Low Tg Multitethered Diblock Copolymers for Directed Self-Assembly

Abstract

Two different block copolymer families having the general structure (I) or (III), compositions thereof, and processes for using these compositions for DSA are disclosed. The B and B1 segments are polar block copolymer segments containing repeating units derived from alkyl 2-methylene alkanoates, lactones, oxiranes, oxetanes, or cyclic carbonates; L and L1 are direct valence bonds or linking moieties derived from 1,1-diarylethenes; the A and A1 segments are nonpolar block copolymer segments containing styrenic repeating units, and E', E'', E', ... 3 and E 4 are different types of end groups, and A2 is a T g and in structure (I), the oligoflexible tethered groups are multi-tethered at various positions as outlined. E'-ALB-E'' (I) E 3 -A1-A2-L1-B1-E 4 (III)

Description

[Technical Field]

[0001] The present invention relates to a family of block copolymers of general structures (I) and (III) and to methods of using compositions of these block copolymers to align microdomains of self-assembling block copolymers (BCPs) to form self-assembled geometries useful for forming arrays of contact holes or lines and spaces. These compositions and methods are useful in the fabrication of electronic devices. [Background technology]

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

[0003] Therefore, in guided or unguided self-assembly of block copolymer films on patterned or unpatterned substrate regions, the self-assembly process of the block copolymer layer typically occurs during annealing of the film overlying a neutral layer. The neutral layer on the semiconductor substrate can be an unpatterned neutral layer, or in chemoepitaxy or graphoepitaxy, the neutral layer can contain graphoepitaxy or chemoepitaxy-guided features, respectively (formed via UV lithography techniques described above). During annealing of the block copolymer film, 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 surface of the underlying neutral layer. These nanophase-separated block copolymer domains form prepatterns (e.g., lines and spaces), which can be transferred into the substrate via an etching process (e.g., plasma etching). In graphoepitaxy or chemoepitaxy, these guiding features can induce 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 thermally 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 graphoepitaxy-guided self-assembly methods, block copolymers self-assemble on substrates that have been prepatterned using conventional lithography (ultraviolet, deep UV, electron beam, or 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-guided self-assembly array, the block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the prepatterned lines, thereby enhancing pattern resolution by dividing the spaces in the trenches between the topographical lines into finer patterns. For example, diblock or triblock copolymers that can microphase separate and contain a carbon-rich block (e.g., containing styrene or some other element such as Si, Ge, or Ti) that is resistant to plasma etching and a block that is easily plasma-etched or removable can provide high-resolution pattern definition. An example of a highly etchable block can be oxygen-rich, refractory-free, and contain a monomer capable of forming a highly etchable block, such as methyl methacrylate. The plasma etching gases used in the etching process to define the self-assembled pattern are typically those used in processes used in integrated circuit (IC) fabrication. In this manner, much finer patterns can be created on a typical IC substrate than can be defined by conventional lithography techniques, thus achieving pattern multiplication. Similarly, using graphoepitaxy, in which a suitable block copolymer aligns itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography, features such as contact holes can also be created at higher densities by forming a denser array of regions of etchable and etch-resistant domains that, when etched, give a denser array of contact holes. Consequently, graphoepitaxy has the potential to provide both pattern modification and pattern multiplication.

[0005] In chemical epitaxy, or pinned chemical epitaxy, block copolymer self-assembly occurs on a surface that has a guiding feature—regions of differing chemical affinity—but no or minimal topography (i.e., non-guiding topography) to serve as the basis for the guided self-assembly process. For example, the surface of a substrate can be patterned using conventional lithography (UV, deep UV, e-beam, or EUV) to produce a line-and-space (L / S) pattern of surfaces with differing chemical affinities, where exposed regions, where the surface chemistry has been modified by radiation, alternate with unexposed regions that exhibit 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, guided self-assembly of a block copolymer with block segments containing etch-resistant repeating units (e.g., styrene repeating units) and fast-etching repeating units (e.g., methyl methacrylate repeating units) would allow for precise placement of the etch-resistant and fast-etching block segments in the 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 it can be fine-tuned by varying chemical differences, allowing for pattern modification, helping to improve line-edge roughness and CD control. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern modified using chemo-epitaxy.

[0006] These neutral layers are layers on substrates or surfaces of treated substrates that have no affinity for any of the block segments of the block copolymers used in the 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, resulting in the proper placement of the etch-resistant and etch-resistant block polymer segments relative to the substrate. For example, in a surface containing line-and-space features defined by conventional radiation lithography, the neutral layer allows for the orientation of the block segments so that they are oriented perpendicular to the surface of the substrate. This orientation is ideal for both pattern modification and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, this segment will lie flat on its surface, maximizing the contact area between the segment and the substrate; such a surface will disrupt the desired vertical alignment, which can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modifying or pinning selected small regions of the substrate so that they interact strongly with one block of the block copolymer, while leaving the rest of the substrate coated with a neutral layer, can be useful for aligning the domains of the block copolymer in a desired direction, and this is the basis for pinned chemo- or graphoepitaxy used for pattern multiplication. [Prior art documents] [Non-patent literature]

[0007] [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,p.315 [Non-patent document 4] Encyclopedia of Polymer Science and Technology,2014,Vol.7,p.625 [Non-patent document 5] David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization”, Journal of Polymer Science:Part A: Polymer Chemistry,Vol.43,6179-6222(2005) Summary of the Invention [Means for solving the problem]

[0008] Directed self-assembly (DSA) of diblock copolymers, such as polystyrene-b-polymethyl methacrylate (PS-b-PMMA) block copolymers, has been widely used as a next-generation lithographic patterning technique. Microphase separation of diblock copolymers has been used for feature size control in lithography. These diblock copolymers can produce thin-film morphologies with single and unidirectional feature sizes using appropriate underlayers or prepatterns for DSA. However, one problem is that the defect-free assembly process of block copolymers requires high thermal energy and long processing times. To address this issue, there is a need for novel diblock copolymers with better block segment mobility and less stringent annealing requirements, which will reduce the number of defects achieved through DSA for fabricating IC features with smaller sizes. [Brief explanation of the drawings]

[0009] [Figure 1] Representative example of a collection of novel diblock copolymers of styrenic and alkyl methacrylate monomers, where at least one of the blocks is multi-tethered with oligoflexible groups and therefore has a low Tg. [Figure 2] Representative example of the assembly of novel AB diblock copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA) improved by the inclusion of additional low Tg segments, such as those containing polyisoprene (PI). [Figure 3] Fingerprint pattern (FP) of a multi-tethered diblock copolymer (example 2, TAB) on the brush-underlying neutral copolymer 1. [Figure 4] 1 FOV SEM image of a multi-tethered diblock copolymer (Example 6, TAB5). The multi-tethered diblock exhibits improved grain size without defects. [Figure 5] 1 FOV SEM image of a standard CH diblock copolymer (Example 1a, AB1). This standard diblock copolymer exhibits numerous defects caused by regions of mixed morphology.

[0010] The defect-free assembly process of block copolymers requires high thermal energy and long times. This problem limits the application of directed self-assembly of block copolymers with large domain spacing and the use of triblock copolymers with double the molecular weight of diblock copolymers for multi-pitch applications in lithographic patterning. The present invention relates to the synthesis of two kinetically enhanced families of AB-type diblock copolymers.

[0011] In both approaches, the Tg of the block segments was lowered in order to enhance the annealing kinetics to reduce the annealing required to achieve defect-free assembly during DSA processing. In the first family, the AB diblock copolymers contain at least one block multi-tethered with oligoflexible tethered groups. In the second family, the AB diblock copolymers contain low Tg units, such as units derived from isoprene. g Repeating units and similar low T g A third block containing olefinic repeating units is included.

[0012] The first strategy, shown in FIG. 1, involves adding low T g We have developed a series of novel multi-tethered copolymer diblock copolymers with comonomers. Non-limiting examples include P(S1-co-S2)-bP(M1-co-M2), P(S1-co-S2)-b-PMMA, and PS-bP(M1-co-M2), which have the desired molecular weights and narrow molecular weight distributions (PDI<1.1) as follows:

[0013] P(S1-co-S2)-bP(M1-co-M2) is a block copolymer comprising a first block P(S1-co-S2) polymer block containing two different types of styrenic repeat units and a second polymer block P(M1-co-M2) containing two different types of methacrylate repeat units, where S1 is styrene, S2 is styrene substituted with an oligoflexible tethered group, M1 is methyl methacrylate, and M2 is methacrylate substituted with an oligoflexible tethered group.

[0014] P(S1-co-S2)-b-PM1 is a block copolymer comprising a first block P(S1-co-S2) polymer containing two different types of styrenic repeat units and a second polymer block PM1 containing a single type of styrenic repeat unit, where S1 is styrene, S2 is styrene substituted with an oligoflexible tethered group, and M1 is methyl methacrylate.

[0015] PS1-bP(M1-co-M2) is a block copolymer comprising a first polymer block PS1 containing a single type of styrenic repeat unit (S1) and a second polymer block P(M1-co-M2) containing two different types of alkyl methacrylates (M1 and M2), where S1 is styrene, M1 is methyl methacrylate, and M2 is a methacrylate substituted with an oligoflexible tethered group.

[0016] Another strategy (Figure 2) is to g The goal is to modify the styrenic / alkyl methacrylate AB type diblock copolymer to include an additional block segment having a low T of about -5°C to about -50°C, including repeating units derived from an olefin or diene, such as isoprene. g and also have a desired molecular weight with a narrow molecular weight distribution (PDI<1.1). A non-limiting example of this type of polymer is PS1-b-PI-b-PMMA below.

[0017] PS1-b-PI-b-PMMA is a block copolymer comprising a first polymer block PS1 containing a single type of styrene repeat unit (S1), a second polymer block (PI) containing isoprene repeat units, and a third block (PMMA) containing poly(methyl methacrylate) repeat units.

[0018] Both modified block copolymer families can be prepared using living anionic polymerization in the presence of an anionic initiator such as s-BuLi initiator.

[0019] More generally, these two types of polymers are the polymer families of the present invention represented by structures (I) and (III), respectively, shown below.

[0020] Polymers of the invention of structure (I) One aspect of the present invention is a block copolymer having the structure (I): The A segment is a non-polar block copolymer segment containing styrene repeating units, the B segment is a polar block copolymer segment containing repeating units derived from an alkyl 2-methylene alkanoate, a lactone, an oxirane, an oxetane, or a cyclic carbonate, L is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; E' is a C1-C12 alkyl terminal group, E'' is an end group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=O-alkyl), and an end group derived from alkyl 2-aryl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0021] Further, in this embodiment of the block copolymer of structure (1), the oligoflexible tethered groups are multi-tethered, and the oligoflexible tethered groups are selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups, and the oligoflexible tethered groups are multi-tethered in at least one of the A segment, the B segment, and L (where L is a linking moiety derived from 1,1-diarylethene), and the block copolymer has a polydispersity ranging from 1 to about 1.09 and an M of at least 40,000. n It has.

[0022] E'-ALB-E'' (I) Polymers of the invention of structure (III) A further aspect of the present invention is a block copolymer having structure (III): A1 is the T from about 50°C to about 100°C. g a styrenic block copolymer segment having: A2 is a T in the range of about -5°C to about -50°C. g wherein the block copolymer segment comprises repeat units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or from a mixture of at least two different olefins selected from this group; B1 is a T from about 50°C to about 100°C. g a polar block copolymer segment having the formula: L1 is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; E 3 is alkyl; E 4is a group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and the terminal group derived from alkyl 2-aryl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0023] Further, in this embodiment of the block copolymer of structure (III), it has a polydispersity ranging from 1 to about 1.09.

[0024] E 3 -A1-A2-L1-B1-E 4 (III) Another aspect of the present invention is a composition comprising an inventive block copolymer of structure (I) or an inventive block copolymer of structure (III) and a spin-casting solvent.

[0025] Another aspect of the invention is a method for using the composition in a self-assembly process and then pattern-transferring the self-assembled pattern into a substrate. DETAILED DESCRIPTION OF THE INVENTION

[0026] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive with respect to the invention as claimed. As used herein, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises" and other verb forms, such as "comprises," is not limiting. Furthermore, references to "elements" or "components" include both elements and components containing one unit and elements or components containing more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. As used herein, the conjunction "and" refers to any combination of the aforementioned elements, including the use of a single element.

[0027] L0 is the natural pitch of the aggregated block copolymer, which tends to be proportional to the size of the copolymer.

[0028] The term C1-C4 alkyl includes methyl and C2-C4 linear alkyl and C3-C4 branched alkyl moieties, such as 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). Similarly, the term "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.).

[0029] The term "C2-C5 alkylene" includes C2-C5 linear alkylene moieties (such as ethylene, propylene, etc.) and C3-C5 branched alkylene moieties (such as -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0030] Diblock and triblock copolymers of styrenic repeating units and repeating units derived from alkyl 2-methylene alkanoates, which are useful as components in the compositions according to the present invention, 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; Macromol. Rapid Commun. 2018, 39, 1800479; A. Deiter Shluter et al. Synthesis of Polymers, 2014, Volume 1, p. 315; Encyclopedia of Polymer Science and Technology, 2014, Vol. 7, p. 625).

[0031] 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 oligo(S-co-MMA). Similarly, the block copolymer poly(styrene-block-methyl methacrylate) is abbreviated as P(Sb-MMA), while the oligomer 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 abbreviation to refer to the random block copolymer element, 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 two blocks are random copolymers.

[0032] FOV is an abbreviation for "field of view" in top-down scanning electron microscope (SEM) images in this application. "L / S" is an abbreviation for "line and space" lithography features.

[0033] The term alkyl 2-methylenealkanoate (alkyl-O—(C═O)—C(alkyl)═CH2) refers to an alkyl ester of 2-methylenealkanoate, where the 2-methylenealkanoate may contain up to 11 carbon atoms, and the alkyl in the alkyl 2-methylenealkanoate may contain up to 8 carbon atoms and is selected from methyl, linear alkyl, branched alkyl, and cyclic alkyl. The following structure shows the general structure of such alkyl 2-methylenealkanoates, where Ralk a and Ralk b are independently selected from C1 to C8 alkyl groups and represent non-limiting examples of alkyl 2-methylene alkanoates within this range.

[0034] [ka] As used herein, the term styrenic, unless otherwise specified, generally includes repeat units derived from styrene derivatives, such as repeat units derived from styrene derivatives having the following structure:

[0035] [ka] The term 1,1-diarylethene, as used herein, unless otherwise indicated, includes a moiety derived from ethene having two substituents at one position that are aryl moieties, as shown below, where Aryl1 and Aryl2 are aryl substituents selected from phenyl or substituted phenyl, and where substituents on either or both Aryl1 and Aryl2 are present, these substituents are independently selected from C1-C5 alkyl, halide, C1-C5 alkyloxy, and oligoflexible tethered groups.

[0036] [ka] The term "end group derived from alkyl 2-aryl acrylate," described using the general structure (-CH2-CH(aryl)(C(=O))-O-alkyl), is more fully defined in the following general structure unless otherwise noted, where * indicates the point of attachment to the end of the block copolymer chain; Aryl3 is an aryl substituent selected from phenyl or substituted phenyl, and if any substituent is present, the substituent is independently selected from C1-C5 alkyl, halide, C1-C5 alkyloxy, and an oligoflexible tethered group; and further, alkyl3 is an unsubstituted C1-C5 alkyl or a C1-C5 alkyl substituted with an oligoflexible tethered group. This end group structure is illustratively formed when a 2-aryl acrylate alkyl ester reacts at the CH2 olefin moiety with a living anion at the end of the polymer chain to form a CH - It can be derivatized by forming an anion, which is then terminated by protonation.

[0037] [ka] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions thereof cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials cited herein conflicts with that herein, the definition herein shall control.

[0038] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be linear or branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties may be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1 to C20 carbons. For structural reasons, linear alkyls are understood to begin at C1, while branched and cyclic alkyls begin at C3 and polycyclic alkyls begin at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy and perfluoroalkyl, are understood to have the same carbon number range unless otherwise specified. Where a different alkyl group length is specified, the above definition of alkyl remains valid in that it encompasses all types of alkyl moieties, and the structural discussion above regarding the minimum carbon number of a given type of alkyl group still applies.

[0039] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (—O—) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkyloxy moieties may be substituted or unsubstituted as described below.

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

[0041] As used herein, the term lactone includes both monolactones (eg, caprolactone) and dilactones (eg, lactide).

[0042] Haloalkyl refers to a saturated linear, cyclic, or branched alkyl group, such as those described above, in which at least one of the hydrogens has been replaced by a halide selected from the group F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0043] Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which all hydrogens have been replaced with fluorine (eg, trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like).

[0044] The term oligoflexible tethered group, as used in describing various embodiments of the inventive polymers or compounds described herein, refers to a group of moieties that include oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups.

[0045] The term oligolinear alkylene tethered group in the various embodiments of the polymers or compounds of the invention described herein refers, in its broadest aspect, to a group having the following general structure: -X1-(CH2) a -CH3, where a is 6 to 19, and X1 is selected from a direct valence bond, a linear C1-C4 alkylene spacer, -O-, -CH2-O-, -O-(C=O)-, -C=OO-, C=O, -CH2-O-(C=O)-, -S-, -SO2-, and -SO-.

[0046] In one embodiment, X1 is a direct valence bond. In another embodiment, X1 is a linear C1-C4 alkylene spacer. In another embodiment, X1 is -O-. In yet another embodiment, it is -CH2-O-, and in yet another embodiment, X1 is -O-(C=O)-. In another embodiment, X1 is -C=OO-. In another embodiment, X1 is carbonyl (C=O). In another embodiment, X1 is -CH2-O-(C=O)-. In another embodiment, X1 is -S-. In another embodiment, X1 is -SO2-. In another embodiment, X1 is -SO-. More specific types of these groups are -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 (where a is 6 to 19). In a more specific embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 7 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 7 to 10. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 8 to 9. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 8. In another more specific embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 7 to 14. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 7 to 13. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a-CH3 has a equal to 8 to 13. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 13. In another more specific embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 7 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 8 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 9 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 10 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 11 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 12 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 13 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 13 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 14 to 19. In an even more preferred embodiment, -O-(CH2) a-CH3 or -CH2-O-(CH2) a -CH3 has a equal to 15 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 16 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 17 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 18 to 19. In an even more preferred embodiment, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 18. These linear alkylene tethered groups can be unsubstituted or substituted with C1 to C8 alkyl groups that form branch points. These linear alkylene tethered groups can be unsubstituted or substituted with C1 to C8 alkyl groups that form branch points.

[0047] The term oligoether tethered group in the various embodiments of the polymers or compounds of the invention described herein refers to a moiety having the following general structure: -O-[(CH) e -O-] e2 -(CH2) e3 -H, and -(CH2) e4 -O-[(CH2) e -O-] e2 -(CH2) e3 -H, where, independently, e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8. In another aspect of this embodiment, this is -O-(CH-CH-O) e2 -(CH2) e3 In one more particular aspect of this embodiment, it is -O-(CH2-CH2-O) e2In one more specific aspect of this embodiment, it is -CH2-O-(CH2-CH2-O)4-CH3; in yet another more specific embodiment, it is O-(CH2-CH2-O)4-CH3. In another more specific embodiment, it is -CH2-O-(CH2-CH2-O) e2 -(CH2) e3 In another more specific embodiment, it is —CH—O—(CH—CH—O) e2 In another more specific aspect of this embodiment, it is —CH—O—(CH—CH—O)—CH—, and in another more specific aspect of this embodiment, it is —CH—O—(CH—CH—O)—CH—. These oligoether tethered groups can be unsubstituted or substituted with C1-C8 alkyl groups that form branch points.

[0048] The term oligodialkylsiloxane tethered group, present in the various embodiments of the inventive polymers or compounds described herein, has the following general structure: -X-[Si(alkyl)-O] s In one more specific aspect of this embodiment, this refers to a group having -Si(alkyl)3, where s is 6 to 18, the alkyl portion is a C1-C8 alkyl, and X2 is a direct valence bond, or a C1-C8 linear alkylene spacer, or -O-. s In one more particular aspect of this embodiment, it is —Si(alkyl)3, which is —O—[Si(CH3)2—O] s In another more specific aspect of this embodiment, it is -CH2-O-[Si(alkyl)2-O] s In one more particular aspect of this embodiment, this is -Si(alkyl)3, which is -CH2-O-[Si(CH3)2-O] s -Si(CH3)3.

[0049] Polymers of the invention of structure (I) One aspect of the present invention is a block copolymer having the structure (I): The A segment is a non-polar block copolymer segment containing styrenic repeat units; L is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; the B segment is a polar block copolymer segment comprising repeating units derived from an alkyl 2-methylene alkanoate, repeating units derived from a lactone, repeating units derived from an oxirane, repeating units derived from an oxetane, or repeating units derived from a cyclic carbonate; E' is a C1-C12 alkyl terminal group; E'' is an end group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=O-alkyl), and an end group derived from alkyl 2-aryl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0050] Further, in this embodiment of the block copolymer of structure (1), the oligoflexible tethered groups are multi-tethered, and the oligoflexible tethered groups are selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups, and the oligoflexible tethered groups are multi-tethered in at least one of the A segment, the B segment, and L (where L is a linking moiety derived from 1,1-diarylethene), and the block copolymer has a polydispersity ranging from 1 to about 1.09 and an M of at least 40,000. n It has.

[0051] E'-ALB-E'' (I) In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is an oligolinear alkylene tethered group.

[0052] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group has the general structure -X1-(CH2) a An oligolinear alkylene tethered group having —CH3, where n is 6 to 19, and X1 is selected from a direct valence bond, a linear C1-C4 alkylene spacer, —O—, —CH2-O- -O-(C═O)—, —C═OO—, C═O, —CH2-O-(C═O)—, —S—, —SO2-, and —SO—.

[0053] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is an oligoether tethered group.

[0054] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is an oligoether tethered group having the formula: -O-[(CH) e -O-] e2 -(CH2) e3 -H, or -(CH2) e4 -O-[(CH2) e -O-] e2 -(CH2) e3 -H, wherein, independently, e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8.

[0055] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

[0056] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group has the formula -X2-[Si(alkyl)2-O] s An oligodialkylsiloxane tethered group having —Si(alkyl)3, where s is 6 to 18, the alkylene moiety is a C1-C8 alkyl, and X2 is a direct valence bond, or a C1-C8 linear alkylene spacer, or —O—.

[0057] In another embodiment of the block copolymer of structure (I) described herein, the polar block copolymer segment B comprises repeat units derived from lactones.

[0058] In another embodiment of the block copolymer of structure (I) described herein, the polar block copolymer segment B comprises repeat units derived from alkyl 2-methylene alkanoate.

[0059] In another embodiment of the block copolymer of structure (I) described herein, the polar block copolymer segment B has a Mw between about 20,000 and about 200,000, and the non-polar styrenic block copolymer segment A has a Mw between 20,000 and about 200,000.

[0060] In another embodiment of the block copolymers of structure (I) described herein, L is a direct valence bond.

[0061] In another embodiment of the block copolymer of structure (I) described herein, L is a linking group derived from 1,1-diarylethene.

[0062] In another embodiment of the block copolymer of structure (I) described herein, E'' is H.

[0063] In another embodiment of the block copolymer of structure (I) described herein, E'' is alkyl.

[0064] In another embodiment of the block copolymer of structure (I) described herein, E'' is carbonylalkyl (-C=O-alkyl).

[0065] In another embodiment of the block copolymer of structure (I) described herein, E'' is carbonyloxyalkyl (-C=OO-alkyl).

[0066] In another embodiment of the block copolymer of structure (I) described herein, E'' is an end group derived from alkyl 2-aryl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0067] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered groups are located on the A segment and are randomly located along this segment on some of its repeat units or are present on each of its repeat units.

[0068] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is located on the B segment and is randomly located along this segment on some of its repeat units or is present on each of its repeat units.

[0069] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is disposed on the linking group L when the linking group L is derived from a 1,1-diarylethene.

[0070] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is located on the A segment, the B segment, or (when L is derived from a 1,1 diarylethene) the linking group L, and is randomly located along the A or B segment on some of their respective repeat units or is present on each of their respective repeat units.

[0071] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered groups are located only on the A segment and are randomly located on some of its repeat units along this segment or are present on each of its repeat units.

[0072] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered groups are located only on the B segment and are randomly located on some of its repeat units along this segment or are present on each of its repeat units.

[0073] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is located only on the linking group L when L is derived from a 1,1-diarylethene.

[0074] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered groups are located only on the A and B segments and are randomly located along the A and B segments on some of their respective repeat units or are present on each of their respective repeat units.

[0075] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered groups are located only on both the A segment and the linking group L when the linking group L is derived from 1,1-diarylethene, and are randomly located along the A segment on some of its repeat units or are present on each of its repeat units.

[0076] In another embodiment of the block copolymer of structure (I) described herein, the oligoflexible tethered group is located only on the B segment and on the linking group L, when the linking group L is derived from 1,1-diarylethene, and is located randomly along the B segment on some of its repeat units or is present on each of its repeat units.

[0077] In another embodiment of the block copolymer of structure (I) described herein, in which the oligoflexible tethered groups are present in either the A segment or the B segment, or both, these oligoflexible tethered groups are present randomly on some of the repeat units along their respective segments.

[0078] In another embodiment of the block copolymers of structure (I) described herein, where the oligoflexible tethered groups are present in either the A segment or the B segment, or both, these oligoflexible tethered groups are present in all of their respective repeat units.

[0079] In another embodiment of the block copolymer of structure (I) described herein, the copolymer has structure (II): a styrenic block consisting of randomly copolymerized styrenic repeat units of structures (STa) and (STb), wherein R1 and R2 are independently selected from H or C1-C4 alkyl, and R5 and R6 are independently selected from H, C1-C4 alkyl, and an oligoflexible tethered group, wherein the oligoflexible tethered group is Oligolinear alkylene tethered groups, oligoether tethered groups, and Oligodialkylsiloxane tethered groups, The styrenic block is selected from A linking moiety of structure (L1), wherein R7 and R8 are independently selected from H, C1-C4 alkyl, and are multi-tethered with oligoflexible tethered groups, the oligoflexible tethered groups being: Oligolinear alkylene tethered groups, oligoether tethered groups, and Oligodialkylsiloxane tethered groups, the linking moiety being selected from a 2-methylenealkanoate derived block, the 2-methylenealkanoate derived block consisting of randomly copolymerized 2-methylenealkanoate repeat units of structures (MEAa) and (MEAb), in which R3 and R4 are independently selected from C1-C4 alkyl; R9 and R 10 are individually selected from C1 to C4 alkyl, and the oligoflexible tethered group is multi-tethered, and the oligoflexible tethered group is Oligolinear alkylene tethered groups, oligoether tethered groups, and Oligodialkylsiloxane tethered groups, a block derived from said 2-methylene alkanoate selected from Including, E' is a C1-C12 alkyl terminal group; E″ is selected from H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═OO-alkyl), and an end group derived from alkyl 2-arylacrylate (—CH—CH(aryl)(C(═O))—O-alkyl); x and x' respectively represent the number of repeat units of structures (STa) and (STb) in the styrenic block having Mw from about 20,000 to about 200,000, which in the non-polar block segment is represented by the brackets designated n; y and y' respectively represent the number of repeat units of the structures (MEAa) and (MEAb) in the block derived from the 2-methylenealkanoate having a Mw of from about 20,000 to about 200,000, and in the polar block segment, this is represented by the bracket designated m, and further include R5, R6, R7, R8, R9 or R 10 At least one of the groups is selected from the oligoflexible tethered groups.

[0080] [ka] In another embodiment of the block copolymer of structure (II) described herein, R5 is an oligoflexible tethered group, R6 is H or C1-C4 alkyl, R7 and R8 are independently selected from H and C1-C4 alkyl, and R9 and R 10 is independently selected from C1-C4 alkyl.

[0081] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are multi-tethered with oligoflexible tethered groups, R7 and R8 are independently selected from H and C1-C4 alkyl, and R9 and R 10 is independently selected from C1-C4 alkyl.

[0082] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are independently selected from H and C1-C4 alkyl, at least one of R8 and R7 is an oligoflexible tethered group, and R9 and R 10 is independently selected from C1-C4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligoflexible tethered groups.

[0083] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are independently selected from H and C1-C4 alkyl, R8 and R7 are independently selected from H and C1-C4 alkyl, and R9 and R 10 At least one of the groups is an oligoflexible tethered group.

[0084] In another embodiment of the block copolymer of structure (II) described herein, R and R 10 are both oligoflexible tethered groups.

[0085] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are independently selected from H and C1-C4 alkyl, at least one of R8 and R7 is an oligoflexible tethered group, and R9 and R 10 are independently selected from C1-C4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligoflexible tethered groups. In another aspect of this embodiment, at least one of R5 and R6, and R9 and R 10 In another aspect of this embodiment, at least one of R5 and R6, and R9 and R 10 Both of these are flexible tethered groups.

[0086] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are independently selected from H and C1-C4 alkyl, at least one of R8 and R7 is an oligoflexible tethered group, and R9 and R 10 is independently selected from C1-C4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligoflexible tethered groups.

[0087] In another embodiment of the block copolymer of structure (II) described herein, at least one of R5 and R6, at least one of R7 and R8, and at least one of R9 and R 10 In another aspect of this embodiment, at least one of R, R, R, R, R, and R is a flexible tethered group. 10 is an oligoflexible tethered group.

[0088] In any embodiment of the block copolymer of structure (II) described herein, where R5 and R6 are independently selected from H and C1-C4 alkyl, at least one of R8 and R7 is an oligoflexible tethered group, and R9 and R 10are independently selected from C1-C4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligoflexible tethered groups, R1 and R2 are H, and R3 and R4 are C1-C3 alkyl. In another aspect of this embodiment, R3 and R4 are C1-C2 alkyl. In another aspect of this embodiment, R3 and R4 are methyl.

[0089] One aspect of the present invention is a block copolymer having structure (III): A1 is the T from about 50°C to about 100°C. g a styrenic block copolymer segment having: A2 is a T in the range of about -5°C to about -50°C. g wherein the block copolymer segment comprises repeat units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or from a mixture of at least two different olefins selected from this group; B1 is a T from about 50°C to about 100°C. g a polar block copolymer segment having the formula: L1 is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; E 3 is alkyl; E 4 is a group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and an end group derived from alkyl 2-arylacrylate (-CH-CH(aryl)(C(=O))-O-alkyl), and The block copolymer has a polydispersity of from about 1 to about 1.09.

[0090] E3 -A1-A2-L1-B1-E 4 (III) In another embodiment of the block copolymer of structure (III) described herein, A2 has repeat units derived from an alkene.

[0091] In another embodiment of the block copolymer of structure (III) described herein, A2 has repeat units derived from an alkadiene. In another aspect thereof, the alkadiene is a conjugated diene.

[0092] In any of the foregoing embodiments of the block copolymer of structure (III) described herein, A2 comprises a mixture of at least two different repeat units having structures (IIIa), (IIIb), (IIIc), and (IIId) derived from alkadiene, where R d , R d1 , R d3 , R d4 , R e , R e1 , R e3 , and R e4 are individually selected from the group consisting of H and C1-C8 alkyl, and further, the total mole percent of olefinic repeat units in the block copolymer is from about 3 mole percent to about 50 mole percent. In another aspect of this embodiment, R d , R d1 , R d3 , and R d4 are the same and are selected from H or C1-C8 alkyl, and R e , R e1 , R e3 , and R e4 is selected from H or C1-C8 alkyl.

[0093] [ka] In another embodiment of the block copolymer of structure (III) described herein, A2 comprises repeat units derived from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isoprene, 3-methylenepent-1-ene, 3-methylenehex-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepent-1-ene, 1,3-butadiene, ethylidenenorbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinylnorbornene (2-vinylbicyclo[2.2.1]hept-2-ene), or chloroprene (2-chlorobuta-1,3-diene), or a mixture comprising at least two thereof.

[0094] In another embodiment of the block copolymer of structure (III) described herein, the repeat units in A2 are derived from an alkadiene that is a conjugated diene.

[0095] In another embodiment of the block copolymer of structure (III) described herein, the repeating units in A2 are derived from an alkatrienes.

[0096] In another embodiment of the block copolymers of structure (III) described herein, A2 has repeat units derived from a mixture of at least two different olefins selected from the group consisting of alkenes, alkadienes, and alkatrienes.

[0097] In any of the block copolymer embodiments of structure (III) described herein, A2 further comprises a styrenic repeat unit.

[0098] In any of the embodiments of the block copolymer of structure (III) described herein, the polar block copolymer segment B1 comprises repeat units derived from lactones.

[0099] In any of the embodiments of the block copolymer of structure (III) described herein, the polar block copolymer segment B1 comprises repeat units derived from alkyl 2-methylene alkanoate.

[0100] In any of the embodiments of the block copolymer of structure (III) described herein, the polar block copolymer segment B1 has a Mw between about 20,000 and about 200,000, and the non-polar styrenic block segment has a Mw between 20,000 and about 200,000.

[0101] In one embodiment of the block copolymer of structure (III) described herein, L1 is a direct valence bond.

[0102] In another embodiment of the block copolymer of structure (III) described herein, L1 is a linking group derived from 1,1-diarylethene.

[0103] In another embodiment of the block copolymer of structure (III) described herein, E 4 is H or alkyl.

[0104] In another embodiment of the block copolymer of structure (III) described herein, E 4 is a group derived from alkylmethyl-2-arylacrylate.

[0105] In another embodiment of the block copolymer of structure (III) described herein, E 3 is alkyl.

[0106] In one embodiment of the block copolymer of structure (III), it has the more specific structure (IIIe): a styrenic block, the styrenic block consisting of randomly copolymerized styrenic repeat units of structures (STc) and (STd), wherein R 1a and R 2aare independently selected from H or C1-C4 alkyl, and R 5a and R 6a are independently selected from H or C1-C4 alkyl, a styrenic block, The linking portion of structure (L1) is R 7a and R 8a are independently selected from H and C1-C4 alkyl, Including, E' is a C1-C12 alkyl terminal group; E″ is selected from H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═OO-alkyl), and an end group derived from alkyl 2-arylacrylate (—CH—CH(aryl)(C(═O))—O-alkyl); X and x' respectively represent the number of repeat units of structures (STc) and (STd) in the styrenic block having Mw of from about 20,000 to about 200,000 in the nonpolar block segment represented by the brackets designated n; y and y' respectively represent the number of repeat units of the structures (MEAc) and (MEAd) in the block derived from said 2-methylenealkanoate having Mw of from about 20,000 to about 200,000 in the polar block segment represented by the brackets designated by m, where R 3a , R 4a , R 9a and R 10a are individually selected from C1-C4 alkyl; A2 is a T in the range of about -5°C to about -50°C. g and comprising repeat units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or from a mixture of at least two different olefins selected from this group.

[0107] [ka] In one embodiment of the block copolymer of structure (IIIe), R 1a , R 2a , R 5a , R 6a is H.

[0108] In one embodiment of the block copolymer of structure (IIIe), R 7a and R 8a is H.

[0109] In another embodiment of the block copolymer of structure (IIIe), R 3a , R 4a , R 9a and R 10a is CH3.

[0110] In another embodiment of the block copolymer of structure (IIIe), A2 comprises a mixture of at least two different repeat units having structures (IIIa), (IIIb), (IIIc), and (IIId), where R d , R d1 , R d3 , R d4 , R e , R e1 , R e3 , and R e4 are individually selected from the group consisting of H and C1-C8 alkyl, and further, the total mole percent of olefinic repeat units in said block copolymer ranges from about 3 mole percent to about 50 mole percent.

[0111] In one embodiment of the block copolymer of structure (IIIe), R d , R d1 , R d3 and R d4 are the same and are selected from H or C1-C8 alkyl, and R e , R e1 , R e3 , and R e4 is selected from H or C1-C8 alkyl.

[0112] [ka] In one embodiment of the block copolymer of structure (IIIe) described herein, A2 is a block copolymer segment having repeat units derived from isoprene or butadiene.

[0113] In one embodiment of the block copolymer of structure (IIIe) described herein, the non-polar block copolymer segment A1 has a Mw between about 20,000 and about 200,000.

[0114] In one embodiment of the block copolymer of structure (IIIe) described herein, E' is a C3-C7 alkyl.

[0115] In one embodiment of the block copolymer of structure (IIIe) described herein, E'' is H.

[0116] Another aspect of the present invention is a composition comprising any of the block copolymers of structure (I) (or substructures thereof) described herein and a spin-cast organic solvent.

[0117] In one aspect of the composition comprising the block copolymer of structure (I), it additionally comprises yet another block copolymer.

[0118] In one aspect of the composition comprising the block copolymer of structure (I), it additionally comprises a homopolymer.

[0119] Another aspect of the present invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof) and a solvent.

[0120] Another aspect of the present invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof) and further comprising other block copolymers.

[0121] Another aspect of the present invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof) and also comprising a homopolymer.

[0122] In the compositions of the present invention described herein comprising a copolymer of Structure (I) or Structure (III) (or a more specific substructure thereof described herein), the spin-casting solvent is, in one embodiment, selected from organic spin-casting solvents that are suitable for dissolving the compositions of the present invention described above, including glycol ether derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids such as diethyl oxylate and diethyl malonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketone alcohol derivatives such as acetol or diacetone alcohol; ketals or acetals such as 1,3 dioxalane and diethoxypropane; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0123] Additionally, the compositions of the present invention can further comprise an additive selected from the group consisting of surfactants, inorganic-containing polymers; additives including small molecules, inorganic-containing molecules, surfactants, photoacid generators, thermal acid generators, quenchers, curing agents, crosslinkers, chain extenders, and the like; and combinations comprising at least one of the foregoing, wherein one or more of the additional components and / or additives co-assemble with the block copolymer to form a block copolymer assembly. Another aspect of the present invention is a method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of block copolymer having periodicity L, comprising the steps of: a) forming a coating layer of a block copolymer on the unpatterned substrate from any of the compositions comprising a block copolymer of structure (I) described herein; and b) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method includes:

[0124] Another aspect of the present invention is a method for vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a periodicity L, wherein the topographical height of the pattern on the substrate is at least 0.7 times L, and aligning the domains with the pattern, the method comprising the steps of: a1) forming a coating layer of a block copolymer on the first topographic substrate from any of the compositions comprising the block copolymer of structure (1) described herein, wherein the average thickness of the coating layer of the block copolymer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; and b1) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within recessed regions; The method includes:

[0125] Another aspect of the present invention is a method of vertically orienting first and second block copolymer domains with a periodicity L on a second patterned substrate having a topographical pattern, wherein said topographical pattern has a topographical height greater than 0.7 times L and a pitch P1, where P1 is a non-zero positive integer multiplied by L, and aligning these domains with said pattern, comprising the steps of: a2) forming a coating layer of a block copolymer on the second patterned substrate from any of the compositions comprising a block copolymer of structure (I) described herein, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b2) annealing the block copolymer layer to produce vertically oriented, positive integer, non-zero first and second block copolymer domains on the second patterned substrate and align them with respect to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern; The method includes:

[0126] Another aspect of the present invention is a method for perpendicularly orienting first and second block copolymer domains on a substrate having a surface chemical pre-pattern with a pitch P2, where the pitch P2 is a non-zero positive integer multiplied by L0, and aligning these domains, comprising the steps of: a3) forming a coating layer of a block copolymer from any of the compositions comprising a block copolymer of structure (I) described herein on said substrate having a surface chemical pre-pattern; and b3) annealing the block copolymer layer to produce vertically oriented first and second block copolymer domains aligned with the substrate having a surface chemical prepattern with pitch P2; The method includes:

[0127] Another aspect of the present invention is a method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of block copolymer having periodicity L, comprising the steps of: a4) forming a coating layer of a block copolymer on the unpatterned substrate from any of the compositions comprising a block copolymer of structure (III) described herein; and b4) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method includes:

[0128] Another aspect of the present invention is a method for vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a periodicity L, wherein the topographical height of the pattern on the substrate is at least 0.7 times L, and aligning the domains with the pattern, the method comprising the steps of: a5) forming a block copolymer coating layer on the first topographic substrate from any of the compositions comprising a block copolymer of structure (III) described herein, wherein the average thickness of the block copolymer coating layer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; and b5) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within the recessed regions; The method includes:

[0129] Another aspect of the present invention is a method of vertically orienting first and second block copolymer domains with a periodicity L on a second patterned substrate having a topographical pattern, wherein said topographical pattern has a topographical height greater than 0.7 times L and a pitch P1, where P1 is a non-zero positive integer multiplied by L, and aligning these domains with said pattern, comprising the steps of: a6) forming a coating layer of a block copolymer on the second patterned substrate from any of the compositions comprising a block copolymer of structure (III) described herein, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b6) annealing the block copolymer layer to produce vertically oriented non-zero positive integer first and second block copolymer domains on the second patterned substrate and aligning them with respect to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern; The method includes:

[0130] Another aspect of the present invention is a method for perpendicularly orienting first and second block copolymer domains on a substrate having a surface chemical pre-pattern with a pitch P2, where the pitch P2 is a non-zero positive integer multiplied by L0, and aligning these domains, comprising the steps of: a7) forming a coating layer of a block copolymer from any of the compositions comprising a block copolymer of structure (III) described herein on said substrate having a surface chemical pre-pattern; and b7) annealing the block copolymer layer to produce vertically oriented first and second block copolymer domains aligned with the substrate having a surface chemical prepattern with pitch P2; The method includes: [Example]

[0131] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich (3050 Spruce Street, St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g., David Uhrig and Jimmy Mays, "Techniques in High-Vacuum Anionic Polymerization," Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0132] Phenyl acrylate derivatives were synthesized by esterifying acryloyl chloride with the corresponding hydroxyl compounds under basic conditions, and DPE derivatives were synthesized by alkoxylating DPE-(m)-CHBr (1-(bromomethyl)-3-(1-phenylvinyl)benzene) with the corresponding hydroxyl compounds under basic conditions.

[0133] All synthesis experiments were carried out in a N2 atmosphere. Lithography experiments were carried out as described herein. The molecular weight of the copolymer was measured using gel permeation chromatography. 3 Å, 10 5 Å and 10 6 Åμ—Gel permeation chromatography equipped with an ultrastyragel column.

[0134] 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).

[0135] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembled film block copolymers of methyl methacrylate and styrene.

[0136] Unless otherwise stated, molecular weight measurements (also known as Mn polydispersity) are given at 100 Å, 500 Å, 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.

[0137] DSC measurements of glass transition temperature were performed using a TA Instruments DSC Q1000 under nitrogen at a heating rate of 10°C / min. g ) was measured in the first heating scan from 0 to 300° C. The midpoint of the endothermic transition was considered.

[0138] 1 1 H NMR spectra were recorded using a Bruker Advanced III 400 MHz spectrometer.

[0139] The molecular weight of the copolymer was determined using gel permeation chromatography. Chemicals were obtained from Sigma-Aldrich Corporation unless otherwise stated.

[0140] These newly developed improved diblock copolymers were tested for fingerprint morphology on a neutral underlayer brushed substrate on SiOx. To evaluate the novel diblock copolymers, we also developed a thick-film fingerprint network defect analysis method. In this analysis, the block copolymers were coated with 2 and 3×L0 and partially dry-etched (using oxygen plasma) to identify and count network defects throughout the film. These results were compared with conventional diblock copolymers. The improved multitethered diblock copolymers exhibited significantly fewer defects and faster dynamic properties. The synthesis of these polymers was accomplished via living anionic copolymerization. The described diblock copolymers exhibit narrow molecular weight distributions (Mw / Mn<1.1) and work effectively with conventional underlayers suitable for PS-b-PMMA DSA.

[0141] Bottom layer neutral copolymer 1: Copolymers of styrene, methyl methacrylate, and 4-vinylbenzylcyclobutene synthesized using AIBN A 2000 ml flask was set up with a condenser, temperature controller, heating mantle, and mechanical stirrer. 87.0 grams (0.84 moles) of styrene (S), 139.8 grams (1.40 moles) of methyl methacrylate (MMA), 72.4 grams (0.56 moles) of 4-vinylbenzocyclobutene (VBCB), 1.83 grams (0.011 moles) of azobisisobutyronitrile (AIBN) initiator, and 600 grams of anisole were added to the flask. The mechanical stirrer was turned on and set to approximately 120 rpm. The reaction solution was then degassed by vigorously bubbling nitrogen through the solution at room temperature for approximately 30 minutes. After 30 minutes of degassing, 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 mantle was turned off, and the reaction solution was allowed to cool to approximately 40°C. The reaction mixture was then poured into 12 L of isopropanol with 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. Approximately 170 grams of polymer was obtained. The dried polymer was dissolved in 600 grams of THF and then filtered through a 0.2 μm nylon filter. The filtered solution was then precipitated again in a stirred solution of 12 L of methanol, and the precipitated polymer was collected and dried under vacuum at 40°C as before. In this way, 150 grams (50% yield) of polymer was obtained after drying. The polymer had a Mw of approximately 38kJ and a polydispersity index (PDI) of 1.5.

[0142] Reference Block Copolymer Synthesis Example 1: Synthesis of PS-b-PMMA PS-b-PMMA was synthesized using the same procedure as in Example 2. The amount of initiator and monomer were varied to achieve the desired Mn and composition of the PS and PMMA blocks. Briefly, 20 g (192 mmol) of styrene was polymerized using 0.31 mL (1.4 M solution) of sec-butyllithium. Then, 0.09 g (0.50 mmol) 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 center had been converted to a delocalized DPE-adducted carbanion. After 2 min of stirring, a small aliquot (2 mL) of the reaction mixture was taken for PS block molecular weight analysis. Methyl methacrylate (22.85 g, 230 mmol) was then 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 (5 times the volume of the polymer solution) containing 10% water, filtration, and drying under vacuum at 55°C for 12 hours to give 40 g of P(Sb-MMA) (94% yield) consisting of 46.9 mol% polystyrene blocks and 53.1 mol% polymethyl methacrylate blocks. The molecular weight of the diblock copolymer obtained by GPC was M n =92K, PDI=1.02.

[0143] Reference Block Copolymer Synthesis Example 1a Synthesis of CH(PS-b-PMMA) The same procedure as in Example 1 was used, except that the polystyrene block was 69 mole % and the polymethyl methacrylate block was 31 mole %. The molecular weight of the diblock polymer obtained by GPC was M n =66.92K, PDI=1.01.

[0144] Synthesis of novel improved AB diblock copolymers The diblock copolymers described are unique and did not require the conformation of an underlayer for perpendicular alignment. These are novel dynamically enhanced diblock copolymers compared to conventional diblock copolymers.

[0145] Synthesis example 2 TAB-1 (line and space) This system demonstrates the synthesis of P(S-co-CS)-bP(MMA-co-CMA) with low Tg octylstyrene copolymerized in the PS block and hexyl methacrylate copolymerized in the PMMA block (TAB): Styrene, octylstyrene, methyl methacrylate, and hexyl methacrylate monomers were distilled in the presence of a dehydrating agent into calibrated ampoules and stored under N2. The liquid was transferred into the reactor under N2 via the ampule or using a stainless steel cannula. 500 mL of anhydrous tetrahydrofuran and 0.35 g of LiCl were added to a dry 1 L round-bottom reactor equipped with a side arm for connecting the ampule, a magnetic stir bar, and a nitrogen / vacuum three-way septum adapter. The temperature of the reactor was reduced to -78 °C using a dry ice-acetone bath. After titration of impurities, 3.6 mL (0.103 M solution) of s-BuLi as initiator was then added to the reactor. A mixture of 3.3 g (0.0152 mol) of n-octylstyrene and 14.23 g (0.137 mol) of styrene was then added from the ampule to the reactor with high-speed stirring. The reaction solution changed color to orange-red, and the reaction was continued for 30 minutes. Then, 0.08 g (0.00044 mol) of 1,1'-diphenylethylene was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark brick red color, indicating that the styryl potassium active center had been converted to a styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for P(S-co-C8S)-DPE block molecular weight analysis. A mixture of methyl methacrylate (14.8 g, 0.148 mol) and hexyl methacrylate (2.80 g, 0.0165 mol) was then added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA and C6MA. The reaction mixture was then quenched with 1 mL of degassed methanol. The block copolymer was recovered by precipitation into excess isopropanol (5 times the volume of the polymer solution) containing 10% water, filtration, and drying under vacuum at 70°C for 12 hours to give 30 g of P(S-co-C8S)-bP(MMA-co-C6MA) (95% yield). 3 Å, 10 5 Å and 10 6Gel permeation chromatography with an Åμ-Ultrastyragel column demonstrated that the first P(S-co-CS)-DPE block exhibited a M α -α β ... n (GPC) = 46,000 g / mol and M w / M n The diblock copolymer molecular weight obtained from GPC was M = 1.03. n,P(S-co-C8S)-b-PS-b-P(MMA-co-C6MA) = 83,000 g / mol, and M w / M n =1.07.

[0146] Table 1 compares the Tg characteristics of standard PS-b-PMMA (Example 1) with the Tg characteristics of the multi-tethered synthetic example 2, TAB-1.

[0147] Other novel multitethered polymers were synthesized in a similar manner, and their properties are summarized in Table 2.

[0148] Synthetic examples TAB1, TAB2, TAB3, and TAB4 were prepared in the same manner as TAB, except that the MW was changed to obtain different L0 values, making these samples suitable for use in line and space (L / S) applications.

[0149] TAB5 The BCP for the contact hole in Example 6 was synthesized using the same procedure as Example TAB (Example 2), except that the following variables were changed to vary the PS mol% and MW characteristics to obtain a multi-tethered block copolymer suitable for use in C-H hole self-assembly:

[0150] Lower layer polymer example 1: Synthesis of random crosslinkable copolymers: Copolymers of styrene, methyl methacrylate, and 4-vinylbenzylcyclobutene synthesized using AIBN A 2000 ml flask was set up with a condenser, temperature controller, heating mantle, and mechanical stirrer. 87.0 grams (0.84 moles) of styrene (S), 139.8 grams (1.40 moles) of methyl methacrylate (MMA), 72.4 grams (0.56 moles) of 4-vinylbenzocyclobutene (VBCB), 1.83 grams (0.011 moles) of azobisisobutyronitrile (AIBN) initiator, and 600 grams of anisole were added to the flask. The mechanical stirrer was turned on and set to approximately 120 rpm. The reaction solution was then degassed by vigorously bubbling nitrogen through the solution at room temperature for approximately 30 minutes. After 30 minutes of degassing, 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 mantle was turned off, and the reaction solution was allowed to cool to approximately 40°C. The reaction mixture was then poured into 12 L of isopropanol with 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. Approximately 170 grams of polymer was obtained. The dried polymer was dissolved in 600 grams of THF and then filtered through a 0.2 μm nylon filter. The filtered solution was then precipitated again in a stirred solution of 12 L of methanol, and the precipitated polymer was collected and dried under vacuum at 40°C as before. In this way, 150 grams (50% yield) of polymer was obtained after drying. The polymer had a Mw of approximately 38kJ and a polydispersity index (PDI) of 1.5.

[0151] Self-assembly of block copolymers (BCP) based on Examples 1 and 2 (Table 1) The polymer of Underlayer Polymer Example 1 was dissolved in PGMEA to prepare a 0.33 wt % solution. This solution was filtered using a 0.02 μm PTFE filter, and then SiO xThe SiOx wafers were coated with a crosslinked neutral layer (8 nm thick) by spin-coating at 1500 rpm onto wafers and subsequently baking each wafer in air at 250 °C for 2 minutes. The wafers were then coated with a 1.4 wt % solution of the TAB polymers, Reference Polymer Example 1 (PS-b-PMMA) and the multi-tethered diblock copolymer (Example 2), in PGMEA, filtered through 0.02 μm PTFE. Both polymers were spin-coated at 1500 rpm, then individually soft-baked at 110 °C for 1 minute and then annealed at 250 °C under N2 for 1 hour. Both materials formed self-assembled patterns containing nanophase-separated lamellae arrays perpendicular to the substrate after annealing the baked films. The arrays contained etchable blocks derived from methyl methacrylate, making them suitable for pattern-transfer etching of line-and-space patterns into substrates. However, the membrane coated with the multi-tethered diblock copolymer (Example 2) was not as good as the conventional diblock copolymer of styrene and methyl methacrylate (PS-b-PMMA) (M n = 92K, PDI = 1.02) (Example 1), it showed a vertical lamellar morphology with a significantly lower number of network defects.

[0152] These novel diblock copolymers exhibited significant Tg reductions in both the segmental Tg and overall Tg (Table 2)-less networks, which were observed along with larger grain sizes, as shown in Figure 3, which shows a 1 FOV SEM image obtained using the following processing: coating a solution of the underlayer neutral copolymer 1 and baking at 250 °C / 1 h (N); AZ® EBR 70 / 30, 2 min, spin-drying, 110 °C / 1 min, FT = 45 nm. The multi-tethered diblock copolymers exhibit improved grain size.

[0153] Processing example 2: To fabricate the film of Example 6 (TAB5), a multi-tethered block copolymer designed for contact hole (CH) self-assembly, most of the processing conditions described in Processing Example 1 were used. The processing conditions were slightly modified as follows: the block copolymer was baked at 260°C for 15 minutes (N), then cleaned with AZ® EBR 70 / 30, spin-dried for 2 minutes, and then baked at 110°C for 1 minute. In this example, a film thickness (FT) of 47 nm was obtained. Figure 4 shows the annealed film formed. The multi-tethered diblock exhibits improved contact hole assembly. In general, with PS-b-PMMA block copolymers, good C / H assembly is achieved at low T g This is achieved when an additive is added. The multi-tethered diblock copolymer of the present invention exhibited good C / H assembly even without additives, suggesting a significant dynamic enhancement. In contrast, as shown in Figure 5, the conventional diblock (i.e., diblock copolymer of styrene and methyl methacrylate (Example 1) (PS-b-PMMA) (M n = 66.92 K, PDI = 1.01) (Example 1a)) was coated and processed in the same manner as the film of Example 6, as described above, and the resulting 34.2 nm contact holes showed large area defects caused by the mixed morphology.

[0154] Yet another advantage of the disclosed novel modified AB diblock copolymer (Example 2) is that it does not require changes to the underlayer and pinning chemistries currently used in DSA processing for unmodified PS-b-PMMA DSA.

[0155] [Table 1]

[0156] [Table 2]

Claims

1. A block copolymer having structure (I): The A segment is a non-polar block copolymer segment containing styrenic repeat units; L is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; the B segment is a polar block copolymer segment comprising repeating units derived from an alkyl 2-methylene alkanoate, repeating units derived from a lactone, repeating units derived from an oxirane, repeating units derived from an oxetane, or repeating units derived from a cyclic carbonate; E' is a C1-C12 alkyl terminal group; E″ is selected from H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═O-O-alkyl), and terminal groups derived from alkyl 2-arylacrylate (—CH ２ an end group selected from —CH(aryl)(C(═O))—O-alkyl), and further The block copolymer of structure (1) is multi-tethered with oligoflexible tethered groups selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups, which are multi-tethered in at least one of the A segment, the B segment, and L (where L is a linking moiety derived from 1,1-diarylethene), and has a polydispersity ranging from 1 to about 1.09 and an M of at least 40,000. ｎ having The block copolymer. E'-A-L-B-E'' (I)

2. The block copolymer of claim 1 , wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

3. The oligoflexible tethered group has the general structure -X1-(CH ２ ) ａ -CH ３ where n is from 6 to 19, and X1 is a direct valence bond, a linear C1-C4 alkylene spacer, —O—, —CH ２ -O- -O-(C=O)-, -C=O-O-, C=O, -CH ２ -O-(C=O)-, -S-, -SO ２ 3. The block copolymer according to claim 1, wherein the aryl group is selected from -, -, -SO-, and -SO-.

4. The block copolymer of claim 1 , wherein the oligoflexible tethered group is an oligoether tethered group.

5. The oligoflexible tethered group has the formula —O—[(CH ２ ) ｅ -O-] ｅ２ - (CH ２ ) ｅ３ -H or -(CH ２ ) ｅ４ -O-[(CH ２ ) ｅ -O-] ｅ２ - (CH ２ ) ｅ３ 5. The block copolymer of claim 1, wherein the oligoether tethered group has a —H, wherein, independently, e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8.

6. The block copolymer of claim 1 , wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

7. The oligoflexible tethered group has the formula —X2-[Si(alkyl) ２ -O] ｓ -Si(alkyl) ３ 10. The composition of claim 1 or 6, wherein the oligodialkylsiloxane tethered group has the formula: wherein s is 6 to 18, the alkyl moiety is a C1-C8 alkyl, and X2 is a direct valence bond, or a C1-C8 linear alkylene spacer, or -O-.

8. 8. The block copolymer according to claim 1, wherein the polar block copolymer segment B comprises repeating units derived from a lactone.

9. 8. The block copolymer of claim 1, wherein the polar block copolymer segment B comprises repeat units derived from alkyl 2-methylene alkanoate.

10. 10. The block copolymer of claim 1, wherein the polar block copolymer segment B has a Mw between about 20,000 and about 200,000, and the non-polar styrenic block copolymer segment A has a Mw between 20,000 and about 200,000.

11. 11. The block copolymer of claim 1, wherein L is a direct valence bond.

12. 11. The block copolymer according to claim 1, wherein L is a linking group derived from 1,1-diarylethene.

13. The block copolymer of any one of claims 1 to 12, wherein E'' is H.

14. The block copolymer of any one of claims 1 to 12, wherein E'' is alkyl.

15. The block copolymer of any one of claims 1 to 12, wherein E'' is carbonyl alkyl (-C=O-alkyl).

16. The block copolymer of any one of claims 1 to 12, wherein E'' is carbonyloxyalkyl (-C=O-O-alkyl).

17. E″ is a terminal group (—CH ) derived from alkyl 2-aryl acrylate. ２ 13. The block copolymer of claim 1, wherein the group is —CH(aryl)(C(═O))—O-alkyl).

18. 18. The block copolymer of any one of claims 1 to 17, wherein the oligoflexible tethered groups are disposed on the A segment and randomly disposed along this segment on some of its repeat units or present on each of its repeat units.

19. 19. The block copolymer of any one of claims 1 to 18, wherein the oligoflexible tethered groups are located on the B segment and randomly located on some of its repeat units along this segment or present on each of its repeat units.

20. 20. The block copolymer of claim 1, wherein the oligoflexible tethered group is disposed on the linking group L when the linking group L is derived from a 1,1-diarylethene.

21. 21. The block copolymer of any one of claims 1 to 20, wherein the oligoflexible tethered groups are disposed on the A segment, the B segment, and, when L is derived from 1,1-diarylethene, the linking group L, and are randomly disposed on some of their respective repeat units along the A segment or B segment, or are present on each of their respective repeat units.

22. 19. The block copolymer of any one of claims 1 to 18, wherein the oligoflexible tethered groups are located only on the A segment and randomly located on some of its repeat units along this segment or present on each of its repeat units.

23. 20. The block copolymer of any one of claims 1 to 17 and 19, wherein the oligoflexible tethered groups are located only on the B segment and are randomly located on some of its repeat units along this segment or are present on each of its repeat units.

24. 21. The block copolymer of any one of claims 1 to 17 and 20, wherein the oligoflexible tethered group is located only on the linking group L when the linking group L is derived from a 1,1-diarylethene.

25. 20. The block copolymer of any one of claims 1 to 19, wherein the oligoflexible tethered groups are located only on the A and B segments and are randomly located along the A and B segments on some of their respective repeat units or are present on each of their respective repeat units.

26. 21. The block copolymer of any one of claims 1 to 18 and 20, wherein when linking group L is derived from 1,1-diarylethene, the oligoflexible tethered groups are located only on both the A segment and the linking group L, and are randomly located along the A segment on some of its repeat units or present on each of its repeat units.

27. 21. The block copolymer of any one of claims 1 to 17, 19, and 20, wherein when linking group L is derived from 1,1-diarylethene, the oligoflexible tethered groups are located only on the B segment and on the linking group L, and are randomly located along the B segment on some of its repeat units or present on each of its repeat units.

28. 22. The block copolymer of any one of claims 1 to 21, wherein the oligoflexible tethered group is present in either the A segment or the B segment, or both, and the oligoflexible tethered group is present randomly along each of those segments on some of their repeat units.

29. 22. The block copolymer of any one of claims 1 to 21, wherein the oligoflexible tethered groups are present in either the A segment or the B segment, or both, and these oligoflexible tethered groups are present in all of their respective repeat units.

30. 30. The block copolymer of any one of claims 1 to 29, wherein the copolymer has the structure (II): a styrenic block, the styrenic block being composed of randomly copolymerized styrenic repeat units of structures (STa) and (STb), in which R １ and R ２ are independently selected from H or C1-C4 alkyl; R ５ and R ６ are individually selected from H or C1-C4 alkyl and oligoflexible tethered groups, said oligoflexible tethered groups being selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups, a styrenic block; Structure (L １ ) in which R ７ and R ８ are individually selected from H, C1-C4 alkyl, and are multi-tethered with oligoflexible tethered groups, said oligoflexible tethered groups being selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups; a 2-methylenealkanoate derived block, the 2-methylenealkanoate derived block consisting of randomly copolymerized 2-methylenealkanoate repeat units of the structures (MEAa) and (MEAb), in which R ３ and R ４ are individually selected from C1-C4 alkyl; R ９ and R １０ are individually selected from C1-C4 alkyl, and are multi-tethered with oligoflexible tethered groups, said oligoflexible tethered groups being selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups; Including, E' is a C1-C10 alkyl terminal group; E″ is selected from H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═O-O-alkyl), and terminal groups derived from alkyl 2-arylacrylate (—CH ２ —CH(aryl)(C(═O))—O-alkyl); x and x' respectively represent the number of repeat units of structures (STa) and (STb) in the styrenic block having a Mw of from about 20,000 to about 200,000, which in the non-polar block segment is represented by the brackets designated n; y and y′ respectively represent the number of repeat units of the structures (MEAa) and (MEAb) in the 2-methylenealkanoate derived block having a Mw of from about 20,000 to about 200,000, and in the polar block segment, this is represented by the brackets designated m, and further R ５ , R ６ , R ７ , R ８ , R ９ or R １０ At least one of the groups is selected from the oligoflexible tethered groups. The block copolymer. 【Chemical 1】

31. R ５ is an oligoflexible tethered group, and R ６ is H or C1-C4 alkyl, and R ７ and R ８ is independently selected from H and C1-C4 alkyl; R ９ and R １０ is individually selected from C1 to C4 alkyl.

32. R ５ and R ６ is a multi-tethered oligo-flexible tethered group, and R ７ and R ８ is independently selected from H and C1-C4 alkyl; R ９ and R １０ is individually selected from C1 to C4 alkyl.

33. R ５ and R ６ is independently selected from H and C1-C4 alkyl; R ８ and R ７ at least one of R is an oligoflexible tethered group, and R ９ and R １０ is individually selected from C1 to C4 alkyl.

34. R ８ and R ７ and n is an integer from 1 to 30. The block copolymer of claim 33, wherein both are oligoflexible tethered groups.

35. R ５ and R ６ is independently selected from H and C1-C4 alkyl; R ８ and R ７ is independently selected from H and C1-C4 alkyl, and R ９ and R １０ 31. The block copolymer of claim 30, wherein at least one of:

36. R ９ and R １０ and are both oligoflexible tethered groups.

37. R ５ and R ６ and at least one of R ９ and R １０ 34. The block copolymer of claim 33, wherein at least one of:

38. R ５ and R ６ Both of these, as well as R ９ and R １０ 38. The block copolymer of claim 37, wherein both of are flexible tethered groups.

39. R ５ and R ６ At least one of R ７ and R ８ and at least one of R ９ and R １０ 34. The block copolymer of claim 33, wherein at least one of:

40. R ５ , R ６ , R ７ , R ８ , R ９ and R １０ is an oligoflexible tethered group.

41. R １ and R ２ The block copolymer of any one of claims 33 to 40, wherein is H.

42. R ３ and R ４ 42. The block copolymer of any one of claims 33 to 41, wherein is a C1 to C3 alkyl.

43. R ３ and R ４ 43. The block copolymer of any one of claims 33 to 42, wherein is a C1 to C2 alkyl.

44. R ３ and R ４ The block copolymer of any one of claims 33 to 43, wherein is methyl.

45. A block copolymer having structure (III): A １ is the T from about 50°C to about 100°C ｇ a styrenic block copolymer segment having A ２ is a T in the range of about -5°C to about -50°C. ｇ wherein the block copolymer segment comprises repeat units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or from a mixture of at least two different olefins selected from this group; B １ is the T from about 50°C to about 100°C ｇ and comprising repeat units derived from alkyl 2-methylene alkanoates, repeat units derived from lactones, repeat units derived from oxiranes, repeat units derived from oxetanes, or repeat units derived from cyclic carbonates; L １ is a direct valence bond or a linking moiety derived from a 1,1-diarylethene; E ３ is alkyl; E ４ is H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═O-O-alkyl), and terminal groups derived from alkyl 2-aryl acrylate (—CH ２ -CH(aryl)(C(=O))-O-alkyl), having a polydispersity ranging from 1 to about 1.09; The block copolymer. E ３ -A １ -A ２ -L １ -B １ -E ４ (III)

46. The above A ２ 46. The block copolymer of claim 45, wherein:

47. The above A ２ 46. The block copolymer of claim 45, wherein has repeat units derived from an alkadiene.

48. 48. The block copolymer of claim 45 or 47, wherein the alkadiene is a conjugated diene.

49. The above A ２ comprises a mixture of at least two different repeat units having structures (IIIa), (IIIb), (IIIc) and (IIId) derived from alkadiene, where R ｄ , R ｄ１ , R ｄ３ , R ｄ４ , R ｅ , R ｅ１ , R ｅ３ , and R ｅ４ are individually selected from the group consisting of H and C1-C8 alkyl, and further, the total mole percent of olefinic repeat units in the block copolymer ranges from about 3 mole percent to about 50 mole percent. 【Chemistry 2】

50. The above A ２ comprises a mixture of at least two different repeat units having structures (IIIa), (IIIb), (IIIc) and (IIId) derived from alkadiene, where R ｄ , R ｄ１ , R ｄ３ , and R ｄ４ are the same and are selected from H or C1-C8 alkyl, and R ｅ , R ｅ１ , R ｅ３ , and R ｅ４ is selected from H or C1-C8 alkyl. 【Chemistry 3】

51. The above A ２ comprises repeat units derived from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isoprene, 3-methylenepent-1-ene, 3-methylenehex-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepent-1-ene, 1,3-butadiene, ethylidenenorbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinylnorbornene (2-vinylbicyclo[2.2.1]hept-2-ene), or chloroprene (2-chlorobuta-1,3-diene), or a mixture comprising at least two of these.

52. 48. The block copolymer of claim 45 or 47, wherein the alkadiene is a non-conjugated diene.

53. 47. The block copolymer of claim 45 or 46, wherein A2 is derived from an alkatriene.

54. 46. The block copolymer of claim 45, wherein A2 has repeating units derived from a mixture of at least two different olefins selected from the group consisting of alkenes, alkadienes, and alkatrienes.

55. The above A ２ The block copolymer according to any one of claims 45 to 51, further comprising a styrene-based repeat unit.

56. The polar block copolymer segment B １ 56. The block copolymer of any one of claims 45 to 55, wherein comprises a repeat unit derived from a lactone.

57. The polar block copolymer segment B １ 56. The block copolymer of any one of claims 45 to 55, wherein comprises repeat units derived from alkyl 2-methylene alkanoate.

58. The polar block copolymer segment B １ has a Mw between about 20,000 and about 200,000, and the non-polar styrenic block segment has a Mw between 20,000 and about 200,000.

59. L １ The block copolymer of any one of claims 45 to 58, wherein is a direct valence bond.

60. L １ is a linking group derived from 1,1-diarylethene.

61. E ４ 61. The block copolymer of any one of claims 45 to 60, wherein is H or alkyl.

62. E ４ The block copolymer according to any one of claims 45 to 60, wherein is a group derived from alkylmethyl-2-arylacrylate.

63. E ３ The block copolymer of any one of claims 45 to 62, wherein is C1 to C8 alkyl.

64. 61. The block copolymer of any one of claims 45-52, 54, 55, 57, 58, or 60 having the structure (IIIe): a styrenic block comprising randomly copolymerized styrenic repeat units of structures (STc) and (STd), wherein R １ａ and R ２ａ is independently selected from H or C1-C4 alkyl, and R ５ａ and R ６ａ is a styrenic block, wherein each is independently selected from H or C1-C4 alkyl; Structure (L １ ) in which R ７ａ and R ８ａ is a linking moiety, wherein is independently selected from H and C1-C4 alkyl; Including, E' is a C1-C20 alkyl terminal group; E″ is selected from H, alkyl, carbonylalkyl (—C═O-alkyl), carbonyloxyalkyl (—C═O-O-alkyl), and terminal groups derived from alkyl 2-arylacrylate (—CH ２ —CH(aryl)(C(═O))—O-alkyl); x and x' respectively represent the number of repeat units of structures (STc) and (STd) in the styrenic block having a Mw of from about 20,000 to about 200,000, which in the non-polar block segment is represented by the brackets designated n; y and y′ respectively represent the number of repeat units of the structures (MEAc) and (MEAd) in the block derived from said 2-methylenealkanoate having Mw of from about 20,000 to about 200,000 in the polar block segment represented by the brackets designated by m, and in these structures, R ３ａ and R ４ａ , R ９ａ and R １０ａ are individually selected from C1-C4 alkyl; A ２ is a T in the range of about -5°C to about -50°C. ｇ and comprising repeat units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or from a mixture of at least two different olefins selected from this group, The block copolymer. 【Chemistry 4】

65. R １ａ , R ２ａ , R ５ａ , R ６ａ is H.

66. R ７ａ and R ８ａ 66. The block copolymer of claim 64 or 65, wherein

67. R ３ａ , R ４ａ , R ９ａ and R １０ａ is CH ３ The block copolymer according to any one of claims 64 to 66,

68. The above A ２ comprises a mixture of at least two different repeat units having the structures (IIIa), (IIIb), (IIIc) and (IIId), where R ｄ , R ｄ１ , R ｄ３ , R ｄ４ , R ｅ , R ｅ１ , R ｅ３ , and R ｅ４ are individually selected from the group consisting of H and C1-C8 alkyl, and further, the total mole percent of olefinic repeat units in the block copolymer ranges from about 3 mole percent to about 50 mole percent. 【Chemistry 5】

69. The above A ２ comprises a mixture of at least two different repeat units having the structures (IIIa), (IIIb), (IIIc) and (IIId), where R ｄ , R ｄ１ , R ｄ３ , and R ｄ４ are the same and are selected from H or C1-C8 alkyl, and R ｅ , R ｅ１ , R ｅ３ , and R ｅ４ is selected from H or C1-C8 alkyl; 69. The block copolymer according to any one of claims 64 to 68. 【Chemistry 6】

70. The above A ２ is a block copolymer segment having repeat units derived from isoprene or butadiene.

71. The non-polar block copolymer segment A １ 71. The block copolymer of any one of claims 64-70, wherein Mw is between about 20,000 and about 200,000.

72. 72. The block copolymer of any one of claims 64 to 71, wherein E' is a C3 to C7 alkyl.

73. 72. The block copolymer of any one of claims 64 to 71, wherein E'' is H.

74. A composition comprising at least one block copolymer according to any one of claims 1 to 44 and a spin-cast organic solvent.

75. 75. The composition of claim 74, further comprising another block copolymer.

76. 75. The composition of claim 74, further comprising a homopolymer.

77. Periodicity L ０ 1. A method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of a block copolymer having the following steps: a) forming a coating layer of a block copolymer from the composition of any one of claims 74 to 76 on the unpatterned substrate; and b) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method comprising:

78. Periodicity L ０ and vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having ０ and a method of aligning these domains in said pattern, comprising the steps of: a1) forming a coating layer of the composition of any one of claims 74 to 76 on the first topographic substrate, wherein the average thickness of the block copolymer coating layer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; and b1) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within recessed regions; The method comprising:

79. A periodic L is formed on a second patterned substrate having a topographical pattern. ０ wherein the first and second block copolymer domains are vertically oriented by the topographical pattern L ０ and a pitch P1 of the topography that is greater than 0.7 times L ０ and a method of aligning these domains with said pattern, comprising the steps of: a2) forming a coating layer of a block copolymer on the second patterned substrate using the composition of any one of claims 74 to 76, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b2) annealing the block copolymer layer to produce vertically oriented, positive integer, non-zero first and second block copolymer domains on the second patterned substrate and align them with respect to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern; The method comprising:

80. The first and second block copolymer domains are vertically oriented on a substrate having a surface chemical prepattern with a pitch P2, where the pitch P2 is L ０ and a method of aligning these domains, comprising the steps of: b3) forming a coating layer of a block copolymer on a substrate having a surface chemical pre-pattern using the composition according to any one of claims 74 to 76; and b3) annealing the block copolymer layer to produce vertically oriented first and second block copolymer domains aligned with the substrate having a surface chemical prepattern with pitch P2; The method comprising:

81. A composition comprising the block copolymer of any one of claims 45 to 73 and a solvent.

82. 82. The composition of claim 81, further comprising another block copolymer.

83. 82. The composition of claim 81, further comprising a homopolymer.

84. Periodicity L ０ 1. A method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of a block copolymer having the following steps: a4) forming a coating layer of a block copolymer from the composition of any one of claims 81 to 83 on the unpatterned substrate; and b4) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method comprising:

85. Periodicity L ０ and vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having ０ and a method of aligning these domains in said pattern, comprising the steps of: a5) forming a coating layer of the composition of any one of claims 81 to 83 on the first topographic substrate, wherein the average thickness of the block copolymer coating layer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; and b5) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within recessed regions; The method comprising:

86. On the second patterned substrate having a topographical pattern, a periodic L ０ and vertically orienting the first and second block copolymer domains having L ０ and a pitch P1 of the topography that is greater than 0.7 times L ０ and a method of aligning these domains with said pattern, comprising the steps of: a6) forming a coating layer of a block copolymer on the second patterned substrate using the composition of any one of claims 81 to 83, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b6) annealing the block copolymer layer to produce vertically oriented, positive integer, non-zero first and second block copolymer domains on the second patterned substrate and align them with respect to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern; The method comprising:

87. The first and second block copolymer domains are vertically oriented on a substrate having a surface chemical prepattern with a pitch P2, where the pitch P2 is L ０ and a method of aligning these domains, comprising the steps of: a7) forming a coating layer of a block copolymer on a substrate having a surface chemical pre-pattern using the composition according to any one of claims 81 to 83; and b7) annealing the block copolymer layer to produce vertically oriented first and second block copolymer domains aligned with the substrate having a surface chemical prepattern with pitch P2; The method comprising:

88. Use of a block copolymer according to any one of claims 1 to 73 or a composition according to claim 74 or 81 in a self-assembly process followed by patterned transfer of the self-assembled pattern onto a substrate.

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