11-(2,6-bis(undec-10-en-1-yloxy)phenoxy)undecan-1-ol (M-11), 10,10'-(1,2-phenylenebis(oxy))bis(decan-1-ol) (M-12), 11,11'-(1,2-phenylenebis(oxy))bis(undecane-1-thiol) (M-13), 1,2-bis((11-azidoundecyl)oxy)benzene (M-14), tetraethyl ((1,2- 11,11'-((4-methyl-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-16), methyl 3,4-bis((11-hydroxyundecyl)oxy)benzoate (M-17), 11,11'-((4-nitro-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-18), dimethyl 4,5-bis((11-hydroxyundecyl)oxy)phthalate (M-19), 3,The composition according to claim 1, wherein the hydroxybenzonitrile is selected from the group consisting of 4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-20), and (E)-11,11'-((4-(hex-1-en-1-yl)-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-21).

4. The composition of claim 1, wherein structure (Ia) has structure (Ia-1) and m is 2, where * indicates the location of the two attachment points. 【Chemistry 3】 5. The composition of claim 4, wherein X is selected from the group consisting of a direct valence bond and oxy (—O—).

6. The compound of formula (I) is (11,11'-(1,2-phenylenebis(oxy))bis(undecan-1-ol) (M-4), 11,11'-(1,2-phenylenebis(oxy))bis(undecan-1-ol) (M-7), 1,2-phenylenebis(oxy))bis(hexadecan-1-ol) (M-9), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-10), 10,10'-(1,2-phenylenebis(oxy))bis(decan-1-ol) (M-12), 11,11'-((4-methyl-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M- 16), methyl 3,4-bis((11-hydroxyundecyl)oxy)benzoate (M-17), 11,11'-((4-nitro-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-18), dimethyl 4,5-bis((11-hydroxyundecyl)oxy)phthalate (M-19), 3,4-bis((11-hydroxyundecyl)oxy)benzonitrile (M-20), and (E)-11,11'-((4-(hex-1-en-1-yl)-1,2-phenylene)bis(oxy))bis(undecan-1-ol) (M-21).

7. The composition of claim 1, wherein in the compound of structure (I), the core moiety A has structure (Ia) and m is 3. 【Chemistry 4】 8. The composition of claim 7, wherein B is selected from the group consisting of -OH, -CH=CH 2 and -SH.

9. The composition of claim 8, wherein X is selected from the group consisting of a direct valence bond and oxy (—O—).

10. The composition of claim 9, wherein the compound of structure (I) is either (11,11',11''-(benzene-1,2,3-triyltris(oxy))tris(undecan-1-ol) (M-3) or 11-(2,6-bis(undec-10-en-1-yloxy)phenoxy)undecan-1-ol (M-11).

11. The composition of claim 1, wherein in the compound of structure (I), the core moiety A has structure (Ib) and m is 3, or has structure (Ib-1) and m is 2, * represents a point of attachment, and B is selected from the group consisting of -OH, -CH=CH2, and -SH. 【Chemistry 5】 12. The composition of claim 11, wherein X is selected from the group consisting of a direct valence bond and oxy (—O—).

13. The composition of claim 1, wherein in the compound of formula (I), the core moiety A has the structure (Ic), * represents a point of attachment, and B is selected from the group consisting of -OH, -CH=CH2, and -SH. 【Chemistry 6】 14. The composition of claim 13, wherein X is selected from the group consisting of a direct valence bond and oxy (—O—).

15. The composition of claim 1, wherein in the compound of structure (I), the core moiety A has structure (Id), where X is methylene (-CH 2 -), and the combination of A and X has structure (Id-1), where * indicates the point of attachment, and B is selected from the group consisting of -OH, -CH=CH 2 and -SH. 【Chemistry 7】 16. The composition of claim 1, wherein in the compound of structure (I), the core moiety A has structure (Id), where X is a 1,4-phenyleneoxy (-Ph-O-) linking group, and the combination of A and X has structure (Id-3), where * indicates the point of attachment, and B is selected from the group consisting of -OH, -CH=CH2, and -SH. 【Chemistry 8】 17. The composition according to claim 1, which is a PMMA-compatible SAM composition, wherein in compound (I), R １ａ and R １ｂ At least one of the following is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), nitro (NO ２ ), N.H. ２ is a polar substituent selected from, and CN; R １ｃ or R １ｄ At least one of the groups is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ a polar substituent selected from —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), and CN; R １ｅ or R １ｆ At least one of the groups is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ a polar substituent selected from —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), and CN; R １ｇ is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH ２ a polar substituent selected from C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl) and CN, and further １ａ and R １ｂ Either one of these or R １ｃ and R １ｄ Either one of these or R １ｅ and R １ｆ If only one of the groups is such a polar substituent, the other substituent is H or C1-C4 alkyl. The composition.

18. The composition according to claim 1, which is a PS-affinity SAM composition, wherein compound (I) is R １ａ or R １ｂ at least one of is C1-C4 alkyl, and R １ｃ or R １ｄ at least one of is C1-C4 alkyl, and R １ｅ or R １ｆ at least one of is C1-C4 alkyl, and R ｇ is C1-C4 alkyl, and further, R １ａ and R １ｂ Either one of these or R １ｃ and R １ｄ Either one of these or R １ｅ and R １ｆ wherein when only one of the groups is C1-C4 alkyl, the other group is H.

19. The composition according to claim 1, which is a neutral affinity SAM composition, wherein in compound (I), R １ａ , R １ｂ , R １ｃ , R １ｄ , R １ｅ , R １ｆ , and R １ｇ is H.

20. 18. A method of coating with a PMMA-compatible SAM composition, comprising the steps of: i) coating a substrate with the PMMA-compatible SAM composition of claim 17; ii) baking at a temperature ranging from about 150°C to about 200°C; iii) washing with an organic spin-casting solvent to form a self-assembled monolayer having an affinity for the PMMA block segment of a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA); The method comprising:

21. 1. A method of coating with a PS-compatible SAM composition, comprising the steps of: ia) coating a substrate with the PS-affine SAM composition of claim 18; iia) baking at a temperature ranging from about 150°C to about 200°C; iiia) washing with an organic spin-casting solvent to form a self-assembled monolayer having an affinity for the PS block segment of a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA); The method comprising:

22. 1. A method of coating with a neutral affinity SAM composition, comprising the steps of: ib) coating a substrate with the neutral affinity SAM composition of claim 19; iib) baking at a temperature ranging from about 150°C to about 200°C; iiib) washing with an organic spin-casting solvent to form a self-assembled monolayer with a neutral affinity for the block segments of a block copolymer of polystyrene (PS) and methyl methacrylate (MMA) (PS-b-PMMA); The method comprising:

23. 1. A method for selective deposition of a self-assembled monolayer followed by directed self-assembly of a block copolymer, comprising the steps of: ic) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iic) coating the substrate with a PMMA-compatible brush polymer or a PMMA-compatible SAM composition, wherein the PMMA-compatible SAM composition is the composition of claim 1, wherein the compound of structure (I) comprises: A is a core moiety selected from structures (Ia), (Ib), (Ic), and (Id) attached through a direct valence bond or a divalent linking group as X, m is the number of linear alkylene moieties of chain length n, where n ranges from 8 to 12, and each of said linear alkylene moieties has a terminal B reactive moiety, and further, * indicates a possible point of attachment of said linear alkylene moiety in each structure, and structures (Ia) and (Ib) have two or three points of attachment on adjacent carbons (m=2 or 3), structure (Ic) has two points of attachment (m=2), and structure (Id) has three points of attachment (m=3); B is -OH, -CH=CH ２ , -O-(P=O)(OR) ２ , -O-(P=O)(OR)Rs, -N ３ and —SH, wherein R and Rs are independently selected from C1-C8 alkyl; R １ａ and R １ｂ are independently H, C1-C4 alkyl, C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH ２ —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), nitro (NO ２ ), N.H. ２ , and CN; R １ｃ , R １ｄ， , R １ｅ , R １ｆ and R １ｇ are independently H, C1-C4 alkyl, C1-C4 alkyloxy, C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), C3-C6 methylcarbonyloxyalkyl (—CH ２ —(C═O)—O-alkyl), and CN, and further R １ａ and R １ｂ At least one of the following is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), nitro (NO ２ ), N.H. ２ is a polar substituent selected from, and CN; R １ｃ or R １ｄ At least one of the groups is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ a polar substituent selected from —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), and CN; R １ｅ or R １ｆ At least one of the groups is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (—CH ２ a polar substituent selected from —(C═O)—O-alkyl), C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl), and CN; R １ｇ is C1-C4 alkyloxy, C3-C6 methyl (carbonyloxyalkyl) (-CH ２ a polar substituent selected from C2-C5 carbonyloxyalkyl (—(C═O)—O-alkyl) and CN, and further １ａ and R １ｂ Either one of these or R １ｃ and R １ｄ Either one of these or R １ｅ and R １ｆ If only one of the groups is such a polar substituent, the other substituent is H or C1-C4 alkyl. iiic) baking at a temperature ranging from 150°C to 200°C; ivc) washing with an organic spin-casting solvent to produce a substrate with PMMA-compatible brushes or PMMA-compatible self-assembled monolayers attached only to the metal lines; vc) coating with the neutral affinity SAM composition of claim 19; vi) baking at a temperature ranging from about 150°C to about 200°C; viic) washing with an organic spin-casting solvent to produce a substrate with PMMA brushes still attached to the metal lines but with the neutral affinity self-assembled monolayer also attached to the non-metal lines; viiiic) coating the substrate formed in step viic) with a block copolymer solution; vivc) annealing the block copolymer coating to form a directed self-assembled block copolymer L / S pattern; The method comprising:

24. The PMMA-compatible SAM composition comprises the compound (I): at least one of R 1a and R 1b is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH 2 -(C═O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C═O)-O-alkyl), nitro(NO 2 ), NH 2 , and CN; at least one of R 1c or R 1d is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH 2 -(C═O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C═O)-O-alkyl), and CN; at least one of R 1e or R 1f is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH 2 -(C═O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C═O)-O-alkyl), and CN; R 1g is a polar substituent selected from C1-C4 alkyloxy, C3-C6 methyl(carbonyloxyalkyl)(-CH 2 -(C═O)-O-alkyl), C2-C5 carbonyloxyalkyl(-(C═O)-O-alkyl) and CN, and further, when only one of R 1a and R 1b , or only one of R 1c and R 1d , or only one of R 1e and R 1f is such a polar substituent, the other substituent is H or C1-C4 alkyl; 24. The method of claim 23, which is a PMMA-compatible SAM composition.

25. 1. A method for selective removal of a self-assembled monolayer and directed self-assembly of a polymer, comprising the steps of: id) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iid) coating with the PS-affining SAM composition of claim 18; iiid) baking at a temperature ranging from about 150°C to about 200°C; ivd) washing with an organic spin-casting solvent to produce a substrate having a PS-affine self-assembled monolayer bonded throughout the substrate on both the metal and non-metal lines; vd) treating with a removal solution to selectively remove the PS-affine self-assembled monolayer, wherein the removal solution is a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents, water, and a pK of about 2.9 to about 5 ａ a tricarboxylic acid having a pK of about 3 to about 5; ａ and an acid component selected from a dicarboxylic acid having the formula: - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and dithiols, and - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and an amine, selected from the group consisting of vid) optionally baking at a temperature ranging from about 100°C to about 200°C; vid) washing with an organic spin-casting solvent to produce a substrate having only a PS-affine self-assembled monolayer on the non-metallic lines over the entire substrate; viii) coating with the neutral affinity SAM composition of claim 19; ixd) baking at a temperature ranging from about 150°C to about 200°C; xd) washing with an organic spin-casting solvent to produce a substrate with a neutral affinity self-assembled monolayer attached to the metal lines and a PS affinity self-assembled monolayer attached to the non-metal lines; xid) coating the substrate formed in step ixd) with a solution of a block copolymer having polar and non-polar block segments; xiid) annealing the block copolymer coating to form a directed self-assembled block copolymer L / S pattern; The method comprising:

26. 1. A method for coating a PMMA-compatible SAM composition onto a chemo-epitaxy array of metal and non-metal lines and selectively removing the SAM deposited on the metal lines, comprising the steps of: ie) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; ii) coating a substrate with the PMMA-compatible SAM composition of claim 17; iii) baking at a temperature ranging from about 150°C to about 200°C; ive) washing with an organic spin-casting solvent to form a PMMA-compatible self-assembled monolayer on both the metal and non-metal lines; ve) selectively removing the PMMA-affinity self-assembled monolayer from the metal lines by treatment with a removal solution, wherein said removal solution comprises: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents, water, and a pK of about 2.9 to about 5 ａ a tricarboxylic acid having a pK of about 3 to about 5; ａ and an acid component selected from a dicarboxylic acid having the formula: - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and dithiols, and - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and an amine, selected from the group consisting of vii) optionally baking at a temperature ranging from about 100°C to about 200°C; vii) treating with an organic spin-casting solvent to remove cleaved SAMs, thereby producing a substrate with a PMMA-affinity self-assembled monolayer bound only to the non-metallic lines; The method comprising:

27. 1. A method for coating a PS-compatible SAM composition on a chemo-epitaxy array of metal and non-metal lines and selectively removing the SAM deposited on the metal lines, comprising the steps of: if) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iif) coating a substrate with the PS-affine SAM composition of claim 18; iiif) baking at a temperature ranging from about 150°C to about 200°C; ivf) washing with an organic spin-casting solvent to form a PS-friendly self-assembled monolayer on both the metal and non-metal lines; vf) selectively removing the PS-affine self-assembled monolayer from the metal lines by treatment with a removal solution, wherein said removal solution comprises: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents, water, and a pK of about 2.9 to about 5 ａ a tricarboxylic acid having a pK of about 3 to about 5; ａ and an acid component selected from a dicarboxylic acid having the formula: - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and dithiols, and - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and an amine, selected from the group consisting of vif) optionally baking at a temperature ranging from about 100°C to about 200°C; viif) removing the cleaved PS-affine self-assembled monolayer from the metal lines by treatment with an organic spin-casting solvent to produce a substrate with the PS-affine self-assembled monolayer attached only on the non-metal lines; The method comprising:

28. 1. A method for coating a neutral affinity SAM composition on chemo-epitaxy lines of metal and non-metal lines and selectively removing the SAM deposited on the metal lines, comprising the steps of: ig) forming a chemo-epitaxy array of metal and non-metal lines on a substrate using lithographic processing; iig) coating a substrate with the neutral affinity SAM composition of claim 19; iiig) baking at a temperature ranging from about 150°C to about 200°C; ivg) washing with an organic spin-casting solvent to form a neutrophilic self-assembled monolayer on both the metal and non-metal lines; vg) selectively removing the neutron-philic self-assembled monolayer from the metal lines by treating with a removal solution, wherein said removal solution comprises: a stripping solution comprising water, glycine, a hydrogen peroxide solution, and a co-acid component selected from a dicarboxylic acid, a tricarboxylic acid, or an alkyl-substituted aryl sulfonic acid, having a pH of about 3 to about 5; Alcohol- and glycol-based spin-cast solvents, water, and a pK of about 2.9 to about 5 ａ a tricarboxylic acid having a pK of about 3 to about 5; ａ and an acid component selected from a dicarboxylic acid having the formula: - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and dithiols, and - A removal solution consisting of an alcohol-based glycol-based spin-cast solvent and an amine, selected from the group consisting of vig) optionally baking at a temperature ranging from about 100°C to about 200°C; viig) treating with an organic spin-casting solvent to remove the cleaved neutrophilic self-assembled monolayer from the metal lines to produce a substrate with the neutrophilic self-assembled monolayer attached only on the non-metallic lines; The method comprising:

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