Multi-pitch tolerant block copolymers with enhanced speed for induced self-assembly applications

Abstract

The present invention provides a method for using a block copolymer composition to align the microdomains of a self-assembling block copolymer so that a self-assembling geometric shape is formed that is useful for forming an array of contact holes or lines and spaces. [Solution] A compound of formula (C1). (In the formula, R 1b , R 2b , R 1c and R 2c At least one of these is an oligoflexible tethered group, and the oligoflexible tethered group is either an oligoether tethered group or an oligodialkylsiloxane tethered group. JPEG2026090608000057.jpg63170

Description

[Technical Field]

[0001] The present invention relates to two different block copolymer families having general structures (1) and (6), respectively, two compositions comprising a block copolymer from one of these two families, and a novel method for using the block copolymer composition to align the microdomains of a self-assembling block copolymer (BCP) so as to form a self-assembling geometric shape useful for forming an array of contact holes or line-and-space. These compositions and methods are useful in the manufacture of electronic devices. [Background technology]

[0002] Self-assembly of block copolymers is a useful method for generating even smaller patterned shapes for the fabrication of microelectronic devices, achieving micro-dimensions (CD) of shapes on the order of nanoscale. Self-assembly methods are desirable to extend the resolving capabilities of microlithography techniques for repeating shapes such as arrays of contact holes or posts. Conventional lithography strategies may use ultraviolet (UV) light to expose a photoresist layer coated on a substrate or layered substrate by passing it through a mask. Positive or negative photoresists are useful, and these may also contain heat-resistant elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive photoresists, UV radiation passing through the mask triggers a photochemical reaction in the photoresist, causing the exposed area to be removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through the mask makes the radiation-exposed area difficult to remove with a developer solution or by conventional IC plasma processing. Integrated circuit patterns, such as gates, vias, or interconnects, are then etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional lithography exposure processes, there are limitations to the graphic dimensions of integrated circuit patterns. Further reduction of pattern dimensions is difficult to achieve using radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Due to the need for large-scale integration, the circuit dimensions and graphics of devices have been continuously reduced. In the past, the final resolution of the graphic depended on the wavelength of light used to expose the photoresist, which itself has limitations. Guided (or guiding) 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 higher resolution and CD control in strategies using EUV, electron beam, deep UV, or immersion lithography. The inductively self-assembling block copolymer comprises blocks of etching-resistant copolymer units and blocks of easily etchable copolymer units, and when this block copolymer is coated, aligned, and etched on a substrate, it provides areas of very high-density patterns.

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

[0004] In graphoepitaxy-induced self-assembly, block copolymers self-assemble around a substrate that has been pre-patterned using conventional lithography (ultraviolet, deep UV, electron beam, or extreme ultraviolet (EUV) exposure sources) to form repeating topographic patterns such as line / space (L / S) or contact hole (CH) patterns. In an example of an L / S-induced self-assembly array, the block copolymers can enhance pattern resolution by dividing the space in the trenches between topographic lines into finer patterns, by forming self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the pre-patterned lines. For example, microphase-separable diblock copolymers or triblock copolymers, including carbon-rich blocks resistant to plasma etching (e.g., styrene, or containing some other element such as Si, Ge, or Ti), and blocks that are highly etchable or removable by plasma, can provide high-resolution pattern definition. Examples of highly etchable blocks include monomers (e.g., methyl methacrylate) that are oxygen-rich, free of heat-resistant elements, and capable of forming highly etchable blocks. Plasma etching gases used in etching processes to define self-assembling patterns are typically gases used in processes for manufacturing integrated circuits (ICs). In this way, much finer patterns can be generated on typical IC substrates compared to those that can be defined by conventional lithography techniques, thus achieving pattern multiplication. Similarly, graphoepitaxy can be used to generate more dense patterns, such as contact holes. In graphoepitaxy, appropriate block copolymers align themselves by induced self-assembly around arrays of contact holes or posts defined by conventional lithography, forming denser arrays of etchable and etch-resistant domains, which, when etched, result in a denser array of contact holes. As a result, graphoepitaxy has the potential to provide both pattern refinement and pattern multiplication.

[0005] In chemical epitaxy or pinned chemical epitaxy, self-assembly of block copolymers is formed on a surface having an inductive pattern, which consists of regions with different chemistry, lacking or not exhibiting significant topography (in other words, non-inductive topography) that underlies the induced self-assembly process. For example, the surface of a substrate can be patterned using conventional lithography (UV, deep UV, electron beam, EUV) to create a line-and-space (L / S) pattern of surfaces with different chemistry, where exposed areas where the surface chemistry has been alternated by radiation are alternating with unexposed areas that do not show chemical changes. These regions do not provide topographic differences but provide surface chemical differences or pinning that induce self-assembly of block copolymer segments. Specifically, the induced self-assembly of block copolymers having block segments containing etch-resistant repeating units (e.g., styrene repeating units) and fast-etchable repeating units (e.g., methyl methacrylate repeating units) allows for the precise placement of etch-resistant and fast-etchable block segments on a pattern. This technique enables the precise placement of these block copolymers and subsequent pattern transfer to a substrate after plasma or wet etching. Chemical epitaxy has the advantage of being fine-tuned by changes in chemical differences, which helps improve line edge roughness and CD control, thus enabling pattern adjustment. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern-adjusted using chemoepitaxy.

[0006] These neutral layers are layers on the substrate or on the surface of the treated substrate that have no affinity for any of the block segments of the block copolymer used for induced self-assembly. Neutral layers are useful in the graphoepitaxy method of induced self-assembly of block copolymers because they allow for proper placement or orientation of the block polymer segments for induced self-assembly, which results in proper placement of etch-resistant and highly etchable block polymer segments on the substrate. For example, on a surface containing line-and-space patterns defined by conventional radiolithography, the neutral layer allows the block segments to be oriented so that they are perpendicular to the surface of the substrate, and such orientation is ideal for both pattern adjustment and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between 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 adjustment or pattern multiplication based on the figure generated by conventional lithography. Modifying or pinning selected small areas of the substrate to strongly interact 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 forms the basis for pinned chemoepitaxy or graphoepitaxy used for pattern multiplication.

[0007] Self-assembly using polystyrene-β-polymethyl methacrylate (PS-β-PMMA) is widely used in lithography as a next-generation patterning material. While the nanolayer separation and assembly process successfully produces aligned domain arrays, this occurs with the formation of a considerable amount of defects when the film thickness exceeds 50 nm. These defects are particularly noticeable in contact hole and line / space multiplication processes, and such defects need to be significantly reduced to improve device yield in any commercially viable IC manufacturing method using induced self-assembly. One problem to be solved is that standard diblock copolymers cannot be used for induced self-assembly for the purpose of pattern multiplication of multipitch patterns. Another problem to be solved is that the defect-free assembly process for block copolymers requires high thermal energy and longer annealing times. This difficulty limits the application of induced self-assembly of block copolymers with large domain spacing and restricts the use of standard AB-type diblock copolymers and standard triblock copolymers. Typically, standard triblock copolymers have twice the molecular weight of standard diblock copolymers and are capable of multi-pitch induced self-assembly. However, this ability to produce valuable multi-pitch application DSAs is hindered by the long annealing time required to achieve defect-free multi-pitch induced self-assembly. For example, a triblock copolymer of PMMA-b-PS-b-PMMA (ABA) with an L0 of 50 nm has been shown to produce 50 nm to 80 nm multi-pitch DSAs, which are crucial for design flexibility in the IC industry (Figure 3 on page 5543 of Ji et al ACS NANO, VOL.6, NO.6, pp. 5440-5448 (Non-Patent Literature 1)). This type of ABA-type triblock copolymer can produce defect-free DSAs at bending angles of 45, 90, and 135° (Figure 6 on page 5445 of Ji et al ACS NANO, VOL.6, NO.6, pp. 5440-5448 (Non-Patent Literature 1)). However, one of the problems to be solved is that the assembly kinetic properties of this type of ABA-type triblock copolymer are larger M wDue to the changes in the rate of loop and bridge formation in the central PS block, it is three times slower than AB-type diblock copolymers. This requires approximately 36 hours of annealing to obtain defect-free DSA on multi-pitch layers, which is impractical for industrial manufacturing. Therefore, the development of novel triblock copolymers that can provide faster kinetic properties and can be oriented in the conventional underlayer for DSA is extremely important. [Brief explanation of the drawing]

[0008] [Figure 1] Structure (1) Family of block copolymer ABA architecture; monotethered oligoflexible tethers at the junctions and edges of the ABA architecture. [Figure 2] Structure (1) Family Block Copolymer ABA Architecture; Multitethered Oligoflexible Tether Copolymer Segments in Copolymerized Segments or at Junctions and Edges of ABA Architecture; a) Tethers on both A and B Blocks, b) Tethers on B Block Only, c) Tethers on A Block Only, d) Short-chain Tethers at Junctions and Edges, e) Long-chain Tethers at Junctions and Edges. [Figure 3] Structure (1) Family Block Copolymer ABA Architecture, Multi-Tethered Oligoflexible Tether copolymerized at the center of the central block of the ABA architecture. [Figure 4] Structure (6) Block copolymer ABA architecture, introduction of low Tg block segments at the junctions of the ABA architecture. [Figure 5] 1FOV SEM image, process conditions: underlayer polymer 1:250℃ / 1 hour (N2); EBR 2 minutes, spin dry, 110℃ / 1 minute, FT=140nm. Etching conditions: O2 (50 sccm): N2 (50 sccm) for 30 seconds, power=50W, RIE=100, using a trion etcher. Total number of defects measured using Hitachi soft wafers. A) Normal non-tethered ABA shows a total number of defects of 101, and B) Monotethered ABA shows 60 defects with improved particle size. [Figure 6] Kinetic enhancement of multi-tethered C8S copolymerized with PS block. 1FOV SEM image, process conditions: Underlayer polymer 1:250°C / 1 hour (N2): EBR 2 minutes, spin dry, 110°C / 1 minute, FT=140nm. Etching conditions: O2 (50 sccm): N2 (50 sccm) for 30 seconds, power=50W, RIE=100, using a trion etcher. [Figure 7] Kinetic enhancement of ABA having low-Tg octylstyrene copolymerized to PS blocks and hexyl methacrylate copolymerized to PMMA blocks. 1FOV SEM image, process conditions: V: 250°C / 1 hour (N2); EBR 2 minutes, spin dry, 110°C / 1 minute, FT=140nm. Etching conditions: O2 (50 sccm): N2 (50 sccm) for 30 seconds, power=50W, RIE=100, using a trion etcher. [Figure 8] Kinetic enhancement of ABA with isoprene at the PS-PMMA junction. 1FOV SEM image, process conditions: V: 250°C / 1 hour (N2); EBR 2 minutes, spin dry, 110°C / 1 minute, FT=50nm. Larger L0 and significantly better particle size compared to conventional ABA. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Ji et al ACS NANO, Ji et al, VOL.6, NO.6, pp. 5440-5448, p. 5543, Figure 3; p. 5445, Figure 6 [Non-Patent Document 2] Macromolecules 2019,52,2987-2994 [Non-Patent Document 3] Macromolecules 2019,52,2987-2994 [Non-Patent Document 4] Macromol.Rapid Commun.2018,39,1800479 [Non-Patent Document 5] A.Deiter Shluter et al Synthesis of Polymers,2014,Volume 1,p315 [Non-Patent Document 6] Encyclopedia of Polymer Science and Technology,2014,Vol 7,p 625 [Non-Patent Document 7] David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization”, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005) [Overview of the Initiative]

[0010] The defect-free assembly process of block copolymers requires high thermal energy and relatively long time. This difficulty limits the application of induced self-assembly of block copolymers with large domain spacing and also limits the use of triblock copolymers, which have a molecular weight twice that of diblock copolymers, for multipitch applications in lithographic patterning. This invention relates to the synthesis of two kinetically enhanced block ABA-type triblock copolymer families.

[0011] The first family of ABA-type block copolymers relates to the ABA triblock copolymers of the present invention having tethered groups, having the structure (1) described herein, where A is an etchable polar block segment and B is a non-polar etch-resistant block segment. The structure (1) described herein encompasses the following general ABA architectures shown in Figures 1-3. Novel mono and multi-tethered ABA-type triblock copolymers derived from the following monomers, namely styrene, substituted styrene, methyl methacrylate, substituted methacrylate, diphenylethylene, and substituted diphenylethylene, as non-limiting examples, are synthesized by living anionic polymerization under suitable conditions. The substitutional strategy, referred to as the tethered configuration, requires tethering (or bonding) of a tether, which is either an oligopolar or oligononpolar tether carbon chain, which may have various sub-side chain carbons and other heteroatoms. The tether is located at the junction of the block chain segments or as shown in any of Figures 1-4.

[0012] Figure 1 schematically shows a block copolymer ABA architecture in the structure (1) family, where the junctions and edges of the ABA architecture are monotethered with oligoflexible tethers.

[0013] Figure 2 shows a family of block copolymer ABAs in which the repeating units copolymerize or at the junctions and edges of the ABA architecture, with a) tethers on both A and B blocks, b) tethers on B blocks only, c) tethers on A blocks only, d) short tethers on the junctions and edges, and e) long tethers on the junctions and edges.

[0014] Figure 3: A block copolymer ABA architecture of the structure (1) family, multi-tethered with repeating units having copolymerized oligoflexible tethers at the center of the central block of the ABA architecture.

[0015] Figure 4: A block copolymer ABA architecture in structure (6), comprising special repeating units derived from monomers tethered with substituents on either a nonpolar or polar block, on a nonpolar block B, a polar block A, or a mixture thereof, with low T at the junction of the ABA architecture. g Introduction of block segments.

[0016] A second family having the general structure (6) has substituents on special monomers, and these substituents are selected so that they can provide kinetic enhancement of the block copolymer through absorption of thermal energy at high-frequency flipping, a decrease in the overall glass transition temperature, and subtle changes in the chi parameter that do not change the surface energy of the block copolymer and do not significantly change the compatibility with conventional underlying brush copolymers consisting of styrene units and methyl methacrylate repeating units.

[0017] More importantly, the present invention discloses the synthesis of specific permutations of block copolymers, such as PMMA-b-PS-b-PMMA, having polar and nonpolar mono and multitethered moieties, as shown in Figures 1-3. Examples of such structures are P(M1-co-M2)-bP(S1-co-S2)-bP(M1-co-M2), PMMA-bP(S1-co-S2)-b-PMMA, P(M1-co-M2)-b-PS-bP(M1-co-M2), P(alkylMA)-b-PMMA-bP(alkyl-S)-b-PS-bP(alkylS)-b-PMMA-bP(alkylMA), PMMA-b-PS-bP(alkylS)-b-PS-b-PMMA, and PMMA-b-PI-b-PS-b-PI-b-PMMA, where S1 and M1 are styrene monomer units and methyl methacrylate monomer units, respectively. S2 and M2 are substituted styrene and substituted methyl methacrylate, respectively, where the substituents are suspension groups containing nonpolar alkyl or polar ethylene oxide or dimethylsilyloxy. These copolymers are produced by living anionic polymerization in the presence of a bidirectional initiator. The copolymers are used to self-assemble to generate periodic domains of compatible blocks within di- or triblock copolymers, thereby forming cylindrical and lamellar shapes depending on the volume composition of polar blocks relative to nonpolar blocks. The present invention also relates to the use of these copolymers as kinetically enhanced block copolymers for faster and simpler self-assembly processes, and to uses covering a wide range of pitches for forming line-and-space or contact-hole assemblies for use in induced self-assembly for lithography template generation under suitable process conditions.

[0018] Another aspect of the present invention is a method of using the composition in a self-assembly process, which is followed by pattern transfer of the self-assembly pattern onto a substrate.

[0019] Another aspect of the present invention is a novel oligodiblock copolymer b-2) having the above-described blocks Ab) and Bb).

[0020] Induced self-assembly (DSA) of polystyrene-β-polymethyl methacrylate (PS-β-PMMA) block copolymers is widely used as a next-generation lithography patterning method. Microphase separation of diblock copolymers is used in lithography for pattern size control. Widely used diblock copolymers such as PS-β-PMMA can generate mono- and unidirectional pattern sizes in thin film form using a suitable underlayer or pre-pattern for DSA applications. However, when attempting to obtain multi-pitch pattern sizes from a single diblock copolymer formulation, extended pitch is not possible with current PS-β-PMMA block copolymers. This is because the L050nm PMMA-b-PS-PMMA (ABA) triblock copolymer has been shown to produce multi-pitch DSAs from 50nm to 80nm, which is crucial for design flexibility in the IC industry (Figure 3 on page 5543 of Ji et al ACS NANO, VOL.6, NO.6, pp. 5440-5448 (Non-Patent Literature 1)). This type of ABA triblock copolymer can produce defect-free DSAs at bending angles of 45, 90, and 135° (Figure 6 on page 5445 of Ji et al ACS NANO, VOL.6, NO.6, pp. 5440-5448 (Non-Patent Literature 1)). However, the problem to be solved is that the assembly kinetic properties of this type of ABA triblock copolymer are larger M w Due to the changes in the rate of loop and bridge formation in the central PS block, it is three times slower than AB-type diblock copolymers. This requires approximately 36 hours of annealing to obtain defect-free DSA on multi-pitch layers, which is impractical for industrial manufacturing. Therefore, the development of novel triblock copolymers that can provide faster kinetic properties and can be oriented in the conventional underlayer for DSA is extremely important.

[0021] In this specification, the inventors disclose their development of a series of novel and modified ABA triblock copolymers having long or short tethers, each nonpolar or polar, with a length of 18 or 6 atoms, located at the joints and ends of the block, for better mobility and faster kinetic properties by using conventional special monomers as comonomers and lowering the overall glass temperature. The inventors also disclose their development of low T in polystyrene blocks (PS) or poly(methyl methacrylate) (PMMA) blocks or both PS and PMMA blocks. g A series of multi-tethered and copolymerized ABAs using comonomers have also been developed. Some examples include P(M1-co-M2)-bP(S1-co-S2)-bP(M1-co-M2), PMMA-bP(S1-co-S2)-b-PMMA, P(M1-co-M2)-b-PS-bP(M1-co-M2), P(alkylMA)-b-PMMA-bP(alkyl-S)-b-PS-bP(alkylS)-b-PMMA-bP(alkylMA), PMMA-b-PS-bP(alkylS)-b-PS-b-PMMA, and PMMA-b-PI-b-PS-b-PI-b-PMMA, where S1 and M1 are styrene monomer units and methyl methacrylate monomer units, respectively. S2 and M2 are substituted styrene and substituted methyl methacrylate, respectively, where the substituents are suspension groups containing nonpolar alkyl or polar ethylene oxide or dimethylsilyloxy.

[0022] All newly developed ABAs were tested for fingerprint shape on a neutral underlayer brush substrate on SiOx. Furthermore, to evaluate the novel triblock copolymers, the inventors also developed a thin-film fingerprint network defect analysis method. In this method, the inventors coated these block copolymers with 2 and 3 × L0 and then partially dry-etched (using oxygen plasma) to identify and count network defects in the bulk of the film. Compared to conventional non-tethered ABA block copolymers, the results showed significantly fewer defects and faster kinetic properties in mono- or multi-tethered ABA block copolymers modified at junctions and edges or copolymerized with specially substituted monomers at less than 20%, without significantly affecting the chi-parameter of the novel block copolymers. Because the synthesis is carried out by living anion copolymerization, the above triblock ABA copolymers have a narrow molecular weight distribution (M w / M n It exhibits <1.1) and functions using a standard underlayer suitable for PS-b-PMMA DSA.

[0023] One aspect of the present invention is a block copolymer having structure (1), wherein segment A is a polar block copolymer segment comprising one of alkyl 2-methylene alkanoate-derived repeating units, lactone-derived repeating units, oxirane-derived repeating units, oxetane-derived repeating units, or cyclic carbonate-derived repeating units; L is a direct valence bond or a linkage derived from 1,1-diarylethene; segment B is a non-polar block copolymer segment comprising styrene-based repeating units, and E is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and alkyl 2-aryl acrylate-derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0024] EALBLAE (1) Furthermore, 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.

[0025] Furthermore, these oligoflexible tethered groups are multi-tethered in the polymer block copolymer of structure (1) at positions selected from the following arrangements: The oligoflexible tethered group is present only in segment A, and is randomly located along this segment on some of its repeating units, or present in each of its repeating units. The oligoflexible tethered group is present only in segment B, and is randomly located along this segment on some of its repeating units, or present in each of its repeating units. The oligoflexible tethered group is present in both segment A and segment B, and is randomly located along these segments on only a portion of their repeating units, or is present in each of their repeating units. When the oligoflexible tethered groups are alkyl-terminated groups or alkyl 2-aryl acrylate derivative-terminated groups (-CH2-CH(aryl)(C(=O))-O-alkyl), the following are present on both E-terminal groups. The oligoflexible tethered group is present on both L when L is a linking portion derived from 1,1-diarylethene. The oligoflexible tethered group is located in the center of segment B, and the oligoflexible tethered group is located on any one of segment A, segment B, L (if L is the connecting portion), and terminal group E.

[0026] Furthermore, the block copolymer of structure (1) exhibits polydispersity ranging from 1 to approximately 1.09.

[0027] One other aspect of the present invention is a block copolymer of structure (6), where A1 is a polar block copolymer segment having a T from about 50°C to about 100°C and including any one of an alkyl 2-methylene alcanoate repeating unit, a lactone repeating unit, an oxirane repeating unit, an oxetane repeating unit, or a cyclic carbonate repeating unit; and B1 is a styrenic block copolymer segment having a T from about 50°C to about 100°C. Also, in this aspect, B2 is a block copolymer segment having a T in the range from about -5°C to about 50°C and including repeating units derived from an olefin selected from the group consisting of an alkene, an alkadiene or an alkatriene, or from a mixture of at least two different olefins selected from this group. Further, in this aspect, L1 is a direct valence bond or a linking moiety derived from 1,1-diarylethene, and E1 is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonylalkyloxy (-C=O-O-alkyl), and alkyl 2-arylacrylate-derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl), and the block copolymer has a polydispersity in the range from 1 to about 1.09. g having a T from about 50°C to about 100°C; and B1 is a styrenic block copolymer segment having a T from about 50°C to about 100°C. g In this aspect as well, B2 is a block copolymer segment having a T in the range from about -5°C to about 50°C and including repeating units derived from an olefin selected from the group consisting of an alkene, an alkadiene or an alkatriene, or from a mixture of at least two different olefins selected from this group. g having a T in the range from about -5°C to about 50°C and including repeating units derived from an olefin selected from the group consisting of an alkene, an alkadiene or an alkatriene, or from a mixture of at least two different olefins selected from this group. Further, in this aspect, L1 is a direct valence bond or a linking moiety derived from 1,1-diarylethene, and E1 is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonylalkyloxy (-C=O-O-alkyl), and alkyl 2-arylacrylate-derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl), and the block copolymer has a polydispersity in the range from 1 to about 1.09.

[0028] E1 - A1 - L1 - B2 - B1 - B2 - L1 - A1 - E1 (6) One other aspect of the present invention is a composition comprising the block copolymer of the present invention of structure (1) or the block copolymer of the present invention of structure (6) and a spin-cast solvent.

[0029] One other aspect of the present invention is a method of use in the self-assembly process of the composition, followed by pattern transfer of the self-assembled pattern into a substrate.

[0030] One other aspect of the present invention is a compound of structure (C1), where R 1b , R 1c , R 2b, and R 2c The group is individually selected from H, halide, C1-C4 alkyl, C1-C4 alkyloxy, and oligoflexible tethered group, however, R 1b , R 2b , R 1c and R 2c At least one of them is an oligoflexible tethered group, and R 3b , R 3c , R 4b , R 4c , R 5b and R 5c These are individually selected from H, halide, C1-C4 alkyl, and C1-C4 alkyloxy.

[0031] [ka] [Modes for carrying out the invention]

[0032] Both the general description above and the detailed description below are illustrative and explanatory, and should be understood not to limit the invention described in the claims. In this application, unless otherwise specifically stated, the use of the singular form includes the plural, the singular form means "at least one," and the use of "or" means "and / or." Furthermore, the use of "includes," and other verb forms such as "included," is not limiting. Also, unless otherwise specifically stated, descriptions such as "element" or "component" include both elements and components containing one constituent unit, and elements or components containing more than one constituent unit. Unless otherwise indicated, the conjunction "and" used herein is intended to be compatible, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. The use of "and / or" used herein refers to any combination of the aforementioned elements, including the use of a single element.

[0033] The term "tethered" refers to the attachment of oligoflexible groups (also known as oligotethers) to various parts of the block copolymer of the present invention having the structure (1) as defined herein.

[0034] L0 is the natural pitch of aggregated block copolymers, which tends to be proportional to the size of the copolymer.

[0035] The term C1-C4 alkyl is a general term for methyl, C2-C4 linear alkyl, and C3-C4 branched alkyl moieties, and examples include methyl (-CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2), and 2-butyl (-CH(CH3)CH2-CH3). Similarly, the term C1-C8 alkyl is a general term for methyl, C2-C8 linear alkyl, C3-C8 branched alkyl, C4-C8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), or C5-C8 alkylene cycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0036] The term C2-C5 alkylene is a general term for C2-C5 linear alkylene moieties (e.g., ethylene, propylene, etc.) and C3-C5 branched alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0037] Diblock and triblock copolymers of styrene-based repeating unit moieties and alkyl 2-methylene alkanoate-derived repeating unit moieties, which are useful as components in the compositions according to the present invention described herein, can be produced by various methods, such as anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-cleavage-chain transfer (RAFT) polymerization, living radical polymerization, and similar methods (Macromolecules 2019, 52, 2987-2994 (Non-Patent Literature 3); Macromol. Rapid Commun. 2018, 39, 1800479 (Non-Patent Literature 4); A. Deiter Shluter et al Synthesis of Polymers, 2014, Volume 1, p315 (Non-Patent Literature 5); Encyclopedia of Polymer Science and Technology, 2014, Vol 7, p 625 (Non-Patent Literature 6)).

[0038] 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 oligomeric form of this material is abbreviated as oligo(Sb-MMA). The oligomer oligo(styrene-co-p-octylstyrene)-block-(methyl methacrylate-co-di(ethylene glycol)methyl ether methacrylate) uses the same abbreviation to indicate random block copolymer elements, specifically oligo(S-co-p-OS)-bP(MMA-co-DEGMEMA) (S=styrene, p-OS=para-octylstyrene, MMA=methacrylate, DEGMEMA=di(ethylene glycol)methyl ether methacrylate) to indicate repeating units in this block copolymer where the two blocks are random copolymers.

[0039] FOV is an abbreviation for top-down scanning electron microscope (SEM) field of view in the SEM drawings of this application. "L / S" is an abbreviation for line-and-space lithography.

[0040] The notation alkyl 2-methylene alkanoate (alkyl-O-(C=O)-C(alkyl)=CH2) refers to an alkyl ester of 2-methylene alkanoate, where the 2-methylene alkanoate may contain up to 11 carbon atoms, and the alkyl in the alkyl 2-methylene alkanoate may contain up to 8 carbon atoms, and is selected from methyl, linear alkyl, branched alkyl, and cyclic alkyl. The following structure gives the general structural formula of such alkyl 2-methylene alkanoate, where Ralk a and Ralk b The alkyl group is selected from C1-C8 alkyl groups, and non-limiting examples of alkyl 2-methylene alkanoates falling within this range are shown.

[0041] [ka] The term "styrene-based" as used herein generally encompasses repeating units derived from styrene derivatives unless otherwise specified, such as repeating units derived from styrene derivatives having the following structure, where the Xsty portion is H or a C1-C4 alkyl group, and the Rsty portion is H, a C1-C5 alkyl group, a halide, a C1-C5 alkyloxy group, or an oligoflexible tethered group, and st is the number of Rsty substituents, which is 1 or 2.

[0042] [ka] The term 1,1-diarylethene as used herein, unless otherwise indicated, encompasses a moiety derived from an ethene having two substituents at position 1, which are aryl moieties, as shown below, where Aryl1 and Aryl2 are aryl substituents selected from phenyl or substituted phenyl, and if substituents are present on either or both Aryl1 and Aryl2, these substituents are independently selected from C1-C5 alkyl, halide, C1-C5 alkyloxy, and oligoflexible tethered groups.

[0043] [ka] The term “alkyl 2-aryl acrylate derived end group,” as described in the general structure (-CH2-CH(aryl)(C(=O))-O-alkyl), is defined in more detail in the following general structure unless otherwise indicated, where * indicates a bond site to the end of a block copolymer chain; Aryl3 is an aryl substituent selected from phenyl or substituted phenyl, and if a substituent is present, this substituent is independently selected from C1-C5 alkyl, halide, C1-C5 alkyloxy and oligoflexible tethered groups; and further, alkyl3 is an unsubstituted alkyl C1-C5 alkyl or a C1-C5 alkyl substituted with an oligoflexible tethered group. This end group structure can be derived by 2-aryl acrylate alkyl esters, as a helpful example for illustration, which react with a living anion at the end of the polymer chain at the CH2 olefinic moiety to form CH - An anion is formed, which is then terminated by protonation.

[0044] [ka] The chapter titles used herein are for the purpose of organizing the document and should not be interpreted as limiting the subject matter. While not limiting, all documents or parts of documents cited herein, including patents, patent applications, articles, books, and professional texts, are considered to have their entire contents included herein for all purposes. In the event of any conflict between the definition of a term in one or more of the documents and similar materials cited herein and those in this specification, the definition in this specification shall prevail.

[0045] Unless otherwise specified, “alkyl” refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and analogues), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and analogues), or polycyclic (e.g., norbornyl, adamantyl, and analogues). These alkyl moieties may be substituted or unsubstituted as described below. The term “alkyl” refers to such moieties having C1–C8 carbon atoms. For structural reasons, linear alkyls are understood to begin at C1, branched alkyls at C3, and polycyclic alkyls at C5. Furthermore, moieties derived from alkyls as described below, e.g., alkyloxys and perfluoroalkyls, are understood to have the same carbon number range unless otherwise specified. If different alkyl group lengths are specified, the above definition of alkyl remains valid in that it encompasses all types of alkyl moieties, and the above structural considerations regarding the minimum carbon number of a given type of alkyl group still apply.

[0046] Alkyloxy (also known as alkoxy) refers to an alkyl group bonded via an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and similar compounds). These alkyloxy moieties may or may not be substituted, as described below.

[0047] A halo or halide refers to a halogen, F, Cl, Br, or I that is bonded to an organic part by a single bond.

[0048] As used herein, the term lactone encompasses both monolactones (e.g., caprolactone) and dilactones (e.g., lactides).

[0049] Haloalkyl refers to linear, cyclic, or branched saturated alkyl groups, such as those described above, in which at least one of the hydrogen atoms is replaced by a halide selected from the group consisting of F, Cl, Br, I, or a mixture of these if more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0050] Perfluoroalkyls refer to linear, cyclic, or branched saturated alkyl groups in which all hydrogen atoms are replaced by fluorine atoms, as defined above (e.g., trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and analogues).

[0051] As used herein to describe various embodiments of the polymers or compounds of the present invention, the term oligoflexible tethered group refers to a group of groups including oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups.

[0052] In the various embodiments of the polymers or compounds of the present invention described herein, the term oligolinear alkylene tezade group, in its broadest embodiment, refers to a group having the following general structure: -X1-(CH2) a -CH3, where a is 6 to 18, and X1 is selected from direct valence bonds, linear C1-C4 alkylene spacers, -O-, -CH2-O-, -O-(C=O)-, -C=OO-, C=O, -CH2-O-(C=O)-, -S-, -SO2-, -SO-.

[0053] In one embodiment, X1 is a direct valence bond. In another embodiment, X1 is a linear C1-C4 alkylene spacer. In yet another embodiment, X1 is -O-, and in yet another embodiment, this is -CH2-O; in yet another embodiment, X1 is -O-(C=O)-. In yet another embodiment, X1 is -C=OO-. In yet another embodiment, X1 is a carbonyl (C=O). In yet another embodiment, X1 is -CH2-O-(C=O)-. In yet another embodiment, X1 is -S-. In yet another embodiment, X1 is -SO2-. In yet another embodiment, X1 is -SO-. A more specific type of these group is -O-(CH2) a -CH3, or -CH2-O-(CH2) a -CH3, where a is 6 to 19. In one more specific form, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 7 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 7 to 10. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 8 to 9. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 8. In one of the other more specific embodiments, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 7 to 14. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 7 to 13. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a-CH3 has a range from 8 to 13. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a equal to 13. In one of the other more specific embodiments, -O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 7 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 8 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 9 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a range from 10 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 11 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 12 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 13 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 13 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 14 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a-CH3 has a from 15 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 16 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 17 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a from 18 to 19. In one of the more selective embodiments, O-(CH2) a -CH3 or -CH2-O-(CH2) a -CH3 has a value of 18 equal to a. These linear alkylene tezade groups may be unsubstituted or substituted with C1-C8 alkyl groups that form a branching point.

[0054] In various embodiments of the polymers or compounds of the present invention described herein, the term oligoether tethered group refers to a material having the following general structure: -O-[(CH2) e -O-] e2 -(CH2) e3 -H, -(CH2) e4 -O-(CH2) e -O-(CH2) e2 -(CH2) e3 -H, where independently, e is from 2 to 8, e2 is from 2 to 8, e3 is from 1 to 8, and e4 is from 1 to 8. In one specific mode, this is -O-(CH2-CH2-O) e2 -(CH2) e3 -H; in one more specific aspect of this embodiment, this is O-(CH2-CH2-O) e2-(CH3); in one more specific aspect of this embodiment, this is -CH2-O-(CH2-CH2-O)4-CH3; in yet another more specific aspect, this is O-(CH2-CH2-O)4-CH3. In one more specific aspect, this is -CH2-O-(CH2-CH2-O) e2 -(CH2) e3 -H. In one more specific aspect, this is -CH2-O-(CH2-CH2-O) e2 -CH3, and in one more specific aspect of this embodiment, this is CH2-O-(CH2-CH2-O)4-CH3, and in one more specific aspect of this embodiment, this is CH2-O-(CH2-CH2-O)2-CH3. These oligoether tethered groups may be unsubstituted or substituted with a C1-C8 alkyl group forming a branch point.

[0055] The term oligo-dialkylsiloxane tethered groups present in various aspects of the polymers or compounds of the invention described herein refers to groups having the following general structure -X2-[Si(alkyl)2-O] s -Si(alkyl)3, where s ranges from 6 to 18, and the alkyl moiety is C1-C8 alkyl, and X2 is a direct valence bond, or a C1-C8 linear alkylene spacer, or -O-. In one more specific aspect of this embodiment, this is -O-[Si(alkyl)2-O] s -Si(alkyl)3, and in one more specific aspect of this embodiment, this is -O-[Si(CH3)2-O] s -Si(CH3)3. In one more specific aspect of this embodiment, this is -CH2-O-[Si(alkyl)2-O] s -Si(alkyl)3, and in one more specific aspect of this embodiment, this is -CH2-O-[Si(CH3)2-O] s -Si(CH3)3.

[0056] One aspect of the present invention is a block copolymer having structure (1), wherein segment A is a polar block copolymer segment comprising one of alkyl 2-methylene alkanoate-derived repeating units, lactone-derived repeating units, oxirane-derived repeating units, oxetane-derived repeating units, or cyclic carbonate-derived repeating units; L is a direct valence bond or a linkage derived from 1,1-diarylethene; segment B is a non-polar block copolymer segment comprising styrene-based repeating units, and E is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and alkyl 2-aryl acrylate-derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0057] EALBLAE (1) Furthermore, 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.

[0058] Furthermore, these oligoflexible tethered groups are multi-tethered in the polymer block copolymer of structure (1) at positions selected from the following arrangements: The oligoflexible tethered group is present only in segment A, and is randomly located along this segment on some of its repeating units, or present in each of its repeating units.

[0059] The oligoflexible tethered group is present only in segment B, and is randomly located along this segment on some of its repeating units, or present in each of its repeating units.

[0060] The oligoflexible tethered group is present in both segment A and segment B, and is randomly located along these segments on only a portion of their repeating units, or is present in each of their repeating units.

[0061] The aforementioned oligoflexible tethered groups are located on both E-terminal groups when they are alkyl-terminal groups or alkyl 2-aryl acrylate derivative terminal groups (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0062] The oligoflexible tethered group is present on both L when L is a linking portion derived from 1,1-diarylethene.

[0063] The aforementioned oligoflexible tethered group is located in the center of the B segment.

[0064] The oligoflexible tethered group is located on at least one of the A segment, B segment, L (if L is the connecting portion), and terminal group E.

[0065] Furthermore, the block copolymer has polydispersity in the range of 1 to about 1.09. In one other aspect of this embodiment, this is in the range of 1 to about 1.08; in yet another embodiment, this is in the range of 1 to about 1.07; in yet another embodiment, this is in the range of 1 to about 1.06; in yet another embodiment, this is in the range of 1 to about 1.05; in yet another embodiment, this is in the range of 1 to about 1.03; in yet another embodiment, this is in the range of 1 to about 1.02; in yet another embodiment, this is in the range of 1 to about 1.01; and in one embodiment, this has polydispersity of 1.

[0066] In one aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A comprises repeating units derived from lactones. In one aspect of this embodiment, the lactone is a monolactone such as caprolactone and analogues. In another aspect of this embodiment, the lactone is a dilactone such as lactide and analogues.

[0067] In one aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A1 comprises repeating units derived from oxiranes. In one aspect of this embodiment, the repeating units are derived from ocetanes. In another aspect of this embodiment, the repeating units are derived from substituted oxetanes. In yet another aspect of this embodiment, they are derived from alkyl-substituted oxetanes.

[0068] In one aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A1 comprises repeating units derived from oxiranes. In one aspect of this embodiment, the repeating units are derived from oxiranes. In another aspect, they are derived from substituted oxiranes. In yet another aspect of this embodiment, they are derived from alkyl-substituted oxiranes. In one aspect of this embodiment, they are derived from 2-methyloxiranes.

[0069] In one aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A1 comprises repeating units derived from a cyclic carbonate. In one aspect of this embodiment, these are derived from 1,3-dioxolan-2-one. In another aspect of this embodiment, these are derived from substituted 1,3-dioxolan-2-one. In yet another aspect of this embodiment, these are derived from 2-alkyl-dioxolan-2-one. In yet another aspect of this embodiment, these are derived from 2-methyl-dioxolan-2-one.

[0070] In another aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A comprises alkyl 2-methylene alcanoate repeating units. In one aspect of this embodiment, the alkyl 2-methylene alcanoate is selected from those having any one of the following structures.

[0071] [Chemical formula] In another aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A has an M between about 20,000 and about 200,000 w and the nonpolar styrenic block copolymer segment B has an M between 20,000 and about 200,000 w In another aspect of this embodiment, the polar block copolymer segment A has an M between about 30,000 and about 170,000 w and the nonpolar styrenic block copolymer segment B has an M between 40,000 and about 160,000 w In another aspect of this embodiment, the polar block copolymer segment A has an M between about 30,000 and about 167,000 w and the nonpolar styrenic block copolymer segment B has an M between 40,000 and about 150,000 w and the nonpolar styrenic block copolymer segment B has an M between 40,000 and about 150,000

[0072] In another aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A has an M between about 20,000 and about 200,000 n and the nonpolar styrenic block copolymer segment B has an M between 20,000 and about 200,000 n In another aspect of this embodiment, the polar block copolymer segment A has an M between about 25,000 and about 170,000 nThe nonpolar styrene-based block copolymer segment B has a mass between 30,000 and about 160,000. n It has. In one other aspect of this embodiment, the polar block copolymer segment A has M between about 28,000 and about 155,000 n The nonpolar styrene-based block copolymer segment B has a mass between 40,000 and about 135,000. n It has.

[0073] In one other view of the block copolymer of structure (1) described herein, L is a direct valence bond. In another view, L is a linkage derived from 1,1-diarylethene.

[0074] In one of the other aspects of the block copolymer of structure (1) described herein, E is either H or an alkyl group. In one of the other aspects of this embodiment, it is H. In one of the other aspects of this embodiment, it is an alkyl group.

[0075] In another aspect of the block copolymer of structure (1) described herein, E is a terminal group derived from an alkyl-2-aryl acrylate.

[0076] In one of the other aspects of the block copolymer of structure (1) described herein, E is a carbonylalkyl (-C=O-alkyl) or carbonyloxyalkyl (-C=OO-alkyl). In another aspect of this embodiment, it is a carbonylalkyl (-C=O-alkyl). In yet another aspect of this embodiment, it is a carbonyloxyalkyl (-C=OO-alkyl).

[0077] In one other aspect of the block copolymer of structure (1), it has structure (2), where R1, R2, R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the aforementioned oligoflexible tethered group, where at least one of R1, R2, R3, R4, R5, R6, and R7 is further selected from the aforementioned oligoflexible tethered group, and n is the number of repeating units. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in another aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0078] [ka] In another aspect of the block copolymer of structure (1), it has structure (3), where R1 and R2 are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the aforementioned oligoflexible tethered group, and R8 and R9 are individually selected from C1-C5 alkyl and the aforementioned oligoflexible tethered group, R 10 is H or C1-C5 alkyl, R 11R1 is H, C1-C5 alkyl, halide, or C1-C5 alkyloxy; where further, at least one of R1, R2, R8, and R9 is selected from the aforementioned oligoflexible tethered group, and n1 is the number of repeating units. In one other aspect of the block copolymer of structure (1), it has structure (2), where R1, R2, R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the aforementioned oligoflexible tethered group, provided that at least one of R1, R2, R3, R4, R5, R6, and R7 is selected from the aforementioned oligoflexible tethered group, and n is the number of repeating units. In one other aspect of the group of this embodiment, R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one further aspect of this embodiment, R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In yet another aspect of this embodiment, R8 is selected from the oligoflexible tethered group, and R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether etherted group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

[0079] In one other aspect of the block copolymer of structure (3), R9 and R8 are individually selected from the oligoflexible tethered groups, and R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In another aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

[0080] In one other aspect of the block copolymer of structure (3), R1, R2, and R8 are individually selected from the oligoflexible tethered groups described above. In another aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position; in another aspect of this embodiment, it is in the meta position; and in yet another aspect, it is in the para position.

[0081] [ka] In another aspect of the block copolymer of structure (1) described herein, it has structure (4), where R1 and R2 are respectively selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the aforementioned oligoflexible tethered group, R 9a and R 9b These are individually selected from C1-C5 alkyl groups and the aforementioned oligoflexible tethered groups, R 10a and R 10b Each is individually selected from H or C1-C5 alkyl, and R12 is H or C1-C5 alkyl, however R1, R2, R 9a and R 9b At least one of the oligoflexible tethered groups is selected, and n2 and n3 are the number of repeating units. In one other aspect of this embodiment, R 9b R is selected from the oligoflexible tethered groups, 9a R1 is a C1-C5 alkyl group, and R1 and R2 are individually selected from H, a C1-C5 alkyl group, a halide, and a C1-C5 alkyloxy group. In one other aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

[0082] In one of the other embodiments of the block copolymer of structure (4) described herein, R 9a and R 9b R1 and R2 are individually selected from C1-C5 alkyl groups, and R1 and R2 are individually selected from H, C1-C5 alkyl groups, halides, and C1-C5 alkyloxy groups, and the oligoflexible tethered group is an oligoether tethered group, wherein at least one of R1 and R2 is selected from the oligoflexible tethered group. In one other aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, the oligodialkylsiloxane tethered group, if present on an aromatic ring, is located in the para or meta position.

[0083] In one of the other embodiments of the block copolymer of structure (4) described herein, R 9a and R9b R1 and R2 are individually selected from the oligoflexible tethered groups, and R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one other aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in one other aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0084] [ka] In one other aspect of the block copolymer of structure (1) described herein, it has structure (5), where R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the oligoflexible tethered group, and at least one of R3, R4, R5, R6, and R7 is selected from the oligoflexible tethered group, provided that the EAL portion in structure (5) does not contain at least one of the oligoflexible tethered groups, and L is either a direct valence bond or a linkage derived from 1,1-diarylethene. Yes, segment A is the polar block copolymer segment comprising one of alkyl 2-methylene alkanoate derived repeating units, lactone derived repeating units, oxirane derived repeating units, oxetane derived repeating units, or cyclic carbonate derived repeating units; E is the terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and alkyl 2-aryl acrylate derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl), and n4 is the number of repeating units. In one aspect of this embodiment, L is a direct valence bond. In another aspect of this embodiment, L is a linkage derived from 1,1-diarylethene. In yet another aspect of this embodiment, L is a linkage derived from a 1,1-diphenylethene derivative. In yet another aspect of this embodiment, R5 and R6 are selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In yet another aspect of this embodiment, R5 and R6 are selected from the oligoflexible tethered group. In yet another aspect of this embodiment, R3, R4, and R7 are selected from the oligoflexible tethered group. In yet another aspect of this embodiment, R3, R4, R5, R6, and R7 are selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.In yet another aspect of this embodiment, the oligoflexible tethered group, if present on an aromatic ring, is in the para or meta position; in yet another aspect of this embodiment, it is in the meta position; and in yet another aspect, it is in the para position.

[0085] [ka] In one other aspect of the block copolymer of structure (5) described herein, EAL has structure (3a), where * represents the bonding site of the EAL moiety to B, R1 and R2 are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the aforementioned oligoflexible tethered group, and R8 and R9 are individually selected from C1-C5 alkyl and the aforementioned oligoflexible tethered group, R 10 is H or C1-C5 alkyl, R 11 is H, C1-C5 alkyl, halide, or C1-C5 alkyloxy; however, at least one of R1, R2, R8, and R9 is selected from the oligoflexible tethered groups, provided that B does not have at least the oligoflexible tethered groups, and n5 is the number of repeating units.

[0086] In one of the other aspects of the block copolymer of structure (5) having structure (3a) described herein, R8 is selected from the oligoflexible tethered groups, and R1 and R2 are selected, respectively, from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one of the other aspects of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in one of the other aspects of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0087] In one of the other aspects of the block copolymer of structure (5) having structure (3a) described herein, R9 and R8 are individually selected from the oligoflexible tethered groups, and R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one of the other aspects of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, R1, R2, and R8 are individually selected from the oligoflexible tethered groups. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in another aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0088] In one of the other aspects of the block copolymer of structure (5) having structure (3a) described herein, R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In yet another aspect of this embodiment, R3, R4, R5, R6, and R7 are in the para or meta position, in another aspect of this embodiment they are in the meta position, and in yet another aspect they are in the para position.

[0089] [ka] In one other aspect of the block copolymer of structure (5) described herein, EAL has structure (4a), where * represents the bonding site of the EAL moiety to B, R1 and R2 are respectively selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the aforementioned oligoflexible tethered group, R 9a and R 9b These are individually selected from C1-C5 alkyl groups and the aforementioned oligoflexible tethered groups, R 10a and R 10b Each is individually selected from H or C1-C5 alkyl, and R 12 is H or C1-C5 alkyl. Furthermore, in this embodiment, R1, R2, R 9a and R 9b At least one of the oligoflexible tethered groups is selected from the oligoflexible tethered groups, unless B has at least one of the oligoflexible tethered groups, where n6 and n7 are the number of repeating units. In one aspect of this embodiment, R 9b R is selected from the oligoflexible tethered groups, 9a R1 is a C1-C5 alkyl group, and R1 and R2 are individually selected from H, a C1-C5 alkyl group, a halide, and a C1-C5 alkyloxy group. In one other aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in one other aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position. In yet another aspect of this embodiment, the oligoflexible tethered group, if present on an aromatic ring, is in the para or meta position; in yet another aspect of this embodiment, it is in the meta position; and in yet another aspect, it is in the para position.

[0090] In another view of the block copolymer having structure (5) in EAL, R 9a and R 9b R1 and R2 are individually selected from C1 to C5, and R1 and R2 are individually selected from H, C1 to C5 alkyl, halide, and C1 to C5 alkyloxy, and the oligoflexible tethered group is an oligoether tethered group, wherein at least one of R1 and R2 is selected from the oligoflexible tethered group. In one other aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoetherether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in one other aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0091] In another view of the block copolymer having structure (5) in EAL, R 9a and R 9b R1 and R2 are individually selected from the aforementioned oligoflexible tethered groups, and R1 and R2 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligolinear alkylene tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligoether tethered group. In yet another aspect of this embodiment, the oligoflexible tethered group is an oligodialkylsiloxane tethered group. In yet another aspect of this embodiment, if the oligoflexible tethered group is present on an aromatic ring, it is in the para or meta position, in yet another aspect of this embodiment, it is in the meta position, and in yet another aspect, it is in the para position.

[0092] In one of the other aspects of the block copolymer of structure (5) having structure (4a) described herein, R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one of the other aspects of the block copolymer of structure (5) having structure (4a) described herein, R3, R4, R5, R6, and R7 are individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy. In one of yet another aspects of this embodiment, R3, R4, R5, R6, and R7 are individually in the para or meta position, in one of the other aspects of this embodiment, they are in the meta position, and in one of yet another aspect, they are in the para position.

[0093] [ka] Another aspect of the present invention is a block copolymer of structure (6), where A1 comprises one of alkyl 2-methylene alkanoate derivative repeating units, lactone derivative repeating units, oxirane derivative repeating units, oxetane derivative repeating units, or cyclic carbonate repeating units, with a temperature range of about 50°C to about 100°C. g It is a polar block copolymer segment having; and B1 is a T from about 50°C to about 100°C. g This is a styrene-based block copolymer segment having a temperature range of approximately -5°C to approximately 50°C. gThe block copolymer segment comprises repeating units derived from any olefin selected from the group consisting of alkenes, alkadienes, or alkatrienes, or from a mixture of at least two different olefins selected from this group. Furthermore, in this embodiment, L1 is either a direct valence bond or a linking moiety derived from 1,1-diarylethene, and E1 is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl), and alkyl2-arylacrylate derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl). Furthermore, the block copolymer of structure (6) has polydispersity in the range of 1 to about 1.09.

[0094] E1-A1-L1-B2-B1-B2-L1-A1-E1(6) In one aspect of the block copolymer of structure (6), the repeating units in B2 are derived from an alkene. In yet another aspect, B2 is derived from an alkadiene. In yet another aspect, B2 derived from an alkadiene is a conjugated diene.

[0095] In another aspect of the block copolymer of structure (6), B2 comprises a mixture of at least two different olefinic repeating units having structures (7a), (7b), (7c), and (7d) derived from an alkadiene, where R d , R d1 , R d2 , R d3 , R e , R e1 , R e2 , and R e3 These are individually selected from the group consisting of H and C1-C8 alkyl groups, and further, the total mole% of these olefin repeating units in the block copolymer is in the range of about 3 mol% to about 50 mol%. In one aspect of this embodiment, R d , R d1 , R d2 , and R d3They are identical, selected from H or C1-C8 alkyl, and R e , R e1 , R e2 , and R e3 This is selected from H or C1-C8 alkyl groups.

[0096] [ka] In one other aspect of the block copolymer of structure (6), B2 comprises repeating units derived from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isoprene, 3-methylenepenta-1-ene, 3-methylenehexa-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepenta-1-ene, 1,3-butadiene, ethylidene norbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinyl norbornene (2-vinylbicyclo[2.2.1]hepta-2-ene), chloroprene (2-chlorobuta-1,3-diene), or a mixture of at least two of these.

[0097] In one aspect of the block copolymer of structure (6) described herein, in which B2 comprises repeating units derived from an alkadiene, the alkadiene is a non-conjugated diene.

[0098] In one other aspect of the block copolymer of structure (6) described herein, B2 comprises repeating units derived from an alkatriene.

[0099] In one other aspect of the block copolymer of structure (6) described herein, B2 comprises repeating units derived from a mixture of at least two different olefins selected from the group consisting of alkenes, alkadienes, and alkatrienes.

[0100] In one other aspect of the block copolymer of structure (6) described herein, B2 further comprises styrene repeating units.

[0101] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises repeating units derived from lactones. In one aspect of this embodiment, the lactone is a monolactone such as caprolactone and analogues. In another aspect of this embodiment, the lactone is a dilactone such as lactide and analogues.

[0102] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises repeating units derived from oxiranes. In one aspect of this embodiment, the repeating units are derived from ocetanes. In another aspect of this embodiment, the repeating units are derived from substituted oxetanes. In yet another aspect of this embodiment, they are derived from alkyl-substituted oxetanes.

[0103] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises repeating units derived from oxiranes. In one aspect of this embodiment, the repeating units are derived from oxiranes. In another aspect, they are derived from substituted oxiranes. In yet another aspect of this embodiment, they are derived from alkyl-substituted oxiranes. In one aspect of this embodiment, they are derived from 2-methyloxiranes.

[0104] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises repeating units derived from a cyclic carbonate. In one aspect of this embodiment, these are derived from 1,3-dioxolan-2-one. In another aspect of this embodiment, these are derived from substituted 1,3-dioxolan-2-one. In yet another aspect of this embodiment, these are derived from 2-alkyl-dioxolan-2-one. In yet another aspect of this embodiment, these are derived from 2-methyl-dioxolan-2-one.

[0105] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises an alkyl 2-methylene alkanoate derived repeating unit. In one aspect of this embodiment, the alkyl 2-methylene alkanoate is selected from having any one of the following structures:

[0106] [ka] In one other aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises methyl methacrylate-derived repeating units.

[0107] In another aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises oxirane-derived repeating units.

[0108] In one aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 comprises carbonate-derived repeating units.

[0109] In one other aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 is between 20,000 and about 200,000 M w The nonpolar block copolymer segment has a ratio of M between 20,000 and about 200,000. w It has. In one other aspect of the block copolymer of structure (6) described herein, the polar block copolymer segment A1 has M between about 20,000 and about 200,000 w The nonpolar styrene-based block copolymer segment B has a M between 20,000 and about 200,000. w It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 30,000 and about 170,000 wThe nonpolar styrene-based block copolymer segment B has a mass between 40,000 and about 160,000. w It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 30,000 and about 167,000 w The nonpolar styrene-based block copolymer segment B has a mass between 40,000 and about 150,000. w It has.

[0110] In one aspect of the block copolymer of structure (1) described herein, the polar block copolymer segment A1 is between approximately 20,000 and approximately 200,000 M n The nonpolar styrene-based block copolymer segment B has a M between 20,000 and about 200,000. n It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 25,000 and about 170,000 n The nonpolar styrene-based block copolymer segment B has a mass between 30,000 and about 160,000. n It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 28,000 and about 155,000 n The nonpolar styrene-based block copolymer segment B has a mass between 40,000 and about 135,000. n It has.

[0111] In another aspect of the block copolymer of structure (6) described herein, L1 is a direct valence bond.

[0112] In another aspect of the block copolymer of structure (6) described herein, L1 is a linking group derived from 1,1-diarylethene.

[0113] In another aspect of the block copolymer of structure (6) described herein, E1 is either H or alkyl.

[0114] In another aspect of the block copolymer of structure (6) described herein, E1 is a group derived from alkyl-2-aryl acrylate.

[0115] In one other aspect of the block copolymer of structure (6) described herein, E is a carbonylalkyl (-C=O-alkyl) or carbonyloxyalkyl (-C=OO-alkyl).

[0116] In another aspect of the block copolymer of structure (6) described herein, it more specifically has structure (7) comprising a central nonpolar styrene-based block copolymer segment bonded to the partial-B2-A1-E1 at both ends, R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , and R 7a R is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, and n8 is the number of repeating units. In one aspect of this embodiment, R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , and R 7a is H. In another aspect of this embodiment, B2 comprises a mixture of at least two repeating units derived from olefins. In another aspect of this embodiment, B2 comprises a mixture of at least two different repeating units derived from alkadienes. In another aspect of this embodiment, B2 comprises a mixture of two different olefinic repeating units derived from conjugated dienes. In another aspect of this embodiment, B2 comprises at least two different repeating units having structures (7a), (7b), (7c) and (7d), where R d , R d1 , R d2 , R d3 , R e , R e1 , R e2 , and R e3,These are individually selected from the group consisting of H and C1-C8 alkyl groups, and furthermore, the total mole% of these olefin repeating units in the block copolymer is in the range of about 3 mol% to about 50 mol%. In one aspect of this embodiment, R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , and R 7a is H. In yet another aspect of this embodiment, R d , R d1 , R d2 , R d3 , R e , R e1 , R e2 , and R e3 These are individually selected from the group consisting of H and C1-C8 alkyl groups, and the total mole% of these olefin repeating units in the block copolymer is in the range of about 3 mol% to about 50 mol%. In yet another aspect of this embodiment, R d , R d1 , R d2 , and R d3 They are identical, and selected from H or C1-C8 alkyl, and R e , R e1 , R e2 , and R e3 is selected from H or C1-C8 alkyl. In one aspect of this embodiment, R d , R d1 , R d2 , R d3 , R e , R e1 , R e2 , and R e3 These exist individually at either the para or meta position, in one of the other embodiments they exist at the para position, and in yet another embodiment they exist at the meta position.

[0117] [ka] In one other aspect of the block copolymer of structure (6) having the more specific structure (7) described herein, B2 is a block copolymer segment having repeating units derived from isoprene or butadiene. In one aspect of this embodiment, it is derived from isoprene. In another aspect of this embodiment, it is derived from butadiene.

[0118] In one aspect of the block copolymer of structure (7) described herein, the polar block copolymer segment A1 is between approximately 20,000 and approximately 200,000 M w The nonpolar styrene-based block copolymer segment B1 has a mass between 20,000 and about 200,000. w It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 25,000 and about 150,000 w The nonpolar styrene-based block copolymer segment B1 has a mass between 40,000 and about 140,000. w It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 29,000 and about 120,000 w The nonpolar styrene-based block copolymer segment B1 has a mass between 45,000 and about 110,000. w It has.

[0119] In one aspect of the block copolymer of structure (7) described herein, the polar block copolymer segment A1 is between approximately 20,000 and approximately 200,000 M n It has, and block copolymer segment B2 has M between 20,000 and about 200,000 n It has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 27,000 and about 145,000 n It has, and block copolymer segment B2 is between 43,000 and approximately 135,000 M nIt has. In one other aspect of this embodiment, the polar block copolymer segment A1 has M between about 28,000 and about 115,000 n It has, and copolymer segment B2 has M between 40,000 and about 100,000 n It has.

[0120] In another aspect of the block copolymer of structure (6) having the more specific structure (7) described herein, the polar block copolymer segment A1 comprises repeating units derived from lactones.

[0121] In one other aspect of the block copolymer of structure (6) having the more specific structure (7) described herein, the polar block copolymer segment A1 comprises alkyl 2-methylene alkanoate derived repeating units.

[0122] In one other aspect of the block copolymer of structure (6) having the more specific structure (7) described herein, E1 is H.

[0123] Another aspect of the present invention is a formulation comprising any one of the various embodiments of the block copolymer of the present invention described herein and a spin-casting solvent. This includes the block copolymer families represented by various embodiments of two different block copolymer families, structure (1) and structure (6), as well as the various embodiments of these two block copolymer families described herein.

[0124] In another aspect of the composition of the present invention, this includes at least two different block copolymers belonging to the block copolymer family represented by structure (1), and various embodiments of this block copolymer described herein.

[0125] In another aspect of the composition of the present invention, this includes at least two different block copolymers belonging to the block copolymer family represented by structure (6), and various embodiments of this block polymer described herein.

[0126] In another aspect of the compositions of the present invention, this includes at least two different block copolymers, of which at least one belongs to the block copolymer family represented by structure (1) and at least one belongs to the block copolymer family represented by structure (6), and various embodiments thereof as described herein.

[0127] In another aspect of the composition of the present invention, it comprises at least one block copolymer belonging to the block copolymer family represented by structure (1), and any of the various embodiments thereof described herein, and further comprises other types of block copolymers. In one aspect of this aspect, the block copolymer would be a diblock or triblock copolymer of styrene-based repeating units and alkyl 2-methylene alkanoate-derived repeating units. In one aspect of this aspect, the block copolymer would be a diblock copolymer of styrene and methyl methacrylate.

[0128] In another aspect of the composition of the present invention, it comprises at least one block copolymer belonging to the block copolymer family represented by structure (6), and any of the various embodiments thereof described herein, and further comprises other types of block copolymers. In one aspect of this aspect, the block copolymer would be a diblock or triblock copolymer of styrene repeating units and alkyl 2-methylene alkanoate derived repeating units. In one aspect of this aspect, the block copolymer would be a diblock copolymer of styrene and methyl methacrylate.

[0129] In another aspect of the composition of the present invention, it belongs to the block copolymer family represented by structure (1) and comprises at least one block copolymer from any of the various embodiments thereof described herein, and further comprises a homopolymer. In one aspect of this aspect, the homopolymer is a homopolymer of alkyl 2-methylene alkanoate. In one aspect of this aspect, the homopolymer is a homopolymer of methyl methacrylate.

[0130] In another aspect of the composition of the present invention, it comprises at least one block copolymer belonging to the block copolymer family represented by structure (6), and any of the various embodiments thereof described herein, and further comprises a homopolymer. In one aspect of this aspect, the homopolymer is a homopolymer of alkyl 2-methylene alkanoate. In one aspect of this aspect, the homopolymer is a homopolymer of methyl methacrylate.

[0131] In the compositions of the present invention 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, including glycol ether derivatives, e.g., 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, e.g., ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, e.g., ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, e.g., diethyl oxilate and diethyl malonate; dicarboxylates of glycols, e.g., ethylene glycol diacetate and propylene Examples include glycol diacetate; 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.

[0132] In addition, the compositions of the present invention described above further comprise surfactants, inorganic polymers; additives including small molecules, inorganic molecules, surfactants, photoacid generators, thermoacid generators, quenchers, curing agents, crosslinking agents, chain extenders, and similars; and additives selected from the group consisting of combinations of at least one of the above, wherein one or more of the additional components and / or additives assemble with the block copolymer to form a block copolymer assembly.

[0133] Another aspect of the present invention is a method for orienting first and second block copolymer domains vertically on an unpatterned substrate using a layer of block copolymer having periodicity L0, the following steps: a) The step of forming a block copolymer coating layer on the unpatterned substrate using the composition of the present invention described herein; and b) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the unpatterned substrate; This method includes [something].

[0134] Another aspect of the present invention is a method for aligning first and second block copolymer domains vertically on a first patterned substrate using a coating comprising a periodic L0 block copolymer, wherein the topographic height of the pattern on the substrate is at least 0.7 times L0, and these domains are aligned in the pattern, the next step being: a1) forming a coating layer of the composition of the present invention on the first topographic substrate using the composition described herein, wherein the average thickness of the block copolymer coating layer is thinner than the topographic height of the first topographic substrate, and the block copolymer layer is laterally enclosed by the topography; b1) Annealing the block copolymer layer to generate first and second block copolymer domains that are oriented perpendicularly to the first patterned substrate and confined within recessed regions; This method includes [something].

[0135] Another aspect of the present invention is a method for aligning first and second block copolymer domains of periodic L0 vertically on a second patterned substrate having a topographic pattern and pitch P1 where the topographic height is more than 0.7 times higher than L0, and where the pitch P1 is a positive integer other than zero multiplied by L0, and aligning these domains in the pattern, the next step being: a2) A block copolymer coating layer is formed on the second patterned substrate using the composition of the present invention as described herein, wherein the thickness of the block copolymer coating layer is greater than the height of the topography of the second patterned substrate; and b2) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the second patterned substrate, and aligning them on the second patterned substrate, where the total number of perpendicularly oriented domains is equal to or greater than the pitch P1 of the topographic pattern; This method includes [something].

[0136] Another aspect of the present invention is a method for aligning first and second block copolymer domains perpendicularly 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 the following steps: a) The step of forming a block copolymer coating layer on the substrate having a surface chemical prepattern using the composition of the present invention described herein; and b) Annealing the block copolymer layer to generate vertically oriented first and second block copolymer domains aligned on the substrate having a surface chemical pre-pattern having pitch P2; The method includes the above.

[0137] Another aspect of the present invention is a compound of structure (C1), where R1b , R 1c , R 2b , and R 2c is individually selected from H, halide, C1-C4 alkyl, C1-C4 alkyloxy, and oligo-flexible tethered group, provided that R 1b , R 2b , R 1c and R 2c of which at least one is an oligo-flexible tethered group, and R 3b , R 3c , R 4b , R 4c , R 5b and R 5c is individually selected from H, halide, C1-C4 alkyl, and C1-C4 alkyloxy.

[0138] [Chemical formula] In one embodiment of the compound of structure (C1), R 1b , R 1c , R 2b and R 2c is individually selected from H and oligo-flexible tethered group.

[0139] In one of the other embodiments of the compound of structure (C1), R 1b or R 2b only one of them, and R 1c and R 2c only one of them is an oligo-flexible tethered group.

[0140] In one of the other embodiments of the compound of structure (C1) above, R 1b or R 2b only one of them, or R 1c and R 2c only one of them is an oligo-flexible tethered group.

[0141] In one of the other embodiments of the compound of structure (C1) above, R 1b alone is an oligo-flexible tethered group.

[0142] In one of the other embodiments of the compound of the above structure (C1), R 2b alone is an oligo-flexible tethered group.

[0143] In one of the other embodiments of the compound of the above structure (C1), R 1b and R 1c alone are oligo-flexible tethered groups.

[0144] In one of the other embodiments of the compound of the above structure (C1), R 2b and R 2c alone are oligo-flexible tethered groups.

[0145] In one of the other embodiments of the compound of the above structure (C1), R 3b , R 3c , R 4b , R 4c , R 5b and R 5c are H.

[0146] In one of the other embodiments of the compound of the above structure (C1), the oligo-flexible tethered group is a linear alkylene tethered group.

[0147] In one of the other embodiments of the compound of the above structure (C1), the flexible oligo-flexible tethered group is an oligoether tethered group.

[0148] In one of the other embodiments of the compound of the above structure (C1), the flexible oligo-flexible tethered group is an oligo-dialkylsiloxane tethered group.

[0149] In one of the other embodiments of the compound of the above structure (C1), this has structure (C1-A), where a is from 7 to 19.

[0150]

Chemical formula

[0151]

Chem.

[0152]

Chem.

[0153]

Chem.

[0154]

Chem.

[0155]

Chem.

[0156]

Chem.

[0157] [ka] In another embodiment of the compound of the above structure (C1), it has structure (C1-I), where s is 6-18 and the alkyl portion is C1-C8 alkyl.

[0158] [ka] In another embodiment of the compound with the above structure (C1), it has structure (C1-J), where s is 6-18 and the alkyl portion is C1-C8 alkyl.

[0159] [ka] In another embodiment of the compound with the above structure (C1), it has the structure (C1-K), where s is 6-18 and the alkyl portion is C1-C8 alkyl.

[0160] [ka] In another embodiment of the compound of the above structure (C1), it has structure (C1-L), where s is 6-18 and the alkyl portion is C1-C8 alkyl.

[0161] [ka] [Examples]

[0162] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma Aldrich (3050 Spruce Street, St. Louis, MO63103). 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) (Non-Patent Literature 7)).

[0163] Phenyl acrylate derivatives were synthesized by esterifying acryloyl chloride with the corresponding hydroxyl compound under basic conditions, and DPE derivatives were synthesized by alkoxylylation of DPE-(m)-CH2Br(1-(bromomethyl)-3-(1-phenylvinyl)benzene) with the corresponding hydroxyl compound under basic conditions.

[0164] All synthesis experiments were performed in an N2 atmosphere. Lithography experiments were performed as described herein. The molecular weight of the copolymer was measured using gel permeation chromatography at 100 Å, 500 Å, and 10 3 Å, 10 5 Å and 10 6 Gel permeation chromatography equipped with an Åμ-ultrastylagel column.

[0165] Lithography experiments were performed using the TEL Clean ACT8 track. SEM images were taken using the NanoSEM 3D from Applied Materials. Scanning electron microscope images are shown at either 1FOV magnification or 2FOV magnification (field of view (FOV) = 5 μm).

[0166] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembling film block copolymers of methyl methacrylate and styrene.

[0167] Unless otherwise specified, molecular weight measurement (also known as M n (Polydispersible) 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 The analysis was performed using gel permeation chromatography (PSS Inc., Germany) with an Åμ-Ultrillagel column, using THF solvent as the eluent. Polystyrene polymer standards were used for calibration.

[0168] The glass transition temperature was measured using DSC (Digital Spectroscopy) with a heating rate of 10°C / min under nitrogen using a TA Instruments DSC Q1000. g The temperature was measured in the first heating scan from 0 to 300°C. The midpoint of the endothermic transition was taken into consideration.

[0169] 1 The 1H NMR spectrum was recorded using a Bruker Advanced III 400MHz spectrometer.

[0170] The molecular weight of the copolymer was measured using gel permeation chromatography. Unless otherwise stated, the chemicals were obtained from Sigma-Aldrich Corporation (St. Louis, Missouri).

[0171] Comparative Example 1: Synthesis of PMMA-b-PS-b-PMMA block copolymer: Styrene, methyl methacrylate, and 1,1'-diphenylethylene (DPE) monomer were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 2.4 mL (0.154 M solution) of potassium naphthalene was added to the reactor as an initiator. Then, 15 g (0.144 mol) of styrene was added to the reactor from the ampoule with rapid stirring. The reaction solution changed color to yellow-orange, and the reaction was stirred for 30 minutes. Next, 0.12 g (0.0007 mol) of 1,1'-diphenylethylene (DPE) was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark brick red color. This suggests that the styryl potassium active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for PS-DPE block molecular weight analysis. Next, methyl methacrylate (15 g, 0.15 mol) was added via an ampoule. This reaction was stopped after 50 minutes with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 28 g of PMMA-b-PS-b-PMMA (yield 94%). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column was performed with the first PS-DPE block at 87,000 g / mol relative to the PS calibration standard. n (GPC) and 1.03 M w / M n It was shown that it possessed the following properties. The molecular weight of the triblock copolymer obtained from GPC is M n,PMMA-b-PS-b-PMMA = 150,000 g / mol, Mw / M n = 1.07.

[0172] Example 2: This system demonstrates the synthesis of monotethered ABA having a C13 nonpolar tethered moiety (Scheme 1).

[0173] Styrene and methyl methacrylate monomers were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 3 mL (0.119 M solution) of potassium naphthalene was added to the reactor as an initiator. Next, 15 g (0.144 mol) of styrene was added from the ampoule to the reactor with vigorous stirring. The reaction solution changed color to yellow-orange, and the reaction was stirred for 30 minutes. Next, 0.17 g (0.00042 mol) of 1,1'-diphenylethylene-C was added. 13 H 25 (DPE-C 13 H 25 The C13 nonpolar tethered moiety was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark brick red color. This suggests that the potassium styryl active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for PS-DPE block molecular weight analysis. Methyl methacrylate (15 g, 0.15 mol) was then added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA. After 50 minutes, 0.25 g (0.00075 mol) of phenyl acrylate C 13 H 25The reaction mixture was then stopped with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 28 g of PMMA-b-PS-b-PMMA (94% yield). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column is performed with the first PS-DPE block at 83,000 g / mol relative to the PS calibration standard. n (GPC) and 1.04 M w / M n It was shown that it possessed the following properties. The molecular weight of the diblock copolymer obtained from GPC is M n,PMMA-b-PS-b-PMMA = 168,000 g / mol and M w / M n = 1.02.

[0174] [ka] Examples 3 and 4 were prepared in the same manner as in Example 2, except that Example 3 used 1-((octadecyloxy)methyl)-3-(1-phenylvinyl)benzene (DPE-C18) and octadecyl 2-phenylacrylate (phenylacrylate C18) (C18 nonpolar tethered moiety), and Example 4 used a DPE-polar tether and a phenylacrylate-polar tether. Their structures are as follows:

[0175] [ka] Example 5: Synthesis of PMMA-b-PDEGMA-b-PS-b-PGEGMA-b-PMMA block copolymer (Scheme 2): Styrene, methyl methacrylate, and 1,1'-diphenylethylene (DPE) monomer were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 3.9 mL (0.176 M solution) of potassium naphthalene was added to the reactor as an initiator. Then, 24 g (0.230 mol) of styrene was added to the reactor from the ampoule with rapid stirring. The reaction solution changed color to yellow-orange, and the reaction was stirred for 30 minutes. Next, 0.12 g (0.00067 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. This suggests that the styryl potassium active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for PS-DPE block molecular weight analysis. Next, 4.8 g (0.0255 mol) of diethylene glycol monomethyl ether (O3) methyl methacrylate (DEGMA) was added via an ampoule. The reaction was continued for 10 minutes to complete the polymerization of DEGMMA. After 10 minutes, 19.2 g (0.192 mol) of methyl methacrylate was added. This reaction was continued for 50 minutes and then stopped with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 45 g of PMMA-b-PDEGMA-b-PS-b-PGEGMA-b-PMMA (yield 95%). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column was performed with the first PS-DPE block at 83,700 g / mol relative to the PS calibration standard. n(GPC) and 1.05 M w / M n It was shown that it possessed the following properties. The molecular weight of the diblock copolymer obtained from GPC is M n,PMMA-b-PDEGMA-b-PS-b-PDEGMA-b-PMMA = 148,000 g / mol and M w / M n = 1.09.

[0176] [ka] Examples 6 and 10 were synthesized using a procedure similar to that described in Example 5. The only difference was that in the synthesis of Example 6, octylstyrene was used instead of DEGMA, and in Example 10, isoprene was used instead of DEGMA.

[0177] Example 7: Low T-block with multi-tethering to the center of the PS block g Synthesis of PMMA-b-PS-b-PC8S-b-PS-b-PMMA containing octylstyrene: Styrene and methyl methacrylate monomers were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 2.4 mL (0.154 M solution) of potassium naphthalene was added to the reactor as an initiator. Next, 3.45 g (0.016 mol) of n-octylstyrene was added to the reactor from the ampoule with rapid stirring. The reaction solution changed color from orange to red, and the reaction continued for 10 minutes. Then, 15 g (0.144 mol) of styrene was added to the reactor from the ampoule. The reaction solution changed color from yellow to orange, and the reaction was stirred for 30 minutes. Next, 0.12 g (0.00066 mol) of 1,1'-diphenylethylene was added to the reactor via an ampoule. The orange color of this reaction mixture changed to a dark brick red. This suggests that the styryl potassium active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for PS-DPE block molecular weight analysis. Next, methyl methacrylate (15 g, 0.15 mol) was added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA. The reaction mixture was then stopped with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 28 g of PMMA-b-PS-b-PC8S-b-PS-b-PMMA (yield 94%). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column was performed with the first PS-DPE block at 122,000 g / mol relative to the PS calibration standard. n (GPC) and 1.03 M w / M n It was shown that it possessed the following properties. The molecular weight of the diblock copolymer obtained from GPC is M n,PMMA-b-PS-b-Pos-b-PS-b-PMMA = 244,000 g / mol and M w / M n = 1.04.

[0178] Example 8: Synthesis of PMMA-bP(S-co-C8S)-b-PMMA having low Tg octyl styrene (PC8S) copolymerized in a PS block. Styrene, octylstyrene, and methyl methacrylate monomer were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 2.7 mL (0.154 M solution) of potassium naphthalene was added to the reactor as an initiator. A mixture of 3.45 g (0.016 mol) of n-octylstyrene and 15 g (0.144 mol) of styrene was then added from the ampoules to the reactor with rapid stirring. The reaction mixture changed color to orange-red, and the reaction continued for 30 minutes. Next, 0.12 g (0.00066 mol) of 1,1'-diphenylethylene was added to the reactor via an ampoule. The orange color of the reaction mixture changed to a dark reddish-brick color. This suggests that the styryl potassium active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for PS-DPE block molecular weight analysis. Next, methyl methacrylate (15 g, 0.15 mol) was added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA. The reaction mixture was then stopped with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 33 g of PMMA-bP(S-co-C8S)-b-PMMA (yield 94%). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 Gel permeabilization chromatography with an Åμ-Ultristor gel column is performed with the first PS-DPE block at 78,000 g / mol relative to the PS calibration standard. n (GPC) and 1.03 M w / M nIt was shown that it possessed the following properties. The molecular weight of the diblock copolymer obtained from GPC is M n,PMMA-b-P(S-co-C8S)-b-PS-b-PMMA = 138,000 g / mol and M w / M n = 1.03.

[0179] Example 9: This system is copolymerized in a PS block with low T g This describes the synthesis of P(MMA-co-C6MA)-bP(S-co-C8S)-bP(MMA-co-C6MA), which has hexyl methacrylate copolymerized in octyl styrene and PMMA blocks.

[0180] Styrene, octylstyrene, methyl methacrylate, and hexyl methacrylate monomers were distilled into calibrated ampoules in the presence of a dehydrating agent and stored under N2. The liquids were transferred to a reactor under N2, either through the ampoules or using stainless steel cannulas. 700 mL of anhydrous tetrahydrofuran was added to a dry 1 L volume round-bottom reactor equipped with side arms for connecting the ampoules, a magnetic stirrer bar, and a nitrogen / vacuum three-way diaphragm adapter. The temperature of the reactor was reduced to -78°C using a dry ice-acetone bath. After titration of impurities, 2.7 mL (0.154 M solution) of potassium naphthalene was added to the reactor as an initiator. A mixture of 3.45 g (0.016 mol) of n-octylstyrene and 15 g (0.144 mol) of styrene was then added from the ampoules to the reactor with rapid stirring. The reaction solution changed color to orange-red, and the reaction continued for 30 minutes. Next, 0.12 g (0.00066 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. This suggests that the styryl potassium active center was converted to the styrene-DPE carbanion. A small amount (2 mL) of the reaction mixture was taken for P(S-co-C8S)-DPE block molecular weight analysis. Next, a mixture of methyl methacrylate (15 g, 0.15 mol) and hexyl methacrylate (2.89 g, 0.017 mol) was added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA and C6MA. The reaction mixture was then stopped with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 40 g of P(MMA-co-C6MA)-bP(S-co-C8S)-bP(MMA-co-C6MA) (yield 94%). 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6Gel permeabilization chromatography with an Åμ-Ultristor gel column was performed with the first P(S-co-C8S)-DPE block at 87,000 g / mol relative to the PS calibration standard. n (GPC) and 1.04 M w / M n It was shown that it possessed the following properties. The molecular weight of the diblock copolymer obtained from GPC is M n,P(MMA-co-C6MA)-b-P(S-co-C8S)-b-PS-b-P(MMA-co-C6MA) = 154,000 g / mol and M w / M n = 1.07. Figure 7 shows copolymerized low T in PS block. g This shows the kinetic enhancement of this ABA terpolymer having copolymerized hexyl methacrylate in octyl styrene and PMMA blocks. 1FOV SEM image, process conditions: V: 250°C / 1 hour (N2); EBR 2 minutes, spin dry, 110°C / 1 minute, FT=140nm.

[0181] Comparative Example 2: Synthesis of a random x-crosslinkable copolymer (underlying polymer 1): A copolymer of styrene, methyl methacrylate, and 4-vinylbenzocyclobutene synthesized using AIBN. A 2000 ml flask equipped with a condenser, temperature controller, heating mantle, and mechanical stirrer was set up. 87.0 g (0.84 mol) of styrene (S), 139.8 g (1.40 mol) of methyl methacrylate (MMA), 72.4 g (0.56 mol) of 4-vinylbenzocyclobutene (VBCB), 1.83 g (0.011 mol) of azobisisobutyronitrile (AIBN) initiator, and 600 g of anisole were added to the flask. The mechanical stirrer was switched on and set to approximately 120 rpm. The reaction solution was then degassed by vigorously bubbling nitrogen into the solution at room temperature for approximately 30 minutes. After 30 minutes of degassing, the heating jacket was switched 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 switched off, and the reaction solution was allowed to cool to approximately 40°C. Next, this reaction mixture was poured into 12 L of isopropanol, and the mixture was stirred mechanically during the addition. During this addition, the polymer precipitated. The precipitated polymer was collected by filtration. The collected polymer was dried in a vacuum furnace at 40°C. Approximately 170 grams of polymer were obtained. This 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, the precipitated polymer was collected, and dried under vacuum at 40°C as described above. In this way, 150 grams (50% yield) of polymer were obtained after drying. This polymer had a Mw of approximately 38 k and a polydispersity (PDI) of 1.5.

[0182] Processing Example 1: Self-assembly of block copolymers (BCPs) Comparative Example 1 vs. Example 2 (Table 1) The polymers of Comparative Example 1 and Example 2 were individually dissolved in PGMEA to form 3.2 wt% solutions of each. These solutions were individually filtered through a 0.02 μm PTFE filter. The filtered 0.33 wt% solution of lower layer polymer 1 was then subjected to SiO2 filtration at 1500 rpm. xSiOx wafers coated with a crosslinked neutral layer (FT8nm) of the underlying polymer 1 were prepared by coating a wafer and then baking it in air at 250°C for 2 minutes. These neutral-coated wafers were then individually coated with a 3.2 wt% PGMEA solution filtered through 0.02 μm PTFE of a standard ABA triblock copolymer of styrene and methyl methacrylate (PMMA-b-PS-b-PMMA) (Comparative Example 1) or a monotethered ABA with a C13 nonpolar tethered moiety (Example 2). These films were spin-coated at 1,500 rpm, then soft-baked at 110°C for 1 minute, and then annealed under N2 at 250°C for 1 hour. Figure 5 shows a comparison of the self-assembly patterns of the films in Comparative Example 1 (Figure 5A) and Example 2 (Figure 5B) after plasma etching. The etching conditions were as follows: O2 (50 sccm):N2 (50 sccm) for 30 seconds, power = 50W, RIE = 100, using a trion etcher. Total number of defects measured. Defect counting using Hitachi software. These figures show that a normal non-tethered ABA (Figure 5A) shows a total number of defects of 101, while a) monotethered ABA shows an improved number of defects of 60 with improved granularity and a faster rate (Figure 5B).

[0183] Processing Example 2: Self-assembly of block copolymers (BCPs) Comparative Example 1 vs. Example 4 (Table 1) The polymer from Example 4 was dissolved in PGMEA to prepare a 3.2% by weight solution. This solution was filtered using a 0.02 μm PTFE filter, and then coated with SiO2 (as described in Processing Example 1) at 1500 rpm. xA coating of the polymer of Example 4 was formed by coating a wafer. This coating of the polymer of Example 4 was heated at 250°C for 1 hour. This material forms a self-assembling pattern in which an array of nanophase-separated lamellae containing etchable blocks derived from methyl methacrylate is formed perpendicular to the substrate. This microphase-separated array is suitable for use in transferring an etched pattern onto a substrate using a line-and-space array. The ABA with polar tethered portions of Example 4 is expected to exhibit fewer network defects and better grain size compared to those observed with a typical non-tethered ABA terpolymer (Figure 5A) (Comparative Example 1).

[0184] Processing Example 3: Self-assembly of block copolymers (BCPs) based on Example 8 (Table 1) The polymer of Example 8 (multitethered C8S copolymerized with PS block) is dissolved in PGMEA to prepare a 3.2% by weight solution. This solution is filtered using a 0.02 μm PTFE filter, and then SiO2 coated with the underlying polymer 1 (as described in Processing Example 1) is processed at 1500 rpm. xThe material is coated onto a wafer, and then the wafer is baked at 250°C for 1 hour. Figure 6 shows that this material forms a self-assembling pattern in which an array of nanophase-separated lamellae containing etchable blocks derived from methyl methacrylate is formed perpendicular to the substrate. This microphase-separated array is suitable for use in line-and-space arrays to transfer etching patterns onto a substrate. Furthermore, the film of this material exhibits fewer network defects and a considerably better grain size compared to the self-assembling film of Comparative Example 1, in that it exhibits a faster rate and better assembly and grain size than the standard ABA triblock copolymer processed under the same conditions as Example 8. Figure 6 shows a 1FOV SEM image of the pattern obtained after etching and processing as follows: Annealing at 250°C / 1 hour (N2); EBR for 2 minutes, spin-drying at 110°C / 1 minute, FT=140nm; and etching at O2 (50 sccm): N2 (50 sccm) for 30 seconds, power=50W, RIE=100, using a trion etcher. Total defect count measurement and 1FOV SEM image. A comparison with Figure 6 using a standard ABA copolymer (Figure 5A) under the same processing conditions shows that this novel multi-tethered polymer exhibited not only a faster processing rate but also improved particle size compared to a conventional non-tethered ABA block copolymer.

[0185] Processing Example 4: Self-assembly of block copolymers (BCPs) based on Example 9 (Table 1) The polymer of Example 9 (a multitether copolymerized with both PS and PMMA blocks) was dissolved in PGMEA to prepare a 3.2% by weight solution. This solution was filtered using a 0.02 μm PTFE filter, and then coated with SiO2 at 1500 rpm (as described in Processing Example 1) with the underlying polymer 1. xThe material was coated onto a wafer, and the wafer was then baked at 250°C for 1 hour. Figure 7 shows that the material formed a self-assembling pattern in which an array of nanophase-separated lamellae containing etchable blocks derived from methyl methacrylate was formed perpendicular to the substrate. This microphase-separated array was suitable for use in etching a line-and-space array onto the substrate for pattern transfer. Furthermore, the film of this material showed fewer network defects and a considerably better grain size compared to the self-assembling film of Comparative Example 1. This suggests that the polymer of Example 9 had a faster rate and better assembly than a standard ABA triblock copolymer. Figure 7 shows low T copolymerized to PS blocks. g The kinetic enhancement observed in the self-assembly of the film of Example 9, which is an ABA having hexyl methacrylate copolymerized with octyl styrene and PMMA blocks, is shown. 1FOV SEM image, process conditions: V: 250°C / 1 hour (N2); EBR 2 minutes, spin dry, 110°C / 1 minute, FT=140 nm. Specifically, Figure 7 shows a 1FOV SEM image of the pattern obtained after etching and processing as follows: annealing at 250°C / 1 hour (N2); EBR 2 minutes, spin dry, 110°C / 1 minute, FT=140 nm; and etching at O2 (50 sccm): N2 (50 sccm) for 30 seconds, power=50W, RIE=100, using a trion etcher. Total defect count measurement and 1FOV SEM image. A comparison of Figure 7 with the result obtained using a standard ABA copolymer (Figure 5A) under the same processing conditions shows that this novel polymer exhibited not only a faster processing rate but also improved particle size compared to conventional non-tethered ABA block copolymers.

[0186] Processing Example 5: Self-assembly of block copolymers (BCPs) based on Example 10 (Table 1) The polymer from Example 10 was dissolved in PGMEA to prepare a 3.2% by weight solution. This solution was filtered using a 0.02 μm PTFE filter, and then coated with SiO2 at 1500 rpm (as described in Processing Example 1) with the underlying polymer 1. xThe material was coated onto a wafer, and this wafer was then baked at 250°C for 1 hour. Figure 8 shows that polymer Example 10 formed a self-assembling pattern in which an array of nanophase-separated lamellae containing etchable blocks derived from methyl methacrylate was formed perpendicular to the substrate. This microphase-separated array was suitable for use in etching a line-and-space array onto the substrate for pattern transfer. Furthermore, the film of this material showed fewer network defects and a considerably better grain size compared to the self-assembling film of Comparative Example 1. This suggests that the polymer of Example 10 had a faster assembly rate and better assembly properties than a standard ABA triblock copolymer. Figure 7 shows the kinetic enhancement observed in the self-assembly of the film of Example 10, which is an ABA with isoprene at the PS-PMMA junction. Specifically, Figure 8 shows a 1FOV SEM image of the pattern obtained after processing as follows. Annealing at 250°C / 1 hour (N2); EBR for 2 minutes, spin-drying at 110°C / 1 minute, FT=140 nm. A comparison with the sample obtained using a standard ABA copolymer under the same processing conditions, as shown in Figure 8, demonstrates that this novel polymer exhibited not only a faster processing rate but also improved particle size compared to conventional non-tethered ABA block copolymers.

[0187] [Table 1]

Claims

1. A block copolymer having structure (1), in structure (1), Segment A is a polar block copolymer segment containing one of the following: alkyl 2-methylene alkanoate-derived repeating units, lactone-derived repeating units, oxirane-derived repeating units, oxetane-derived repeating units, or cyclic carbonate-derived repeating units; L is a direct valence bond or a linkage derived from 1,1-diarylethene; Segment B is a nonpolar block copolymer segment containing styrene-based repeating units. E is H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=O-O-alkyl), and alkyl 2-aryl acrylate derivative end group (-CH ２ -CH(aryl)(C(=O))-O-alkyl) is a terminal group selected from; however, The block copolymer of structure (1) is multitethered with oligoflexible tethered groups selected from oligolinear alkylene tethered groups, oligoether tethered groups, and oligodialkylsiloxane tethered groups, and these oligoflexible tethered groups are multitethered in the polymer block copolymer of structure (1) at positions selected from the following arrangements: the oligoflexible tethered groups are present only on segment A and randomly located along this segment on some of its repeating units, or present on each of its repeating units. The oligoflexible tethered group is present only on segment B, and is randomly located along this segment on some of its repeating units, or present in each of its repeating units. The oligoflexible tethered group is present on both segment A and segment B, and is randomly located along these segments on only a portion of their repeating units, or is present on each of those repeating units. The oligoflexible tethered group has an alkyl or alkyl 2-aryl acrylate derivative end group (-CH) at its E-terminus. ２ In the case of -CH(aryl)(C(=O))-O-alkyl), the groups present on both E-terminal groups are The oligoflexible tethered group is present on both L when L is a linking portion derived from 1,1-diarylethene. The oligoflexible tethered group is located in the center of the B segment; and The oligoflexible tethered group is located on at least one of the A segment, B segment, L (where L is the connecting portion), and terminal group E, however, The block copolymer has polydispersity in the range of 1 to about 1.

09. The aforementioned block copolymer. E-A-L-B-L-AE (1)

2. The block copolymer according to claim 1, wherein the polar block copolymer segment A comprises repeating units derived from lactones.

3. The block copolymer according to claim 1, wherein the polar block copolymer segment A comprises repeating units derived from alkyl 2-methylene alkanoate.

4. The block copolymer according to any one of claims 1 to 3, wherein the polar block copolymer segment A has an Mw between about 20,000 and about 200,000, and the non-polar styrene-based block copolymer segment B has an Mw between 20,000 and about 200,000.

5. The block copolymer according to claim 1 or 4, wherein L is a direct valence bond.

6. The block copolymer according to any one of claims 1 to 4, wherein L is a linking group derived from 1,1-diarylethene.

7. The block copolymer according to any one of claims 1 to 6, wherein E is either H or an alkyl group.

8. The block copolymer according to any one of claims 1 to 6, wherein E is a group derived from alkyl-2-aryl acrylate.

9. The block copolymer according to any one of claims 1 to 6, wherein E is a carbonyl alkyl (-C=O-alkyl) or a carbonyl oxyalkyl (-C=O-O-alkyl).

10. The block copolymer according to claim 1 or 4 having structure (2), wherein in structure (2), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ are each independently selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the oligoflexible tethered group, provided that at least one of R １ , R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ is selected from the oligoflexible tethered group, and n is the number of repeating units, said block copolymer. 【Chemistry 1】

11. A block copolymer according to any one of claims 1, 4, and 10 having structure (3), in structure (3), R １ and R ２ These are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the oligoflexible tethered group, R ８ and R ９ These are individually selected from C1-C5 alkyl groups and the oligoflexible tethered group. R １０ is H or C1-C5 alkyl, R １１ is H, C1-C5 alkyl, halide, or C1-C5 alkyloxy; however, R １ , R ２ , R ８ , and R ９ At least one of these is selected from the oligoflexible tethered groups, and n1 is the number of repeating units. The aforementioned block copolymer. 【Chemistry 2】

12. R ８ R is selected from the oligoflexible tethered groups, １ and R ２ The block copolymer according to claim 11, wherein each is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

13. The block copolymer according to claim 11 or 12, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

14. The block copolymer according to claim 11 or 12, wherein the oligoflexible tethered group is an oligoether tethered group.

15. The block copolymer according to claim 11 or 12, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

16. R ９ and R ８ However, individually selected from the oligoflexible tethered groups, R １ and R ２ The block copolymer according to claim 11, wherein each component is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

17. The block copolymer according to claim 11 or 16, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

18. The block copolymer according to claim 11 or 16, wherein the oligoflexible tethered group is an oligoether tethered group.

19. The block copolymer according to claim 11 or 16, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

20. R １ , R ２ and R ８ The block copolymer according to claim 11, wherein each oligoflexible tethered group is individually selected.

21. The block copolymer according to claim 11 or 20, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

22. The block copolymer according to claim 11 or 20, wherein the oligoflexible tethered group is an oligoether tethered group.

23. The block copolymer according to claim 11 or 20, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

24. A block copolymer according to claim 1 or 2 having structure (4), in structure (4), R １ and R ２ These are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the oligoflexible tethered group, R ９ａ and R ９ｂ These are individually selected from C1-C5 alkyl groups and the oligoflexible tethered group. R １０ａ and R １０ｂ These are individually selected from H or C1-C5 alkyl groups. R １２ is H or C1-C5 alkyl, however, R １ , R ２ , R ９ａ and R ９ｂ At least one of these is selected from the oligoflexible tethered group, and n2 and n3 are the number of repeating units. The aforementioned block copolymer. 【Transformation 3】

25. R ９ｂ However, selected from the oligoflexible tethered groups, R ９ａ However, it is C1-C5 alkyl, R １ and R ２ However, individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, The block copolymer according to claim 24.

26. The block copolymer according to claim 24 or 25, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

27. The block copolymer according to claim 24 or 25, wherein the oligoflexible tethered group is an oligoether tethered group.

28. The block copolymer according to claim 24 or 25, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

29. R ９ａ and R ９ｂ However, they are individually selected from C1 to C5 alkyl groups. R １ and R ２ However, each is selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, and the oligoflexible tethered group is an oligoether tethered group, provided that R １ and R ２ At least one of these is selected from the oligoflexible tethered groups, The block copolymer according to claim 24.

30. The block copolymer according to claim 24 or 29, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

31. The block copolymer according to claim 24 or 29, wherein the oligoflexible tethered group is an oligoether tethered group.

32. The block copolymer according to claim 24 or 29, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

33. R ９ａ and R ９ｂ However, individually selected from the oligoflexible tethered groups, R １ and R ２ However, individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, The block copolymer according to claim 24.

34. The block copolymer according to claim 24 or 33, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

35. The block copolymer according to claim 24 or 33, wherein the oligoflexible tethered group is an oligoether tethered group.

36. The block copolymer according to claim 24 or 33, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

37. A block copolymer according to any one of claims 1 to 36, having structure (5), R ３ , R ４ , R ５ , R ６ , and R ７ These are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy, and the oligoflexible tethered group, however, R ３ , R ４ , R ５ , R ６ , and R ７ At least one of these is selected from the oligoflexible tethered groups, unless the portion E-A-L in structure (5) contains at least one of the oligoflexible tethered groups. L is either a direct valence bond or a linkage derived from 1,1-diarylethene; Segment A is the polar block copolymer segment comprising any of the alkyl 2-methylene alkanoate derivative repeating units, lactone derivative repeating units, oxirane derivative repeating units, oxetane derivative repeating units, or cyclic carbonate derivative repeating units; E is H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=O-O-alkyl), and alkyl 2-aryl acrylate derivative end group (-CH ２ The terminal group is selected from -CH(aryl)(C(=O))-O-alkyl), and n4 is the number of repeating units. The aforementioned block copolymer. 【Chemistry 4】

38. The block copolymer according to claim 37, wherein L is a direct valence bond.

39. The block copolymer according to claim 37, wherein L is a linking portion derived from 1,1-diarylethene.

40. The block copolymer according to claim 37, wherein L is a linking portion derived from a 1,1-diphenylethene derivative.

41. R ５ , R ６ The block copolymer according to any one of claims 37 to 40, wherein H, C1-C5 alkyl, halide, and C1-C5 alkyloxy are selected.

42. R ５ , R ６ The block copolymer according to any one of claims 37 to 40, wherein the oligoflexible tethered group is selected from the above-mentioned oligoflexible tethered group.

43. R ３ , R ４ , and R ７ The block copolymer according to any one of claims 37 to 40, wherein the oligoflexible tethered group is selected from the above-mentioned oligoflexible tethered group.

44. R ３ , R ４ , R ５ , R ６ , and R ７ The block copolymer according to any one of claims 37 to 40, wherein the component is selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

45. In structure (5), E-A-L has structure (3a), where, * indicates the connection point of the E-A-L portion to B. R １ and R ２ These are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the oligoflexible tethered group, R ８ and R ９ These are individually selected from C1-C5 alkyl groups and the oligoflexible tethered group. R １０ is H or C1-C5 alkyl, R １１ is H, C1-C5 alkyl, halide or C1-C5 alkyloxy; provided that R １ , R ２ , R ８ , and R ９ of which at least one is selected from the oligoflexible tethered groups when B has no less than one of the oligoflexible tethered groups, and n5 is the number of repeating units. The block copolymer according to any one of claims 37 to 43. 【Transformation 5】

46. R ８ is selected from the oligoflexible tethered groups, R １ and R ２ are each independently selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, the block copolymer according to claim 45.

47. The block copolymer according to claim 45 or 46, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

48. The block copolymer according to claim 45 or 46, wherein the oligoflexible tethered group is an oligoether tethered group.

49. The block copolymer according to claim 45 or 46, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

50. R ９ and R ８ However, individually selected from the oligoflexible tethered groups, R １ and R ２ The block copolymer according to claim 45, wherein each component is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

51. The block copolymer according to claim 45 or 50, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

52. The block copolymer according to claim 45 or 50, wherein the oligoflexible tethered group is an oligoether tethered group.

53. The block copolymer according to claim 45 or 50, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

54. R １ , R ２ and R ８ The block copolymer according to claim 45, wherein each oligoflexible tethered group is individually selected.

55. The block copolymer according to claim 45 or 54, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

56. The block copolymer according to claim 45 or 54, wherein the oligoflexible tethered group is an oligoether tethered group.

57. The block copolymer according to claim 45 or 54, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

58. In the above B, R ３ , R ４ , R ５ , R ６ , and R ７ The block copolymer according to any one of claims 45 to 57, wherein each component is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

59. In structure (5), E-A-L has structure (4a), where, * indicates the connection point of the E-A-L portion to B. R １ and R ２ These are individually selected from H, C1-C5 alkyl, halide, C1-C5 alkyloxy and the oligoflexible tethered group, R ９ａ and R ９ｂ These are individually selected from C1-C5 alkyl groups and the oligoflexible tethered group. R １０ａ and R １０ｂ These are individually selected from H or C1-C5 alkyl groups. R １２ is H or C1-C5 alkyl, however, R １ , R ２ , R ９ａ and R ９ｂ At least one of the oligoflexible tethered groups is selected from the oligoflexible tethered groups if B does not have at least one of the oligoflexible tethered groups, and n6 and n7 are the number of repeating units. The block copolymer according to any one of claims 37 to 43. 【Transformation 6】

60. R ９ｂ However, selected from the oligoflexible tethered groups, R ９ａ However, it is C1-C5 alkyl, R １ and R ２ However, individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, The block copolymer according to claim 59.

61. The block copolymer according to claim 59 or 60, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

62. The block copolymer according to claim 59 or 60, wherein the oligoflexible tethered group is an oligoether tethered group.

63. The block copolymer according to claim 59 or 60, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

64. R ９ａ and R ９ｂ However, they are individually selected from C1 to C5 alkyl groups. R １ and R ２ However, each is selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, and the oligoflexible tethered group is an oligoether tethered group, provided that R １ and R ２ At least one of these is selected from the oligoflexible tethered groups, The block copolymer according to claim 59.

65. The block copolymer according to claim 59 or 64, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

66. The block copolymer according to claim 59 or 64, wherein the oligoflexible tethered group is an oligoether tethered group.

67. The block copolymer according to claim 59 or 64, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

68. R ９ａ and R ９ｂ However, individually selected from the oligoflexible tethered groups, R １ and R ２ However, individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, The block copolymer according to claim 59.

69. The block copolymer according to claim 59 or 68, wherein the oligoflexible tethered group is an oligolinear alkylene tethered group.

70. The block copolymer according to claim 59 or 68, wherein the oligoflexible tethered group is an oligoether tethered group.

71. The block copolymer according to claim 59 or 68, wherein the oligoflexible tethered group is an oligodialkylsiloxane tethered group.

72. R ３ , R ４ , R ５ , R ６ , and R ７ The block copolymer according to any one of claims 59 to 68, wherein the component is selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

73. In the above B, R ３ , R ４ , R ５ , R ６ , and R ７ The block copolymer according to any one of claims 59 to 71, wherein each component is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy.

74. A block copolymer having structure (6), in structure (6), A １ This includes one of the alkyl 2-methylene alkanoate derivative repeating units, lactone derivative repeating units, oxirane derivative repeating units, oxetane derivative repeating units, or cyclic carbonate derivative repeating units, and is suitable for temperatures from approximately 50°C to approximately 100°C. ｇ It is a polar block copolymer segment having; B １ The temperature range is from approximately 50°C to approximately 100°C. ｇ It is a styrene-based block copolymer segment having; B ２ This comprises repeating units derived from an olefin selected from the group consisting of alkenes, alkadienes, and alkatrienes, or a mixture of at least two different olefins selected from this group, in the range of about -5°C to about -50°C. ｇ It is a block copolymer segment having; L １ is either a direct valence bond or a linkage derived from 1,1-diarylethene; where, E １ These include H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=O-O-alkyl), and alkyl 2-aryl acrylate derivative end groups (-CH ２ A terminal group selected from -CH(aryl)(C(=O))-O-alkyl), however, The block copolymer has polydispersity in the range of 1 to about 1.

09. The aforementioned block copolymer. E １ -A １ -L １ -B ２ -B １ -B ２ -L １ -A １ -E １ (6)

75. B ２ The block copolymer according to claim 74, having repeating units derived from an alkene.

76. B ２ The block copolymer according to claim 74, having repeating units derived from an alkadiene.

77. The block copolymer according to claim 74 or 76, wherein the alkadiene is a conjugated diene.

78. B ２ However, it comprises a mixture of at least two different olefin repeating units having structures (7a), (7b), (7c) and (7d) derived from an alkadiene, where R ｄ , R ｄ１ , R ｄ２ , R ｄ３ , R ｅ , R ｅ１ , R ｅ２ , and R ｅ３ The block copolymer according to any one of claims 74, 76, and 77, wherein each of the following is individually selected from the group consisting of H and C1-C8 alkyl groups, wherein the total mol% of these olefin repeating units in the block copolymer is in the range of about 3 mol% to about 50 mol%. 【Transformation 7】

79. R ｄ , R ｄ１ , R ｄ２ , and R ｄ３ They are identical, selected from H or C1-C8 alkyl, and R ｅ , R ｅ１ , R ｅ２ , and R ｅ３ The block copolymer according to claim 78, wherein H or C1-C8 alkyl is selected. 【Transformation 8】

80. B ２ The block copolymer according to claim 74, comprising repeating units derived from any of the following: ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isoprene, 3-methylenepenta-1-ene, 3-methylenehexa-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepenta-1-ene, 1,3-butadiene, ethylidene norbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinyl norbornene (2-vinylbicyclo[2.2.1]hepta-2-ene), or chloroprene (2-chlorobuta-1,3-diene), or a mixture of at least two of these.

81. The block copolymer according to claim 74 or 76, wherein the alkadiene is a non-conjugated diene.

82. The block copolymer according to claim 74, wherein B2 is derived from an alkatriene.

83. The block copolymer according to claim 74, wherein B2 has repeating units derived from a mixture of at least two different olefins selected from the group consisting of alkenes, alkadienes, and alkatrienes.

84. B ２ The block copolymer according to any one of claims 74 to 80, further comprising styrene repeating units.

85. The aforementioned polar block copolymer segment A １ The block copolymer according to any one of claims 74 to 85, wherein it includes repeating units derived from lactones.

86. The aforementioned polar block copolymer segment A １ The block copolymer according to any one of claims 74 to 85, wherein it contains alkyl 2-methylene alkanoate derived repeating units.

87. The aforementioned polar block copolymer segment A １ The block copolymer according to any one of claims 74 to 85, wherein the Mw is between approximately 20,000 and approximately 200,000, and the nonpolar styrene-based block segment has an Mw between 20,000 and approximately 200,000.

88. L １ The block copolymer according to any one of claims 74 to 85, wherein the valence bond is a direct bond.

89. L １ The block copolymer according to any one of claims 74 to 85, wherein the linking group is derived from 1,1-diarylethene.

90. E １ The block copolymer according to any one of claims 74 to 89, wherein the component is either H or alkyl.

91. E １ The block copolymer according to any one of claims 74 to 89, wherein the group is derived from alkyl-2-aryl acrylate.

92. E １ The block copolymer according to any one of claims 74 to 89, wherein the carbonyl alkyl (-C=O-alkyl) or carbonyloxyalkyl (-C=O-O-alkyl).

93. Both ends are part B ２ -A １ -E １ A block copolymer according to any one of claims 74 to 87 and 89 to 91, having structure (7) comprising a central nonpolar styrene-based block copolymer segment bonded to R １ａ , R ２ａ , R ３ａ , R ４ａ , R ５ａ、 R ６ａ , and R ７ａ The block copolymer is individually selected from H, C1-C5 alkyl, halide, and C1-C5 alkyloxy, where n8 is the number of repeating units. 【Chemistry 9】

94. R １ａ , R ２ａ , R ３ａ , R ４ａ , R ５ａ , R ６ａ , and R ７ａ The block copolymer according to claim 93, wherein is H.

95. B ２ However, it comprises a mixture of at least two different olefin repeating units having structures (7a), (7b), (7c), and (7d), where R ｄ , R ｄ１ , R ｄ２ , R ｄ３ , R ｅ , R ｅ１ , R ｅ２ , and R ｅ３ The block copolymer according to claim 93 or 94, wherein each of the following is individually selected from the group consisting of H and C1-C8 alkyl groups, wherein the total mol% of these olefin repeating units in the block copolymer is in the range of about 3 mol% to about 50 mol%. 【Chemistry 10】

96. R ｄ , R ｄ１ , R ｄ２ , and R ｄ３ They are identical, selected from H or C1-C8 alkyl, and R ｅ , R ｅ１ , R ｅ２ , and R ｅ３ The block copolymer according to claim 95, wherein H or C1-C8 alkyl is selected. 【Chemistry 11】

97. B ２ The block copolymer according to any one of claims 93 to 96, wherein the block copolymer segment comprises repeating units derived from isoprene or butadiene.

98. The aforementioned polar block copolymer segment A １ However, it has an Mw between approximately 20,000 and approximately 200,000, and the central nonpolar styrene-based block copolymer segment B １ The block copolymer according to any one of claims 93 to 97, wherein the Mw is between 20,000 and about 200,000.

99. The aforementioned polar block copolymer segment A １ The block copolymer according to any one of claims 93 to 98, wherein it includes repeating units derived from lactones.

100. The aforementioned polar block copolymer segment A １ The block copolymer according to any one of claims 93 to 98, wherein it comprises repeating units derived from alkyl 2-methylene alkanoate.

101. E １ The block copolymer according to any one of claims 93 to 100, wherein is H.

102. A composition comprising at least one block copolymer and a spin-casting solvent as described in any one of claims 1 to 73.

103. The composition according to claim 102, further comprising other block copolymers.

104. The composition according to claim 102, further comprising a homopolymer.

105. Periodicity L ０ A method for orienting first and second block copolymer domains vertically on an unpatterned substrate using a layer of block copolymer having the following steps: a) The step of forming a block copolymer coating layer on the unpatterned substrate from the composition according to any one of claims 102 to 104; and b) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the unpatterned substrate; The method comprising the above.

106. Periodicity L ０ Using a coating containing a block copolymer having the above, first and second block copolymer domains are vertically oriented on a first patterned substrate, where the topographic height of the pattern on the substrate is L ０ The number is at least 0.7 times, and a method for aligning these domains in the pattern, the next step being: a1) forming a coating layer of the composition according to any one of claims 102 to 104 on the first topographic substrate, wherein the average thickness of the block copolymer coating layer is thinner than the height of the topography of the first topographic substrate, and the side surfaces of the block copolymer layer are confined by the topography; and b1) annealing the block copolymer layer to generate first and second block copolymer domains that are oriented perpendicularly to the first patterned substrate and confined within recessed regions; The method, including the method described above.

107. Periodicity L ０ The first and second block copolymer domains having L ０ Topographic height and pitch P1 (P1 is L) is more than 0.7 times ０ A method for orienting these domains perpendicularly on a second patterned substrate having a topographic pattern having (a non-zero positive integer multiplied by) and aligning these domains in the pattern, the next step being: a2) A block copolymer coating layer is formed on the second patterned substrate using the composition according to any one of claims 102 to 104, wherein the thickness of the block copolymer coating layer is greater than the height of the topography of the second patterned substrate; and b2) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the second patterned substrate, and aligning them on the second patterned substrate, where the total number of perpendicularly oriented domains is equal to or greater than the pitch P1 of the topographic pattern; The method, including the method described above.

108. The first and second block copolymer domains are oriented perpendicularly on a substrate having a surface chemical pre-pattern with pitch P2, where pitch P2 is L ０ A non-zero positive integer obtained by multiplying by , and a way to align these domains, the next step: a) The step of forming a block copolymer coating layer on a substrate having a surface chemical pre-pattern using the composition described in any one of claims 102 to 104; and b) Annealing the block copolymer layer to generate vertically oriented first and second block copolymer domains aligned on the substrate having a surface chemical pre-pattern having a pitch P2; The method, including the method described above.

109. A composition comprising a block copolymer according to any one of claims 74 to 101 and a solvent.

110. The composition according to claim 109, further comprising other block copolymers.

111. The composition according to claim 109, further comprising a homopolymer.

112. Periodicity L ０ A method for orienting first and second block copolymer domains vertically on an unpatterned substrate using a layer of block copolymer having the following steps: a) The step of forming a block copolymer coating layer on the unpatterned substrate from the composition according to any one of claims 109 to 111; and b) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the unpatterned substrate; The method, including the method described above.

113. Periodicity L ０ Using a coating containing a block copolymer having the above, first and second block copolymer domains are vertically oriented on a first patterned substrate, where the topographic height of the pattern on the substrate is L ０ The number is at least 0.7 times, and a method for aligning these domains in the pattern, the next step being: a1) A coating layer of the composition according to any one of claims 109 to 111 is formed on the first topographic substrate, wherein the average thickness of the block copolymer coating layer is thinner than the height of the topography of the first topographic substrate, and the side surface of the block copolymer layer is confined by the topography; and b1) Annealing the block copolymer layer to generate first and second block copolymer domains that are oriented perpendicularly to the first patterned substrate and confined within recessed regions; The method, including the method described above.

114. Periodicity L ０ The first and second block copolymer domains having L ０ The height and pitch P1 of the topography are more than 0.7 times (pitch 1 is L ０ A method for orienting these domains perpendicularly onto a second patterned substrate having a topographic pattern (which is a non-zero positive integer multiplied by a), and aligning these domains in the pattern, the following steps: a2) A block copolymer coating layer is formed on the second patterned substrate using the composition according to any one of claims 109 to 111, wherein the thickness of the block copolymer coating layer is greater than the height of the topography of the second patterned substrate; and b2) Annealing the block copolymer layer to generate first and second block copolymer domains of non-zero positive integers, oriented perpendicularly to the second patterned substrate, and aligning them on the second patterned substrate, where the total number of perpendicularly oriented domains is equal to or greater than the pitch P1 of the topographic pattern; The method, including the method described above.

115. The first and second block copolymer domains are oriented perpendicularly on a substrate having a surface chemical pre-pattern with pitch P2, where pitch P2 is L ０ A non-zero positive integer obtained by multiplying by , and a way to align these domains, the next step: a) The step of forming a block copolymer coating layer on a substrate having a surface chemical pre-pattern using the composition according to any one of claims 109 to 111; and b) Annealing the block copolymer layer to generate vertically oriented first and second block copolymer domains aligned on the substrate having a surface chemical pre-pattern having a pitch P2; The method, including the method described above.

116. A compound having structure (C1), wherein in structure (C1), R １ｂ , R １ｃ , R ２ｂ and R ２ｃ The group is individually selected from H, halide, C1-C4 alkyl, C1-C4 alkyloxy, and oligoflexible tethered group, however, R １ｂ , R ２ｂ , R １ｃ and R ２ｃ At least one of them is an oligoflexible tethered group, R ３ｂ , R ３ｃ , R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ The compounds are individually selected from H, halide, C1-C4 alkyl, and C1-C4 alkyloxy. 【Chemistry 12】

117. R １ｂ , R １ｃ , R ２ｂ and R ２ｃ The compound according to claim 116, wherein H and an oligoflexible tethered group are selected individually.

118. R １ｂ or R ２ｂ Only one of the following, and R １ｃ and R ２ｃ The compound according to claim 116 or 117, wherein only one of them is an oligoflexible tethered group.

119. R １ｂ or R ２ｂ Only one of the above, or R １ｃ and R ２ｃ The compound according to claim 116 or 117, wherein only one of them is an oligoflexible tethered group.

120. R １ｂ The compound according to any one of claims 116, 117, and 119, wherein only the oligoflexible tethered group is present.

121. R ２ｂ The compound according to any one of claims 116, 117, and 119, wherein only the oligoflexible tethered group is present.

122. R １ｂ and R １ｃ The compound according to any one of claims 116, 117, and 118, wherein only the oligoflexible tethered group is an oligoflexible tethered group.

123. R ２ｂ and R ２ｃ The compound according to any one of claims 116, 117, and 118, wherein only the oligoflexible tethered group is an oligoflexible tethered group.

124. R ３ｂ , R ３ｃ , R ４ｂ , R ４ｃ , R ５ｂ and R ５ｃ The compound according to any one of claims 116 to 123, wherein is H.

125. The compound according to any one of claims 116 to 124, wherein the flexible oligoflexible tethered group is a linear alkylene tethered group.

126. The compound according to any one of claims 116 to 124, wherein the flexible oligoflexible tethered group is an oligoether tethered group.

127. The compound according to any one of claims 116 to 124, wherein the flexible oligoflexible tethered group is an oligodialkylsiloxane tethered group.

128. A compound according to any one of claims 116, 117, 118, 123, and 125, having the structure (C1-A) and wherein a is 7 to 19. 【Chemistry 13】

129. A compound according to any one of claims 116, 117, 119, 121, and 125, having the structure (C1-B) and having a value of 7 to 19. 【Chemistry 14】

130. A compound according to any one of claims 116, 117, 118, 123, and 125, having a structure (C1-C) and a being between 7 and 19. 【Chemistry 15】

131. A compound according to any one of claims 116, 117, 119, 121, and 125, having a structure (C1-D) and a being between 7 and 19. 【Chemistry 16】

132. A compound according to any one of claims 116, 117, 118, 123, and 126, having a structure (C1-E), where e2 is 2 to 8 and e3 is 1 to 8. 【Chemistry 17】

133. A compound according to any one of claims 116, 117, 119, 121, and 126, having a structure (C1-F), where e2 is 2 to 8 and e3 is 1 to 8. [Chemistry 18]

134. A compound according to any one of claims 116, 117, 118, 123, and 126, having a structure (C1-G), where e2 is 2 to 8 and e3 is 1 to 8. 【Chemistry 19】

135. A compound according to any one of claims 116, 117, 119, 121, and 125, having a structure (C1-H), with e2 being 2 to 8 and e3 being 1 to 8. 【Chemistry 20】

136. The compound according to any one of claims 116, 117, 118, 123, and 127, having a structure (C1-I), with s being 6 to 18, and the alkyl portion being C1 to C8 alkyl. 【Chemistry 21】

137. The compound according to any one of claims 116, 117, 119, 121, and 127, having a structure (C1-J), with s being 6 to 18, and the alkyl portion being C1 to C8 alkyl. 【Chemistry 22】

138. The compound according to any one of claims 116, 117, 118, 123, and 127, having a structure (C1-K), with s being 6 to 18, and the alkyl portion being C1 to C8 alkyl. 【Chemistry 23】

139. The compound according to any one of claims 116, 117, 119, 121, and 127, having a structure (C1-L), with s being 6 to 18, and the alkyl portion being C1 to C8 alkyl. 【Chemistry 24】

140. Use of the composition according to any one of claims 102 to 104 or 109 to 111 in a self-assembly process in which a pattern transfer of a self-assembly pattern into a substrate is subsequently performed.

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