Low Tg multi-tether copolymerized diblock copolymers for directed self-assembly

Abstract

Disclosed are two different groups of block copolymers having the general structure (I) or (III), compositions thereof, and methods of using these compositions in DSA; wherein the B fragment and the B1 fragment are polar block copolymer fragments comprising a 2-methylene alkanoic acid alkyl ester-derived repeat unit, a lactone-derived repeat unit, an ethylene oxide-derived repeat unit, an oxetane or cyclic carbonate-derived repeat unit; l and L1 are a direct valence bond or a linking moiety derived from 1, 1-diarylethene; fragments A and A1 are non-polar block copolymer fragments comprising styrenic repeat units, E ', E' ', E3 and E4 are different types of end groups, A2 is a block fragment derived from an olefinic hydrocarbon or diene having a Tg of from about-5 DEG C to about-50 DEG C, and in structure (I), is multi-linked by an oligomeric flexible tether group at different positions as summarized: E'-A-L-B-E ''(I) E3-A1-A2-L1-B1-E4 (III).

Description

Technical Field

[0001] The present invention relates to a family of block copolymers of general structures (I) and (III), and to methods of using compositions of these block copolymers to align microdomains of self-assembling block copolymers (BCPs) to form self-assembled geometries that can be used to form arrays of contact holes or lines and spaces. These compositions and methods can be used to manufacture electronic devices. Background Art

[0002] The self-assembly of block copolymers is a method suitable for producing smaller and smaller patterned features for manufacturing microelectronic devices, wherein the critical dimension (CD) of features of about nanometer scale can be achieved. The self-assembly method is suitable for expanding the resolution capability of microlithography for repeating features such as contact holes or column arrays. In conventional photolithography methods, ultraviolet (UV) radiation can be used to expose to a photoresist layer coated on a substrate or a layered substrate via a mask. Positive or negative photoresists are useful, and these can also contain refractory elements (such as silicon) to be able to be developed without water by conventional integrated circuit (IC) plasma treatment. In positive photoresists, UV radiation transmitted through the mask causes a photochemical reaction in the photoresist, so that the exposed area is removed using a developer solution or by conventional IC plasma treatment. On the contrary, in negative photoresists, UV radiation transmitted through the mask causes the area exposed to the radiation to become more unremovable with a developer solution or by conventional IC plasma treatment. Integrated circuit features (such as gates, vias, or interconnects) are subsequently etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional photolithography exposure methods, the feature size of integrated circuit features is limited. Due to limitations on aberrations, focusing, proximity effects, minimum achievable exposure wavelengths, and maximum achievable numerical apertures, it is difficult to achieve further reductions in pattern size by radiation exposure. The demand for large-scale integration has led to continued reductions in circuit size and features in devices. In the past, the final resolution of features has depended on the wavelength of light used to expose photoresists, which has its own limitations. Directed (also referred to as guided) self-assembly techniques (e.g., graphoepitaxy and chemoepitaxy using block copolymer imaging) of patterned regions on application substrates are highly desirable techniques for improving resolution while reducing CD variations. These techniques can be applied to enhance conventional UV lithography or to achieve even higher resolution and CD control in methods using EUV, electron beams, deep UV, or immersion lithography. Directed self-assembly block copolymers include blocks of etch-resistant copolymer units and blocks of highly etchable copolymer units, which, when coated, aligned, and etched on a substrate, produce regions with extremely high density patterns.

[0003] For the directional (guiding) or non-guided self-assembly of the block copolymer film on the patterned or non-patterned substrate area respectively, the self-assembly method of this block polymer layer usually occurs during the annealing of this film covered on the neutral layer. This neutral layer above the semiconductor substrate can be an unpatterned neutral layer, or in chemical epitaxy or graphic epitaxy, this neutral layer can contain graphic epitaxy or chemical epitaxy guiding features (formed by UV lithography as described above) respectively. During the annealing of the block copolymer film, the bottom neutral layer guides the nano-phase separation of the block copolymer domain. An example is to form a phase-separated domain, which is a thin layer or cylinder perpendicular to the bottom neutral layer surface. These nano-phase separation block copolymer domains form pre-patterns (such as lines and gaps L / S), which can be transferred to the substrate by etching methods (such as plasma etching). In graphic epitaxy or in chemical epitaxy, these guiding features can indicate both pattern rectification (pattern rectification) and pattern multiplication. In the case of an unpatterned neutral layer, this produces a repeating array of, for example, L / S or CH. For example, in conventional block copolymers such as poly(styrene-b-methyl methacrylate (P(Sb-MMA)) where the two blocks have similar surface energies at the BCP-air interface, this can be achieved by coating the block copolymer on a layer of non-preferential or neutral material grafted or crosslinked at the polymer-substrate interface and thermally annealing it.

[0004] In the pattern epitaxy directed self-assembly method, block copolymers self-organize around a substrate pre-patterned using conventional photolithography (ultraviolet, deep UV, electron beam, extreme UV (EUV) exposure light source) to form repeating topographical features, such as line / space (L / S) or contact hole (CH) patterns. In the example of L / S directed self-assembled arrays, the block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different spacings in the grooves between the pre-patterned lines, thereby improving the pattern resolution by subdividing the gaps in the grooves between the topographic lines into finer patterns. For example, diblock copolymers or triblock copolymers that are capable of microphase separation and contain blocks rich in carbon (such as styrene or containing some other elements, such as Si, Ge, Ti) that are resistant to plasma etching and blocks that are highly plasma etchable or removable can provide high-resolution pattern definition. Examples of highly etchable blocks can include monomers that are rich in oxygen and free of refractory elements and that are capable of forming highly etchable blocks, such as methyl methacrylate. The plasma etching gas used for the etching process of defining the self-assembled pattern is generally those gases used in the method for manufacturing integrated circuits (ICs). In this way, extremely fine patterns other than those defined by conventional photolithography can be produced in a typical IC substrate, thereby achieving pattern multiplication. Similarly, features such as contact holes can be made denser by using graphic epitaxy, in which suitable block copolymers are arranged by directed self-assembly around the contact holes or column arrays defined by conventional photolithography, thereby forming a denser array of etchable domains and etching-resistant domains, which produce a denser array of contact holes when etching. Therefore, graphic epitaxy has the potential to provide both pattern correction and pattern multiplication.

[0005] In chemical epitaxy or pinning chemical epitaxy, the self-assembly of block copolymers is formed on the surface of the region whose guiding feature is different chemical affinity, and the surface does not have or has no significant morphology (also called non-guided morphology) indicating the directed self-assembly process. For example, the surface of the substrate can be patterned using conventional photolithography (UV, deep UV, electron beam, EUV) to produce a surface of different chemical affinity in a line and gap (L / S) pattern, wherein the exposed area where the surface chemistry has been modified by radiation alternates with the unexposed area and does not show chemical changes. There is no morphological difference in these areas, but there is a surface chemical difference or pinning to the directed self-assembly of the block copolymer fragments. Specifically, the directed self-assembly of the block copolymer whose block fragments contain etching-resistant repeating units (such as styrene repeating units) and fast etching repeating units (such as methyl methacrylate repeating units) will allow the etching-resistant block fragments and highly etchable block fragments to be accurately placed above the pattern. This technology allows these block copolymers to be accurately placed after plasma or wet etching treatment and the subsequent pattern transfer of the pattern to the substrate. The advantage of chemical epitaxy is that it can be finely tuned through changes in chemical differentiation to help improve line-edge roughness and CD control, thus allowing pattern correction. Other types of patterns, such as repeating contact hole (CH) arrays can also be pattern corrected using chemical epitaxy.

[0006] These neutral layers are layers on the surface of substrates or treated substrates, which have no affinity for any of the block segments of the block copolymers used in directional self-assembly. In the graphic epitaxy method of directional self-assembly of block copolymers, a neutral layer is used because it allows the correct placement or orientation of the block polymer segments for directional self-assembly, which allows the etching-resistant block polymer segments and the highly etchable block polymer segments to be correctly placed relative to the substrate. For example, in a surface containing line and gap features defined by conventional radiation lithography, the neutral layer allows the block segments to be oriented so that the block segments are oriented perpendicular to the surface of the substrate, depending on the length of the block segments in the block copolymer, such as related to the length between the lines defined by conventional photolithography, which is ideal for both pattern correction and pattern multiplication. If the substrate interacts too strongly with one of the block segments, it will cause the segment to be flatly located on the surface of the substrate to maximize the contact surface between the segment and the substrate; this surface will interfere with the required vertical alignment that can be used to achieve pattern correction or pattern multiplication based on features generated by conventional photolithography. Tailoring a selected small area or pinning substrate so that it interacts strongly with one block of the block copolymer and coating the rest of the surface with a neutral layer can be useful for forcing the domains of the block copolymer to align in a desired direction and is the basis of pinned chemical epitaxy or graphic epitaxy for pattern multiplication.

[0007] Directed self-assembly (DSA) of diblock copolymers such as polystyrene-b-polymethyl methacrylate (PS-b-PMMA) block copolymers is widely used as the next generation of photolithographic patterning. The microphase separation of diblock copolymers is used for feature size control in photolithography. These diblock copolymers can produce unidirectional and unidirectional feature sizes in film morphology with suitable bottom layers or pre-patterns for DSA applications. However, one problem is that the defect-free assembly process of block copolymers requires high thermal energy and longer time. New diblock copolymers are needed to solve this problem, and the diblock copolymers have better block segment mobility and less stringent annealing requirements, which will reduce the number of defects caused by DSA processing with smaller IC patterns. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 : Representative examples of the assembly of novel diblock copolymers of styrenic monomers and alkyl methacrylate monomers, wherein at least one of these blocks has a low T g , because it is multiply tethered by oligomeric flexible groups.

[0009] Figure 2 : Representative examples of the assembly of novel AB diblock copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA) by including additional low T g The block segments, such as the block segments comprising polyisoprene (PI), are modified.

[0010] Figure 3 : Fingerprint pattern (FP) of multi-tethered diblock copolymer (EX 2, TAB) on the brush-based neutral copolymer 1

[0011] Figure 4 : 1 FOV SEM image of multi-tethered diblock copolymer (EX 6, TAB 5). Multi-tethered diblock shows improved crystallite size without defects.

[0012] Figure 5 : 1 FOV SEM image of a standard CH diblock copolymer (EX 1a, AB1) showing a large number of defects arising from domains of mixed morphology. Summary of the invention

[0013] Defect-free assembly methods of block copolymers require high thermal energy and extended time. This difficulty limits the use of directed self-assembly of block copolymers with large domain spacing and triblock copolymers that double the molecular weight of diblock copolymers in multi-spacing applications in photolithographic patterning. The present invention relates to the synthesis of two families of kinetically enhanced AB diblock copolymers.

[0014] In both methods, the T of the block fragmentg The AB diblock copolymers in the first family contain at least one block that is multi-tethered by oligomeric flexible tethering groups. In the second family, the AB diblock copolymers contain a third block that contains a low T g Repeating units (e.g. derived from isoprene and similar low T g olefinic repeating unit).

[0015] ( Figure 1 ) is to develop a series of low T g Novel multi-tethered copolymeric diblocks of comonomers, for example in PS blocks or in PMMA blocks or in both PS and PMMA blocks. Non-limiting specific examples are P(S1-co-S2)-bP(M1-co-M2), P(S1-co-S2)-b-PMMA and PS-bP(M1-co-M2) having target molecular weights showing narrow molecular weight distribution (PDI<1.1), as follows:

[0016] P(S1-co-S2)-bP(M1-co-M2) is a block copolymer comprising a first polymer block P(S1-co-S2) containing two different types of styrene repeating units, and a second polymer block P(M1-co-M2) containing two different types of methacrylate repeating units, wherein S1 is styrene, S2 is styrene substituted with an oligomeric flexible tethering group, M1 is methyl methacrylate, and M2 is methacrylate substituted with an oligomeric flexible tethering group.

[0017] P(S1-co-S2)-b-PM1 is a block copolymer comprising a first block P(S1-co-S2) polymer containing two different types of styrene repeating units and a second polymer block PM1 containing a single type of styrene repeating unit, wherein S1 is styrene, S2 is styrene substituted with an oligomeric flexible tethering group, and M1 is methyl methacrylate.

[0018] PS1-bP(M1-co-M2) is a block copolymer comprising a first polymer block PS1 containing a single type of styrene repeating unit (S1) and a second polymer block P(M1-co-M2) containing two different types of alkyl methacrylates (M1 and M2), wherein S1 is styrene, M1 is methyl methacrylate, and M2 is methacrylate substituted with oligomeric flexible tethering groups.

[0019] Another method ( Figure 2 ) is a modified styrenic / alkyl methacrylate AB diblock copolymer to include a low T gFor example, in a diblock copolymer, the PS and PMMA blocks introduce additional block segments having a low T of about -5°C to about -50°C. g , comprising repeating units derived from olefins or dienes, such as repeating units derived from isoprene (PI), which also have a target molecular weight exhibiting a narrow molecular weight distribution (PDI < 1.1). A non-limiting example of this type of polymer is PS1-b-PI-b-PMMA as follows:

[0020] PS1-b-PI-b-PMMA is a block copolymer comprising a first polymer block PS1 containing a single type of styrene repeating unit (S1), a second polymer block (PI) containing isoprene repeating units and a third block (PMMA) containing polymethyl methacrylate repeating units.

[0021] Both families of modified block copolymers can be prepared using living anionic polymerization in the presence of an anionic initiator such as s-Bu Li initiator.

[0022] More generally, these two types of polymers are families of polymers of the present invention, described by structures (I) and (III), respectively, as shown below.

[0023] The polymer of the present invention of structure (I)

[0024] One aspect of the present invention is a block copolymer having structure (I), wherein

[0025] The A segment is a non-polar block copolymer segment containing styrene repeating units,

[0026] The B segment is a polar block copolymer segment comprising repeating units derived from 2-methylenealkanoic acid alkyl esters, repeating units derived from lactones, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonates;

[0027] L is a direct bond or a linking moiety derived from 1,1-diarylethene

[0028] E' is a C-1 to C-12 alkyl terminal group,

[0029] E" is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0030] Furthermore, in this embodiment of the block copolymer of structure (1), the oligomeric flexible tethering groups selected from the group consisting of oligomeric linear alkylene tethering groups, oligomeric ether tethering groups, and oligomeric dialkylsiloxane tethering groups are multi-tethered, and these oligomeric flexible tethering groups are multi-tethered on at least one of the A segments, the B segments, and L (if L is a linking moiety derived from 1,1-diarylethene), and the block copolymer has a polydispersity in the range of 1 to about 1.09 and an M of at least 40,000. n .

[0031] E'-ALBE" (I)

[0032] The polymer of structure (III) of the present invention

[0033] Another aspect of the present invention is a block copolymer having structure (III), wherein

[0034] A1 is T g A styrenic block copolymer segment having a temperature of about 50°C to about 100°C, wherein

[0035] A2 is T g a block copolymer segment in the range of about -5°C to about -50°C comprising repeating units derived from an olefin selected from the group consisting of olefins, dienes and trienes or a mixture of at least two different olefins selected from the group;

[0036] B1 is a product having a T of about 50°C to about 100°C. g a polar block copolymer segment comprising repeating units derived from alkyl 2-methylene alkanoate, repeating units derived from lactone, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonate;

[0037] L1 is a direct bond or a linking moiety derived from 1,1-diarylethene; wherein

[0038] E 3 is an alkyl group,

[0039] E 4 It is a group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0040] Furthermore, in this embodiment of the block copolymer of structure (III), it has a polydispersity ranging from 1 to about 1.09:

[0041] E 3 -A1-A2-L1-B1-E 4 (III).

[0042] Another aspect of the present invention is a composition comprising a block copolymer of structure (I) of the present invention or a block copolymer of structure (III) of the present invention and a spin casting solvent.

[0043] Another aspect of the present invention is a method of using the above composition in a self-assembly process and subsequently transferring the self-assembled pattern to a substrate.

[0044] DETAILED DESCRIPTION OF THE INVENTION

[0045] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not restrictive to the subject matter claimed. In the present application, the use of the singular includes the plural, the word "a" or "an" means "at least one", and the use of "or" means "and / or", unless otherwise specifically stated. In addition, the use of the term "including" and other forms such as "includes" and "included" is not restrictive. In addition, terms such as "element" or "component" cover both elements and components containing one unit and elements or components containing more than one unit, unless otherwise specifically stated. As used herein, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive, unless otherwise stated. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the aforementioned elements, including the use of a single element.

[0046] L0 is the natural spacing of assembled block copolymers, which tends to scale with the size of the copolymer.

[0047] The term C-1 to C-4 alkyl includes methyl and C-2 to C-4 straight chain alkyl and C-3 to C-4 branched alkyl moieties, for example as follows: methyl (-CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2, n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2, 2-butyl (-CH(CH3)CH2-CH3). Similarly, the term C-1 to C-8 includes methyl, C-2 to C-8 straight chain, C-3 to C-8 branched alkyl, C-4 to C-8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) or C-5 to C-8 alkylene cycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0048] The term C-2 to C-5 alkylene includes C-2 to C-5 straight chain alkylene moieties (e.g., ethylene, propylene, etc.) and C-2 to C-5 branched chain alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0049] Diblock and triblock copolymers of styrene and 2-methylene alkanoic acid alkyl ester derived repeating unit moieties suitable for use as components in the inventive compositions described herein can be prepared by a variety of methods (e.g., anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT) polymerization, living radical polymerization, etc.) (Macromolecules 2019, 52, 2987-2994; Macromol. Rapid Commun. 2018, 39, 1800479; A. Deiter Shluter et al., Synthesis of Polymers, 2014, Vol. 1, p. 315; Encyclopedia of Polymer Science and Technology, 2014, Vol. 7, p. 625).

[0050] 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) and the oligomer of this material is abbreviated as oligo(Sb-MMA). The oligomer oligo(styrene-co-p-octylstyrene)-block-(methyl methacrylate-co-di(ethylene glycol)methyl ether methacrylate) uses the same abbreviation to represent the random block copolymer element, specifically oligo(S-co-p-OS)-bP(MMA-co-DEGMEMA) where S = styrene, p-OS = p-octylstyrene, MMA = methacrylate, DEGMEMA = di(ethylene glycol)methyl ether methacrylate, indicating that the two blocks are repeating units in this block copolymer that are random copolymers.

[0051] FOV is an abbreviation for "Field of View" of a top-down scanning electron micrograph (SEM) of the SEM images in this application. "L / S" is an abbreviation for "Line and Space" lithographic features.

[0052] The term alkyl 2-methylene alkanoate (alkyl-O-(C=O)-C(alkyl)=CH2) refers to an alkyl ester of a 2-methylene alkanoate, wherein the 2-methylene alkanoate may have up to 11 carbon atoms bonded thereto, and the alkyl group in the 2-methylene alkanoate may have up to 8 carbon atoms bonded thereto, selected from methyl, straight chain alkyl, branched chain alkyl and cyclic alkyl. The following structure gives the general structure of such an alkyl 2-methylene alkanoate, wherein Ralk a and Ralk b Independently selected from C-1 to C-8 alkyl, and non-limiting examples of alkyl 2-methylenealkanoates falling within this range are shown.

[0053]

[0054] Unless otherwise indicated, the term styrenic as used herein encompasses repeating units derived from styrene derivatives, typically, for example, repeating units derived from styrene derivatives having the following structure, wherein the Xsty moiety is H or C-1 to C-4 alkyl, the Rsty moiety is H, C-1 to C-5 alkyl, halo, C-1 to C-5 alkoxy, or an oligomeric flexible tethering group, and st is the number of Rsty substituents and is 1 or 2.

[0055]

[0056] Unless otherwise indicated, the term 1,1-diarylethene as used herein encompasses a moiety derived from ethylene having two substituents at the 1-position which are aryl moieties as shown below, wherein Aryl1 and Aryl2 are aryl substituents selected from phenyl or substituted phenyl, and if substituents are present in one or both of Aryl1 and Aryl2, these substituents are independently selected from C-1 to C-5 alkyl, halide, C-1 to C-5 alkoxy and oligomeric flexible tethering groups.

[0057]

[0058] Unless otherwise indicated, the term "2-aryl alkyl acrylate derived end group" is described by the general structure (-CH2-CH(aryl)(C(=O))-O-alkyl), which is defined in more detail in the general structure below, wherein * represents the point of attachment to the end of the block copolymer chain; Aryl3 is an aryl substituent selected from phenyl or substituted phenyl, and if a substituent is present in either, wherein the substituent is independently selected from C-1 to C-5 alkyl, halide, C-1 to C-5 alkoxy and oligomeric flexible tethering groups, and further wherein Alkyl3 is an unsubstituted alkyl C-1 to C-5 alkyl or a C-1 to C-5 alkyl substituted with an oligomeric flexible tethering group. As an illustrative example, such an end group structure can be obtained by reacting a 2-aryl alkyl ester at the CH2 olefinic portion with an active anion at the end of the polymer chain to form a CH - The anion is then terminated by protonation.

[0059]

[0060] The section headings used herein are for organizational purposes and shall not be construed as limiting the subject matter described. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that one or more incorporated references and similar materials define a term in a manner inconsistent with the definition of that term in this application, the present application controls.

[0061] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be straight chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties may be substituted or unsubstituted as described below. The term "alkyl" refers to such a portion having C-1 to C-20 carbons. It should be understood that for structural reasons, straight chain alkyls start with C-1, while branched and cyclic alkyls start with C-3 and polycyclic alkyls start with C-5. In addition, it should be further understood that, unless otherwise indicated, the moieties derived from alkyls described below (e.g., alkoxy and perfluoroalkyl) have the same carbon number range. If the length of the alkyl group is specified to be different from that described above, the alkyl definition described above still holds true with respect to its inclusion of all types of alkyl moieties as described above, and structural considerations regarding the minimum carbon number of a given type of alkyl group still apply.

[0062] Alkyloxy (also known as Alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkyloxy moieties may be substituted or unsubstituted as described below.

[0063] Halo or halogen refers to a halogen, F, Cl, Br or I, attached to an organic moiety through a bond.

[0064] As used herein, the term lactone encompasses both monolactones (eg, caprolactone) and dilactones (eg, lactide).

[0065] Haloalkyl refers to a linear, cyclic or branched saturated alkyl group such as defined above, wherein if more than one halo moiety is present, at least one of the hydrogens has been replaced by a halo selected from F, Cl, Br, I or mixtures thereof. Fluoroalkyl is a specific subgroup of these moieties.

[0066] Perfluoroalkyl refers to a straight chain, cyclic or branched saturated alkyl group as defined above in which hydrogen has been completely replaced by fluorine (eg, trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.).

[0067] The term oligomeric flexible tethering group, as used in describing various embodiments of the inventive polymers or compounds described herein, refers to the group of moieties that include oligomeric linear alkylene tethering groups, oligomeric ether tethering groups, and oligomeric dialkylsiloxane tethering groups.

[0068] In the various embodiments of the polymers or compounds of the present invention described herein, the term oligomeric linear alkylene tether group refers in the broadest embodiment to a group having the following general structure: -X1-(CH2) a -CH3, wherein a is 6 to 19, and X1 is selected from a direct valence bond, a straight chain C-1 to C-4 alkylene spacer, -O-, -CH2-O-, -O-(C=O)-, -C=OO-, C=O, -CH2-O-(C=O)-, -S-, -SO2-, -SO-.

[0069] In one embodiment, X1 is a direct valence bond. In another embodiment, X1 is a linear C-1 to C-4 alkylene spacer. In another embodiment, X1 is -O-. In still another embodiment, it is -CH2-O-; in still another, X1 is -O-(C=O)-. In another embodiment, X1 is -C=OO-. In another embodiment, X1 is a carbonyl (C=O). In another embodiment, X1 is -CH2-O-(C=O)-. In another embodiment, X1 is -S-. In another embodiment, X1 is -SO2-. In another embodiment, X1 is -SO-. A more specific type of these groups is -O-(CH2) a -CH3, or -CH2-O--(CH2) a -CH3, wherein a is 6 to 19. In a more specific embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 7 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 7 to 10. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 8 to 9. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a equal to 8. In another more specific embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 7 to 14. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 7 to 13. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 8 to 13. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a equal to 13. In another more specific embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2)a -CH3 has a value of 7 to 19. In a more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 8 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 9 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 10 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 11 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 12 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 13 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 13 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 14 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 15 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 16 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a value of 17 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2--O--(CH2) a-CH3 has a value of 18 to 19. In a still more selective embodiment, -O-(CH2) a -CH3 or -CH2-O--(CH2) a -CH3 has a equal to 18. These linear alkylene tethering groups can be unsubstituted or substituted with C-1 to C-8 alkyl groups forming branching points. These linear alkylene tethering groups can be unsubstituted or substituted with C-1 to C-8 alkyl groups forming branching points.

[0070] The term oligoether tethering group in various embodiments of the polymers or compounds of the present invention described herein refers to a moiety having the following general structure: -O-[(CH2) e -O-] e2 -(CH2) e3 -H, and -(CH2) e4 -O-[(CH2) e -O-] e2 -(CH2) e3 -H, wherein independently e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8. In a specific embodiment, another aspect of this embodiment is -O-(CH2-CH2-O) e2 -(CH2) e3 -H; in a more specific aspect of this embodiment, it is -O-(CH2-CH2-O) e2 -(CH3); in a more specific aspect of this embodiment, it is -CH2-O-(CH2-CH2-O)4-CH3; in yet another more specific embodiment, it is O-(CH2-CH2-O)4-CH3. In another more specific embodiment, it is -CH2-O-(CH2-CH2-O) e2 -(CH2) e3 In another more specific embodiment, it is -CH2-O-(CH2-CH2-O) e2 -CH3, in another more specific aspect of this embodiment, it is -CH2-O-(CH2-CH2-O)4-CH3, in another more specific aspect of this embodiment, it is -CH2-O-(CH2-CH2-O)2-CH3. These oligoether tethering groups can be unsubstituted or substituted with C-1 to C-8 alkyl groups forming branching points.

[0071] The term oligomeric dialkylsiloxane tethering group present in various embodiments of the polymers or compounds of the present invention described herein refers to a group having the following general structure: -X2-[Si(alkyl)2-O] s-Si(alkyl)3, wherein s is 6 to 18, the alkyl moiety is C-1 to C-8 alkyl, X2 is a direct bond, or a C-1 to C-8 linear alkylene spacer, or -O-. In a more specific aspect of this embodiment, it is -O-[Si(alkyl)2-O] s -Si(alkyl)3, in a more specific aspect of this embodiment, it is -O-[Si(CH3)2-O] s -Si(CH3)3. In another more specific aspect of this embodiment, it is -CH2-O-[Si(alkyl)2-O] s -Si(alkyl)3, in a more specific aspect of this embodiment, it is -CH2-O-[Si(CH3)2-O] s -Si(CH3)3.

[0072] The polymer of structure (I) of the present invention

[0073] One aspect of the present invention is a block copolymer having structure (I), wherein

[0074] The A segment is a non-polar block copolymer segment comprising styrene repeating units;

[0075] L is a direct bond or a linking moiety derived from 1,1-diarylethene;

[0076] The B segment is a polar block copolymer segment comprising repeating units derived from 2-methylene alkanoic acid alkyl esters, repeating units derived from lactones, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonates

[0077] E' is a C-1 to C-12 alkyl terminal group;

[0078] E" is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0079] Furthermore, in this embodiment of the block copolymer of structure (1), the oligomeric flexible tethering groups selected from the group consisting of oligomeric linear alkylene tethering groups, oligomeric ether tethering groups, and oligomeric dialkylsiloxane tethering groups are multi-tethered, and these oligomeric flexible tethering groups are multi-tethered on at least one of the A segments, the B segments, and L (if L is a linking moiety derived from 1,1-diarylethene), and the block copolymer has a polydispersity of 1 to about 1.09 and an M of at least 40,000. n .

[0080] E'-ALBE" (I).

[0081] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is an oligomeric linear alkylene tethering group.

[0082] In another embodiment of the block copolymer of structure (I) described herein, the oligomeric flexible tethering group is a group having the general structure -X1-(CH2) a A low-polymer straight-chain alkylene tethered group of -CH3, wherein n is 6 to 19, X1 is and X1 is selected from a direct valence bond, a straight-chain C-1 to C-4 alkylene spacer, -O-, -CH2-O-, -O-(C=O)-, -C=OO-, C=O, -CH2-O-(C=O)-, -S-, -SO2- and -SO-.

[0083] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is an oligomeric ether tethering group.

[0084] In another embodiment of the block copolymer of structure (I) described herein, the oligomeric flexible tethering group is an oligomeric ether tethering group having the following general structure: -O-[(CH2) e -O-] e2 -(CH2) e3 -H or -(CH2) e4 -O-[(CH2) e -O-] e2 -(CH2) e3 -H, wherein independently e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8.

[0085] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is an oligomeric dialkylsiloxane tethering group.

[0086] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is a polymer having the formula -X2-[Si(alkyl)2-O] s -Si(alkyl)3 oligomeric dialkylsiloxane tethered groups, wherein s is 6 to 18, the alkyl portion is a C-1 to C-8 alkyl, and X2 is a direct bond, or a C-1 to C-8 linear alkylene spacer, or -O-.

[0087] In another embodiment of the block copolymers of structure (I) described herein, the polar block copolymer segment B comprises repeating units derived from a lactone.

[0088] In another embodiment of the block copolymers of structure (I) described herein, the polar block copolymer segment B comprises repeating units derived from alkyl 2-methylene alkanoate.

[0089] In another embodiment of the block copolymers of structure (I) described herein, the polar block copolymer segment B has an Mw between about 20,000 and about 200,000 and the non-polar styrenic block copolymer segment A has an Mw between 20,000 and about 200,000.

[0090] In another embodiment of the block copolymers of structure (I) described herein, L is a direct bond.

[0091] In another embodiment of the block copolymers of structure (I) described herein, L is a linking group derived from 1,1-diarylethene.

[0092] In another embodiment of the block copolymers of structure (I) described herein, E" is H.

[0093] In another embodiment of the block copolymers of structure (I) described herein, E" is alkyl.

[0094] In another embodiment of the block copolymers of structure (I) described herein, E" is carbonylalkyl (-C=O-alkyl).

[0095] In another embodiment of the block copolymers of structure (I) described herein, E" is carbonyloxyalkyl (-C=OO-alkyl).

[0096] In another embodiment of the block copolymers of structure (I) described herein, E" is a 2-aryl alkyl acrylate derived end group (-CH2-CH(aryl)(C(=O))-O-alkyl).

[0097] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is located on the A segment and is randomly located on some of the repeating units along the segment or is present on every repeating unit thereof.

[0098] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is located on the B segment and is randomly located on some or present on every repeating unit along the segment.

[0099] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering group is located on the linking group L (when it is derived from a 1,1-diarylethene).

[0100] In another embodiment of the block copolymer of structure (I) described herein, the oligomeric flexible tethering group is located on the A segment, the B segment and the linking group L (if L is derived from 1,1-diarylethene), and is randomly located on some of their respective repeating units or present on each of their respective repeating units along the A segment or along the B segment.

[0101] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering groups are located only on the A segment and are either randomly located along the segment on some of the repeating units thereof or are present on every repeating unit thereof.

[0102] In another embodiment of the block copolymers of structure (I) described herein, the oligomeric flexible tethering groups are located only on the B segment and are either randomly located along the segment on some of the repeating units thereof or are present on every repeating unit thereof.

[0103] In another embodiment of the block copolymers of structure (I) described herein, wherein the oligomeric flexible tethering groups are only located on the linking group L (if L is derived from 1,1-diarylethene).

[0104] In another embodiment of the block copolymer of structure (I) described herein, the oligomeric flexible tethering group is located only on the A segment and the B segment, and is randomly located on some of their respective repeating units along the A segment and the B segment, or is present on each of their respective repeating units.

[0105] In another embodiment of the block copolymer of structure (I) described herein, the oligomeric flexible tethering group is located only on the A segment and the linking group L (if it is derived from 1,1-diarylethene), and is either randomly located along the A segment on some of its repeating units, or is present on each of its repeating units.

[0106] In another embodiment of the block copolymer of structure (I) described herein, wherein the oligomeric flexible tethering group is located only on the B segment and the linking group L (if it is derived from 1,1-diarylethene), and either the B segment is randomly located on some of its repeating units, or is present on every repeating unit thereof.

[0107] In another embodiment of the block copolymers of structure (I) described herein, wherein the oligomeric flexible tethering groups are present on the A segments or the B segments or both, these oligomeric flexible tethering groups are randomly present on some of their repeating units along their respective segments.

[0108] In another embodiment of the block copolymers of structure (I) described herein, wherein the oligomeric flexible tethering groups are present on the A segments or the B segments or both, these oligomeric flexible tethering groups are present on all repeating units of each thereof.

[0109] In another embodiment of the block copolymer of structure (I) described herein, the copolymer has structure (II), comprising

[0110] A styrenic block composed of randomly copolymerized styrenic repeating units of structures (STa) and (STb), wherein R1 and R2 are each selected from H or C-1 to C-4 alkyl, and R5 and R6 are each selected from H, C-1 to C-4 alkyl, and an oligomeric flexible tethering group selected from the following

[0111] · Oligomeric linear alkylene tethering groups,

[0112] Oligoether tethering groups, and

[0113] Oligomeric dialkylsiloxane tethering groups,

[0114] The linking portion of structure (L1), wherein R7 and R8 are each selected from H, C-1 to C-4 alkyl, and are multi-tethered by an oligomeric flexible tethering group selected from the following

[0115] · Oligomeric linear alkylene tethering groups,

[0116] Oligoether tethering groups, and

[0117] Oligomeric dialkylsiloxane tethering groups,

[0118] A 2-methylene alkanoate derived block composed of randomly copolymerized 2-methylene alkanoate repeating units of the structures (MEAa) and (MEAb), wherein R3 and R4 are independently selected from C-1 to C-4 alkyl, R9 and R 10 Each selected from C-1 to C-4 alkyl groups and multi-tethered with an oligomeric flexible tethering group selected from

[0119] · Oligomeric linear alkylene tethering groups,

[0120] Oligoether tethering groups, and

[0121] Oligomeric dialkylsiloxane tethering groups,

[0122] E' is a C-1 to C-12 alkyl terminal group,

[0123] E" is selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl);

[0124] x and x' represent the number of repeating units of structures (STa) and (STb), respectively, in said styrenic block having a Mw of about 20,000 to about 200,000, in the non-polar block segment, which is delimited by brackets denoted by n,

[0125] y and y' represent the number of repeating units of structures (MEAa) and (MEAb), respectively, in the 2-methylene alkanoate derived block, the block having an Mw of about 20,000 to about 200,000, and in the polar block segment, which is bounded by brackets denoted by m, and further wherein at least one of structures (STa), (STb), (L1), (MEAa) and (MEAb), respectively, has R5, R6, R7, R8, R9 or R 10 , selected from the oligomeric flexible tethering group.

[0126]

[0127] In another embodiment of the block copolymer of structure (II) described herein, R5 is an oligomeric flexible tethering group, R6 is H or C-1 to C-4 alkyl, R7 and R8 are each selected from H and C-1 to C-4 alkyl, R9 and R 10 Each is selected from C-1 to C-4 alkyl groups.

[0128] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are multi-tethered with an oligomeric flexible tethering group, R7 and R8 are each selected from H and C-1 to C-4 alkyl, R9 and R 10 Each is selected from C-1 to C-4 alkyl groups.

[0129] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are each selected from H and C-1 to C-4 alkyl, at least one of R8 and R7 is an oligomeric flexible tethering group, and R9 and R 10 Each is selected from C-1 to C-4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligomeric flexible tethering groups.

[0130] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are each selected from H and C-1 to C-4 alkyl, R8 and R7 are each selected from H and C-1 to C-4 alkyl, and R9 and R 10 At least one of the is an oligomeric flexible tethering group.

[0131] In another embodiment of the block copolymer of structure (II) described herein, R9 and R 10 Both are oligomeric flexible tethering groups.

[0132] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are each selected from H and C-1 to C-4 alkyl, at least one of R8 and R7 is an oligomeric flexible tethering group, and R9 and R 10 In another aspect of this embodiment, both R8 and R7 are oligomeric flexible tethering groups. In another aspect of this embodiment, at least one of R5 and R6, and R9 and R 10 In another aspect of this embodiment, both R5 and R6 and R9 and R 10 Both are flexible tether groups.

[0133] In another embodiment of the block copolymer of structure (II) described herein, R5 and R6 are each selected from H and C-1 to C-4 alkyl, at least one of R8 and R7 is an oligomeric flexible tethering group, and R9 and R 10 Each is selected from C-1 to C-4 alkyl. In another aspect of this embodiment, both R8 and R7 are oligomeric flexible tethering groups.

[0134] In another embodiment of the block copolymer of structure (II) described herein, at least one of R5 and R6, at least one of R7 and R8, and R9 and R 10 In another aspect of this embodiment, R5, R6, R7, R8, R9 and R 10 It is an oligomeric flexible tethering group.

[0135] In any of the embodiments of the block copolymer of structure (II) described herein, wherein R5 and R6 are each selected from H and C-1 to C-4 alkyl, at least one of R8 and R7 is an oligomeric flexible tethering group, R9 and R 10 Each is selected from C-1 to C-4 alkyl. In another aspect of this embodiment, R8 and R7 are both oligomeric flexible tethering groups, and the block copolymer also has R1 and R2 are H, and R3 and R4 are C-1 to C-3 alkyl. In another aspect of this embodiment, R3 and R4 are C-1 to C-2 alkyl. In another aspect of this embodiment, R3 and R4 are methyl.

[0136] Another aspect of the present invention is a block copolymer having structure (III), wherein

[0137] A1 is a styrene block copolymer segment, whose T g From about 50°C to about 100°C

[0138] A2 is T ga block copolymer segment in the range of about -5°C to about -50°C comprising repeating units derived from an olefin selected from the group consisting of olefins, dienes and trienes or a mixture of at least two different olefins selected from the group;

[0139] B1 is a polar block copolymer segment having a T of about 50°C to about 100°C. g , comprising repeating units derived from 2-methylenealkanoic acid alkyl esters, repeating units derived from lactones, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonates;

[0140] L1 is a direct bond or a linking moiety derived from 1,1-diarylethene; wherein

[0141] E 3 is an alkyl group,

[0142] E 4 is a group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl), and further wherein

[0143] The block copolymer has a polydispersity ranging from 1 to about 1.09;

[0144] E 3 -A1-A2-L1-B1-E 4 (III).

[0145] In another embodiment of the block copolymers of structure (III) described herein, said A2 has repeating units derived from an olefin.

[0146] In another embodiment of the block copolymer of structure (III) described herein, the A2 has repeating units derived from a diene. In another aspect, the diene is a conjugated diene.

[0147] In any of the above embodiments of the block copolymers of structure (III) described herein, A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc) and (IIId) derived from a diene; wherein R d , R d1 , R d3 , R d4 , R e , R e1 , R e3 and R e4Each is selected from H and C-1 to C-8 alkyl, and further wherein the total mole % of olefinic repeating units in the block copolymer is from about 3 mole % to about 50 mole %. In another aspect of this embodiment, R d , R d1 , R d3 and R d4 are the same and are selected from H or C-1 to C-8 alkyl, and R e , R e1 , R e3 and R e4 is selected from H or C-1 to C-8 alkyl,

[0148]

[0149]

[0150] In another embodiment of the block copolymer of structure (III) described herein, A2 comprises repeating units derived from ethylene, propylene, butene, pentene, hexene, heptene, octene, isoprene, 3-methylenepent-1-ene, 3-methylenehex-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepent-1-ene, 1,3-butadiene, ethylidene norbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinyl norbornene (2-vinylbicyclo[2.2.1]hept-2-ene) or chloroprene (2-chlorobut-1,3-diene), or a mixture of at least two of these.

[0151] In another embodiment of the block copolymers of structure (III) described herein, wherein the repeating units in A2 are derived from a diene, it is a non-conjugated diene.

[0152] In another embodiment of the block copolymers of structure (III) described herein, the repeating units in A2 are derived from a triene.

[0153] In another embodiment of the block copolymers of structure (III) described herein, A2 has repeating units derived from a mixture of at least two different olefins selected from olefins, dienes, and trienes.

[0154] In any of the embodiments of the block copolymer of structure (III) described herein, wherein said A2 may further comprise styrenic repeating units.

[0155] In any of the embodiments of the block copolymers of structure (III) described herein, the polar block copolymer segment B1 comprises repeating units derived from a lactone.

[0156] In any of the embodiments of the block copolymers of structure (III) described herein, the polar block copolymer segment B1 comprises repeating units derived from alkyl 2-methylene alkanoate.

[0157] In any of the embodiments of the block copolymers of structure (III) described herein, the polar block copolymer segment Bl has an Mw between about 20,000 and about 200,000 and the non-polar styrene block segment has an Mw between 20,000 and about 200,000.

[0158] In one of the embodiments of the block copolymer of structure (III) described herein, wherein L1 is a direct valence bond.

[0159] In another embodiment of the block copolymers of structure (III) described herein, L1 is a linking group derived from 1,1-diarylethene.

[0160] In another embodiment of the block copolymers of structure (III) described herein, E 4 is H or alkyl.

[0161] In another embodiment of the block copolymers of structure (III) described herein, E 4 is a group derived from methyl-2-arylacrylate alkyl ester.

[0162] In another embodiment of the block copolymers of structure (III) described herein, E 3 It is an alkyl group.

[0163] In one embodiment of the block copolymer of structure (III), it has a more specific structure (IIIe), comprising

[0164] The styrene block is composed of random copolymerized styrene repeating units of structures (STc) and (STc), wherein R 1a and R 2a are each selected from H or C-1 to C-4 alkyl, R 5a and R 6a are each selected from H or C-1 to C-4 alkyl,

[0165] The connecting part of structure (L1), wherein R 7a and R 8a are each selected from H and C-1 to C-4 alkyl,

[0166] E' is a C-1 to C-12 alkyl terminal group,

[0167] E" is selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl);

[0168] x and x' designate the number of repeating units of structures (STc) and (STd), respectively, in the styrenic block, the repeating units having an Mw of about 20,000 to about 200,000, in the non-polar block segments, delimited by brackets designated by n,

[0169] y and y' designate the number of repeating units of structures (MEAc) and (MEAd), respectively, in the 2-methylene alkanoate derived block having an Mw of about 20,000 to about 200,000, in the polar block segment, bounded by brackets designated by m, wherein R 3a , R 4a , R 9a and R 10a each selected from C-1 to C-4 alkyl,

[0170] A2 is T g A block copolymer segment having a temperature of about -5°C to about -50°C, comprising repeating units derived from an olefin selected from the group consisting of olefins, dienes and trienes or a mixture of at least two different olefins selected from the group;

[0171]

[0172] In one embodiment of the block copolymer of structure (IIIe), R 1a , R 2a , R 5a , R 6a It's H.

[0173] In one embodiment of the block copolymer of structure (IIIe), R 7a and R 8a It's H.

[0174] In another embodiment of the block copolymer of structure (IIIe), R 3a , R 4a , R 9a and R 10a It is CH3.

[0175] In any of the embodiments of the block copolymer of structure (IIIe), A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc), and (IIId); wherein R d , R d1 , Rd3 , R d4 , R e , R e1 , R e3 and R e4 Each is selected from H and C-1 to C-8 alkyl, and further wherein the total mole % of olefinic repeating units in the block copolymer is from about 3 mole % to about 50 mole %.

[0176] In one embodiment of the block copolymer of structure (IIIe), R d , R d1 , R d3 and R d4 are the same and are selected from H or C-1 to C-8 alkyl, and R e , R e1 , R e3 and R e4 is selected from H or C-1 to C-8 alkyl,

[0177]

[0178] In one of the embodiments of the block copolymers of structure (IIIe) described herein, A2 is a block copolymer segment whose repeating units are derived from isoprene or butadiene.

[0179] In one of the embodiments of the block copolymers of structure (IIIe) described herein, the non-polar block copolymer segment A1 has a Mw of between about 20,000 and about 200,000.

[0180] In one of the embodiments of the block copolymers of structure (IIIe) described herein, E' is a C-3 to C-7 alkyl group.

[0181] In one of the embodiments of the block copolymers of structure (IIIe) described herein, E″ is H.

[0182] Another aspect of the present invention is a composition comprising a block copolymer of any structure (I) (or substructure thereof) described herein and a spin-cast organic solvent.

[0183] In one aspect of the composition comprising a block copolymer of structure (I), it further comprises another block copolymer.

[0184] In one aspect of the composition comprising the block copolymer of structure (I), it also comprises a homopolymer.

[0185] Another aspect of the present invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof) and a solvent.

[0186] Another aspect of the invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof), further comprising another block copolymer.

[0187] Another aspect of the present invention is a composition comprising a block copolymer of structure (III) (or a substructure thereof), further comprising a homopolymer.

[0188] In the inventive composition described herein comprising a copolymer of structure (I) or structure (III) (or their more specific substructures as described herein), in one embodiment, the spin casting solvent is selected from organic spin casting, which is a suitable solvent for dissolving the above-mentioned inventive composition, including glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate or propylene glycol monomethyl ether acetate (PGMEA); carboxylic acid esters, such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylic acid esters of dibasic acids, such as diethyl oxalate (diethyloxylate) and diethyl malonate; dicarboxylic acid esters of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate and ethyl 3-hydroxypropionate; ketoesters, such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylates, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketoether derivatives, such as diacetone alcohol methyl ether; ketoalcohol derivatives, such as acetone alcohol or diacetone alcohol; ketals or acetals, such as 1,3-dioxolane and diethoxypropane; lactones, such as butyrolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0189] In addition, the above-mentioned composition of the present invention may further include additives selected from the following: surfactants, polymers containing inorganic substances; additives, including small molecules, molecules containing inorganic substances, surfactants, photoacid generators, thermal acid generators, quenchers, hardeners, cross-linkers, chain extenders, etc.; and a combination comprising at least one of the foregoing, wherein one or more additional components and / or additives are assembled together with the block copolymer to form a block copolymer assembly.

[0190] Another aspect of the present invention is a method for vertically aligning first and second block copolymer domains on an unpatterned substrate using a block copolymer layer having a periodicity of L0, the method comprising the steps of:

[0191] a) forming a block copolymer coating on the unpatterned substrate from any composition described herein comprising a block copolymer of structure (I); and

[0192] b) annealing the layer of block copolymer to produce a non-zero positive integer number of first and second block copolymer domains that are vertically oriented on the unpatterned substrate.

[0193] Another aspect of the invention is a method for vertically aligning first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a L0 periodicity, wherein the topography height of the pattern on the substrate is at least 0.7 times the L0, and aligning the domains with the pattern, the method comprising the steps of:

[0194] a1) forming a block copolymer coating on said first topographical substrate from any composition described herein comprising a block copolymer of structure (I), wherein an average thickness of the block copolymer coating has a thickness less than a height of a topography of the first topographical substrate, wherein the block copolymer layer is laterally confined by the topography; and

[0195] b1) annealing the block copolymer layer to produce first and second block copolymer domains, the first and second block copolymer domains being vertically oriented on the first patterned substrate and confined within the recessed regions.

[0196] Another aspect of the invention is a method of vertically aligning first and second block copolymer domains having a periodicity of L0 on a second patterned substrate having a topographic pattern having a topographic height greater than 0.7 times L0 and a pitch P1, wherein the pitch P1 is a non-zero positive integer multiplied by L0, and aligning the domains with the pattern, the method comprising the steps of:

[0197] a2) forming a block copolymer coating on the second patterned substrate from any of the compositions described herein comprising a block copolymer of structure (I), wherein the thickness of the block copolymer coating is greater than the height of the topography of the second patterned substrate; and

[0198] b2) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the second patterned substrate and aligning them to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographic pattern.

[0199] Another aspect of the present invention is a method for vertically aligning first and second block copolymer domains and aligning the domains on a substrate having a surface chemical pre-pattern (the surface chemical pre-pattern has a spacing P2, wherein the spacing P2 is a non-zero positive integer multiplied by L0), the method comprising the steps of:

[0200] a3) forming a block copolymer coating from any of the compositions described herein comprising a block copolymer of structure (I) on a substrate having a surface chemical pre-pattern; and

[0201] b3) annealing the block copolymer layer to produce homeotropically oriented first and second block copolymer domains aligned with the substrate, the substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2.

[0202] Another aspect of the present invention is a method for vertically aligning first and second block copolymer domains on an unpatterned substrate using a block copolymer layer having a periodicity of L0, the method comprising the steps of:

[0203] a4) forming a block copolymer coating on the unpatterned substrate from any composition described herein comprising a block copolymer of structure (III); and

[0204] b4) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the unpatterned substrate.

[0205] Another aspect of the invention is a method for vertically aligning first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a L0 periodicity, wherein the topography height of the pattern on the substrate is at least 0.7 times the L0, and aligning the domains with the pattern, the method comprising the steps of:

[0206] a5) forming a block copolymer coating on said first topographical substrate from any composition described herein comprising a block copolymer of structure (III), wherein the average thickness of the block copolymer coating is less than the height of the topography of the first topographical substrate, wherein the block copolymer layer is laterally confined by the topography; and

[0207] b5) annealing the block copolymer layer to produce first and second block copolymer domains, the first and second block copolymer domains being vertically oriented on the first patterned substrate and confined within the recessed regions.

[0208] Another aspect of the present invention is a method of vertically aligning first and second block copolymer domains of periodicity L0 on a second patterned substrate having a topographic pattern with a topographic height greater than 0.7 times L0 and a pitch P1, wherein the pitch P1 is a non-zero positive integer multiplied by L0, and aligning the domains with the pattern, the method comprising the steps of:

[0209] a6) forming a block copolymer coating on the second patterned substrate from any composition described herein comprising a block copolymer of structure (III), wherein the thickness of the block copolymer coating is greater than the height of the topography of the second patterned substrate; and

[0210] b6) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the second patterned substrate and aligning them to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographic pattern.

[0211] Another aspect of the present invention is a method for vertically aligning first and second block copolymer domains and aligning the domains on a substrate having a surface chemical pre-pattern (the surface chemical pre-pattern has a spacing P2, wherein the spacing P2 is a non-zero positive integer multiplied by L0), the method comprising the steps of:

[0212] a7) forming a block copolymer coating from any of the compositions described herein comprising a block copolymer of structure (III) on a substrate having a surface chemical pre-pattern; and

[0213] b7) annealing the block copolymer layer to produce homeotropically oriented first and second block copolymer domains aligned with the substrate, the substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2. Example

[0214] Chemicals

[0215] Unless otherwise stated, all chemicals were obtained from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g., Techniques in High-Vacuum Anionic Polymerization by David Uhrig and Jimmy Mays, and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0216] Phenyl acrylate derivatives are synthesized by esterification of acryloyl chloride with corresponding hydroxy compounds under alkaline conditions, and DPE derivatives are synthesized by alkoxylation of DPE-(m)-CH2Br (1-(bromomethyl)-3-(1-phenylvinyl)benzene) with corresponding hydroxy compounds under alkaline conditions.

[0217] All synthesis experiments were performed under N2 atmosphere. Photolithography experiments were performed as described in the text. The molecular weight of the copolymers was measured by gel permeation chromatography. The gel permeation chromatograph was equipped with and μ-ultrastyragel column.

[0218] The photolithography experiment was completed using a TEL Clean ACT8 coating and developing machine (track). The SEM images were taken using an Applied Materials NanoSEM_3D scanning electron microscope, and the images were displayed at 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm).

[0219] For the self-assembled monolayer block copolymers of methyl methacrylate and styrene, etching experiments were performed using standard isotropic oxygen etching conditions.

[0220] Unless otherwise stated, molecular weight measurements (also referred to as M n polydispersity) is obtained by and The chromatography was performed on a gel permeation chromatography (PSS Inc. Germaby) using a μ-ultrastyragel column of 1000nm using THF solvent as eluent. Polystyrene polymer standards were used for calibration.

[0221] DSC measurements of glass transition temperature were performed using a TA Instruments DSC Q1000 under nitrogen at a heating rate of 10°C / min. The glass transition temperature (T g ). Consider the midpoint of the endothermic transition.

[0222] Recorded using a Bruker Advanced III 400 MHz spectrometer 1 H NMR spectroscopy.

[0223] The molecular weight of the copolymers was measured using gel permeation chromatography. Chemicals were purchased from Sigma-Aldrich unless otherwise stated.

[0224] These newly developed modified diblocks were tested for fingerprint morphology on neutral underlayer brush substrates on SiOx. To evaluate the new novel diblock copolymers, we also developed a thick film fingerprint grid defect analysis method, where we coated these block copolymers at 2 and 3×Lo and partially dry etched (with oxygen plasma) to identify and count grid defects in the bulk of the film. Comparing these results to conventional diblocks, the modified multi-tethered diblock copolymers showed very few defects and faster kinetics. The synthesis of these polymers was done by living anionic copolymerization and the diblock copolymers showed narrow molecular weight distribution (Mw / Mn<1.1) and worked well with normal underlayers suitable for PS-b-PMMA DSA.

[0225] Bottom layer neutral copolymer 1:

[0226] Copolymer of styrene, methyl methacrylate and 4-vinylbenzocyclobutene synthesized with AIBN

[0227] A 2000ml flask equipped with a condenser, a temperature controller, a heating jacket and a mechanical stirrer is installed. In the flask, 87.0 grams (0.84 mole) of styrene (S), 139.8 grams (1.40 moles) of methyl methacrylate (MMA), 72.4 grams (0.56 moles) of 4-vinylbenzocyclobutene (VBCB), 1.83 grams (0.011 moles) of azobisisobutyronitrile (AIBN) initiators and 600 grams of anisole are added. The mechanical stirrer is turned on and set at about 120rpm. Then the reaction solution is degassed by bubbling nitrogen through the solution for about 30 minutes at room temperature. After degassing for 30 minutes, the heating jacket is turned on, and the temperature controller is set at 70°C, and the stirred reaction mixture is kept at this temperature for 20 hours. After this time, the heating jacket is turned off, and the reaction solution is allowed to cool to about 40°C. Then the reaction mixture is poured into 12L isopropanol and stirred with mechanical stirring during the addition. During the addition, the polymer is precipitated. The precipitated polymer is collected by filtration. The collected polymer was dried in a vacuum oven at 40°C. About 170 g of polymer was obtained. The dried polymer was dissolved in 600 g of THF and then filtered through a 0.2 um nylon filter. The filtered solution was then precipitated again into a stirred 12 L methanol solution, and the precipitated polymer was collected and dried under vacuum at 40°C as described above. In this way, 150 g (50% yield) of polymer was obtained after drying. The M of the polymer was w It is about 38k and the polydispersity (PDI) is 1.5.

[0228] Reference Block Copolymer Synthesis Example 1 Synthesis of PS-b-PMMA)

[0229] PS-b-PMMA was synthesized using the same procedure as described in Example 2. nand the composition of the PS and PMMA blocks, changing the amount of initiator and the amount of monomer. Briefly, 20 g (192 mmol) of styrene was polymerized with 0.31 mL (1.4 M solution) of sec-butyl lithium. Then 0.09 g (0.50 mmol) of 1,1'-diphenylethylene (DPE) dissolved in 2.5 mL of anhydrous toluene was added to the reactor via an ampoule. The orange color of the reaction mixture turned into a dark brick red, indicating that the styryl lithium active center was converted into a delocalized DPE adduct carbon anion. After stirring for 2 minutes, a small amount (2 mL) of the reaction mixture was taken out for PS block molecular weight analysis. Methyl methacrylate (22.85 g, 230 mmol) was then added via an ampoule. After 30 minutes, the reaction was terminated with 1 ml of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (5 times the polymer solution) containing 10% water, filtered, and dried under vacuum at 55° C. for 12 hours to obtain 40 g of P(Sb-MMA) consisting of 46.9 mol % polystyrene blocks and 53.1 mol % polymethyl methacrylate blocks (94% yield). The molecular weight of the diblock copolymer obtained by GPC was M n =92K, PDI=1.02).

[0230] Synthesis of CH(PS-b-PMMA) with reference to block copolymer synthesis example 1a

[0231] The same procedure as in Example 1 was used except that the polystyrene block was 69 mol% and the polymethyl methacrylate block was 31 mol%. The diblock molecular weight obtained by GPC was M n =66.92K, PDI=1.01).

[0232] Synthesis of a novel modified AB diblock polymer

[0233] The diblock copolymers are unique and do not require a matching underlayer for homeotropic orientation. These are new kinetically enhanced diblock copolymers compared to conventional diblock copolymers.

[0234] Synthesis Example 2TAB-1 (Lines and Spaces)

[0235] This system demonstrates the synthesis of P(S-co-C8S)-bP(MMA-co-C6MA) with low T g Octylstyrene is copolymerized in PS block, and hexyl methacrylate is copolymerized in PMMA block (TAB):

[0236] In the presence of a dehydrating agent, styrene, octyl styrene, methyl methacrylate, and hexyl methacrylate monomers were distilled into calibrated ampoules and stored under N2. The liquid was transferred to the reactor through an ampoule or using a stainless steel cannula under N2. 500 mL of dry tetrahydrofuran and 0.35 g of LiCl were added to a dry 1 L round bottom reactor equipped with a side arm for connecting the ampoule, a magnetic stirring bar, and a nitrogen / vacuum three-way septum adapter. The temperature of the reactor was lowered to -78 ° C using a dry ice-acetone bath. Then, after titration of impurities, 3.6 ml (0.103 M solution) of s-BuLi was added to the reactor as an initiator. A mixture of 3.3 g (0.0152 mol) of n-octyl styrene and 14.23 g (0.137 mol) of styrene was then added to the reactor from an ampoule under rapid stirring. The reaction mixture turned orange-red and the reaction continued for 30 minutes. Subsequently, 0.08 g (0.00044 mol) of 1,1'-diphenylethylene was added to the reactor via an ampoule. The orange color of the reaction mixture turned into a dark brick red, indicating that the styryl potassium active center was converted into a styrene-DPE carbon anion. A small amount (2 mL) of the reaction mixture was taken out for P(S-co-C8S)-DPE block molecular weight analysis. A mixture of methyl methacrylate (14.8 g, 0.148 mol) and hexyl methacrylate (2.80 g, 0.0165 mol) was then added via an ampoule. The reaction was continued for 50 minutes to complete the polymerization of MMA and C6MA. The reaction mixture was then terminated with 1 ml of degassed methanol. The block copolymer was recovered by precipitation in an excess of isopropanol (5 times the polymer solution) containing 10% water, filtered, and dried in vacuo at 70°C for 12 hours to obtain 30 g of P(S-co-C8S)-bP(MMA-co-C6MA) (95% yield). Equipped with and Gel permeation chromatography using a μ-ultrastyragel column showed that the M of the first P(S-co-C8S)-DPE block was n (GPC) = 46,000 g / mol, M w / M n =1.03. The molecular weight of the diblock copolymer obtained by GPC is M n,P(S-co-C8S)-b-PS-b-P(MMA-co-C6MA) =83,000 g / mol, M w / M n =1.07.

[0237] Table 1 compares the T g Characteristics and Multi-tether Synthesis Example 2 TAB-1 g characteristic

[0238] Other novel multi-tethers were synthesized in a similar manner and their properties are summarized in Table 2 .

[0239] Synthesis Examples TAB 1, TAB 2, TAB 3, TAB 4 were manufactured in the same manner as TAB, but by changing the MW to obtain different L0s, so these samples are suitable for use in line and space (L / S) applications.

[0240] TAB 5 Example 6 Contact Hole BCP was synthesized using the same procedure described in Example TAB (Example 2), but by changing the following variables to change the characteristics of PS mol% and MW to obtain a multi-tethered block copolymer suitable for CH pore self-assembly.

[0241] Bottom Layer Polymer Example 1:

[0242] Synthesis of random x-linkable copolymers

[0243] Copolymers of styrene, methacrylate and 4-vinylbenzocyclobutene synthesized using AIBN

[0244] A 2000ml flask equipped with a condenser, a temperature controller, a heating jacket and a mechanical stirrer is installed. 87.0 grams (0.84 mole) of styrene (S), 139.8 grams (1.40 moles) of methyl methacrylate (MMA), 72.4 grams (0.56 moles) of 4-vinylbenzocyclobutene (VBCB), 1.83 grams (0.011 moles) of azobisisobutyronitrile (AIBN) initiator and 600 grams of anisole are added to the flask. The mechanical stirrer is turned on and set at about 120rpm. The reaction solution is then degassed by bubbling nitrogen through the solution for about 30 minutes at room temperature. After degassing for 30 minutes, the heating jacket is turned on, and the temperature controller is set at 70°C, and the stirred reaction mixture is kept at this temperature for 20 hours. After this time, the heating jacket is turned off, and the reaction solution is allowed to cool to about 40°C. The reaction mixture is then poured into 12L isopropanol and stirred with mechanical stirring during the addition. During the addition, the polymer is precipitated. The precipitated polymer is collected by filtration. The collected polymer was dried in a vacuum oven at 40°C. About 170 g of polymer was obtained. The dried polymer was dissolved in 600 g of THF and then filtered through a 0.2 μm nylon filter. The filtered solution was then precipitated again into a stirred 12 L methanol solution, and the precipitated polymer was collected and dried under vacuum at 40°C as described above. In this way, 150 g (50% yield) of polymer was obtained after drying. The M of the polymer was 1.3447 W / m. w It is about 38k and the polydispersity (PDI) is 1.5.

[0245] Self-assembly of block copolymers (BCPs) based on Examples 1 and 2 (Table 1)

[0246] The polymer of Example 1 was dissolved in PGMEA to form a 0.33 wt% solution. The solution was filtered using a 0.02 μm PTFE filter and then coated on a SiO x The wafers were then each baked at 250°C for 2 minutes in air to produce SiOx wafers coated with a cross-linked neutral layer (FT 8nm). The wafers were then coated with a 1.4 wt% solution of 0.02 μm PTFE filtered in PGMEA of reference polymer Example 1 (PS-b-PMMA) and TAB (polymer of the multi-tethered diblock copolymer (Example 2)), both of which were spin coated at 1,500 rpm and then soft-baked at 110°C for 1 minute, respectively, and then annealed at 250°C for 1 hour under N2. After this annealing bake, the film of either material formed a self-assembled pattern in which a nanophase-separated lamellar array perpendicular to the substrate was formed, which contained etchable blocks derived from methyl methacrylate, which was a microphase-separated array suitable for etching line and spacer array patterns transferred into the substrate. However, compared with the conventional diblock (Example 1) diblock copolymer of styrene and methyl methacrylate (PS-b-PMMA) (M n =92K, PDI=1.02) (Example 1), the film coated with the multi-tethered diblock copolymer (Example 2) also showed a perpendicular lamellar morphology with a significantly lower number of grid defects.

[0247] These novel diblock copolymers have a g and total T g (Table 2) showed significant T g Reduce. Figure 3 ), fewer grids with higher particle size were observed, which shows a 1 FOV SEM image obtained by the following treatment: coating and baking a solution of the bottom layer neutral copolymer 1 under the following conditions: 250 ° C (N2) for 1 hour; EBR 70 / 30 2 min, spin dry, 110°C / 1 min, FT = 45 nm. Multi-tethered diblock shows improved crystallite size.

[0248] Processing Example 2:

[0249] The processing example conditions described in Processing Example 1 were primarily used to prepare the membrane of Example 6 (TAB 5), which is a multi-tethered block copolymer designed for self-assembly of contact holes (CH). The processing conditions were only slightly modified as follows: the block copolymer was baked at 260°C for 15 minutes (N2) and then heated with EBR 70 / 30 rinse, spin drying for 2 minutes followed by baking for 1 minute at 110° C. In this case a film thickness (FT) of 47 nm was obtained. Figure 4The annealed film formed is shown. The multi-tethered diblock shows improved contact hole assembly. In general, when low T g When the additive is added, the PS-b-PMMA block copolymer obtains good C / H assembly. The multi-tethered diblock copolymer of the present invention shows good C / H assembly without any additive, indicating significant kinetic enhancement. In contrast, Figure 5 As shown, when a conventional diblock film (Example 1) (also known as a diblock copolymer of styrene and methyl methacrylate (PS-b-PMMA) (M n =66.92K, PDI=1.01) (Example 1a)), the obtained 34.2nm contact hole showed large area defects caused by the mixed morphology.

[0250] Another advantage of the newly disclosed modified AB diblock copolymer (Example 2) is that, for unmodified PS-b-PMMA DSA, no changes to the primer and pinning chemistry currently used in DSA processing are required.

[0251] Table 1. Td and T of conventional PS-b-PMMA and modified P(S-co-C8S)-bP(MMA-co-C6MMA) g

[0252]

[0253] Table 2. Synthesis and characterization data of diblock copolymers

[0254]

Claims

1. A block copolymer having structure (I), wherein The A segment is a non-polar block copolymer segment comprising styrene repeating units, L is a direct bond or a linking moiety derived from 1,1-diarylethene; The B segment is a polar block copolymer segment, comprising repeating units derived from 2-methylene alkanoic acid alkyl esters, repeating units derived from lactones, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonates; E' is a C-1 to C-12 alkyl terminal group, E" is a terminal group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a 2-aryl alkyl acrylate derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl); and further The block copolymer of structure (I) is multi-tethered by oligomeric flexible tethering groups selected from oligomeric linear alkylene tethering groups, oligomeric ether tethering groups and oligomeric dialkylsiloxane tethering groups, and if L is a linking moiety derived from 1,1-diarylethene, these oligomeric flexible tethering groups are multi-tethered on at least one of the A segment, the B segment and L, and the block copolymer has a polydispersity ranging from 1 to about 1.09 and an Mn of at least 40,000: E'-ALBE" (I). 2 . The block copolymer of claim 1 , wherein the oligomeric flexible tethering group is an oligomeric linear alkylene tethering group.

3. The block copolymer according to claim 1 or 2, wherein the oligomeric flexible tethering group is a block copolymer having a general structure -X1-(CH2) a A low-polymer straight-chain alkylene tethered group of -CH3, wherein n is 6 to 19 and X1 is and X1 is selected from a direct valence bond, a straight-chain C-1 to C-4 alkylene spacer, -O-, -CH2-O-, -O-(C=O)-, -C=OO-, C=O, -CH2-O-(C=O)-, -S-, -SO2- and -SO-. The block copolymer of claim 1 , wherein the oligomeric flexible tethering group is an oligomeric ether tethering group.

5. The block copolymer according to claim 1 or 4, wherein the oligomeric flexible tethering group is an oligomeric ether tethering group having the formula -O-[(CH2) e -O-] e2 -(CH2) e3 -H or -(CH2) e4 -O-[(CH2) e -O-] e2 -(CH2) e3 -H, wherein independently e is 2 to 8, e2 is 2 to 8, e3 is 1 to 8, and e4 is 1 to 8.

6. The block copolymer of claim 1, wherein the oligomeric flexible tethering group is an oligomeric dialkylsiloxane tethering group.

7. The composition of claim 1 or 6, wherein the oligomeric flexible tethering group is a poly(alkyl)- ... s -Si(alkyl)3 oligomeric dialkylsiloxane tether groups, wherein s is 6 to 18, and the alkyl portion is a C-1 to C-8 alkyl, and X2 is a direct bond, or a C-1 to C-8 linear alkylene spacer, or -O-.

8. The block copolymer according to any one of claims 1 to 7, wherein the polar block copolymer fragment B comprises repeating units derived from lactone.

9. The block copolymer according to any one of claims 1 to 7, wherein the polar block copolymer fragment B comprises repeating units derived from alkyl 2-methylene alkanoate.

10. The block copolymer of any one of claims 1 to 9, wherein the polar block copolymer segment B segments have an Mw between about 20,000 and about 200,000, and the non-polar styrenic block copolymer segment A segments have an Mw between 20,000 and about 200,000.

11. The block copolymer according to any one of claims 1 to 10, wherein L is a direct valence bond.

12. The block copolymer according to any one of claims 1 to 10, wherein L is a linking group derived from 1,1-diarylethene.

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

14. The block copolymer according to any one of claims 1 to 12, wherein E" is an alkyl group.

15. The block copolymer according to any one of claims 1 to 12, wherein E" is a carbonylalkyl group (-C=O-alkyl).

16. The block copolymer according to any one of claims 1 to 12, wherein E" is a carbonyloxyalkyl group (-C=OO-alkyl).

17. The block copolymer according to any one of claims 1 to 12, wherein E" is a 2-aryl alkyl acrylate derived terminal group (-CH2-CH(aryl)(C(=O))-O-alkyl).

18. The block copolymer according to any one of claims 1 to 17, wherein the oligomeric flexible tethering groups are located on the A segment and are either randomly located along the segment on some of its repeating units or are present on every repeating unit thereof.

19. The block copolymer according to any one of claims 1 to 18, wherein the oligomeric flexible tethering group is located on the B segment and is either randomly located along the segment on some of its repeating units or is present on every repeating unit thereof. 20 . The block copolymer according to claim 1 , wherein the oligomeric flexible tethering group is located on the linking group L when the linking group L is derived from 1,1-diarylethene.

21. The block copolymer according to any one of claims 1 to 20, wherein if L is derived from 1,1-diarylethene, the oligomeric flexible tethering groups are located on the A segments, the B segments and the linking group L, and are either randomly located along the A segments or the B segments on some of their respective repeating units, or are present on each of their respective repeating units.

22. The block copolymer according to any one of claims 1 to 18, wherein the oligomeric flexible tethering group is located only on the A segment and is either randomly located along the segment on some of its repeating units or is present on every repeating unit thereof.

23. The block copolymer according to any one of claims 1 to 17 and 19, wherein the oligomeric flexible tethering groups are located only on the B segment and are either randomly located along the segment on some of its repeating units or are present on every repeating unit thereof.

24. The block copolymer according to any one of claims 1 to 17 and 20, wherein the oligomeric flexible tethering group is only located on the linking group L if L is derived from 1,1-diarylethene.

25. The block copolymer according to any one of claims 1 to 19, wherein the oligomeric flexible tethering groups are located only on the A segment and the B segment, and are either randomly located on some of their respective repeating units along the A segment and the B segment, or are present on each of their respective repeating units.

26. The block copolymer according to any one of claims 1 to 18 and 20, wherein if the linking group L is derived from 1,1-diarylethene, the oligomeric flexible tethering group is located only on both the A segment and the linking group L, and is either randomly located along the A segment on some of its repeating units or is present on each of its repeating units.

27. The block copolymer according to any one of claims 1 to 17, 19 and 20, wherein if L is derived from 1,1-diarylethene, the oligomeric flexible tethering group is located only on the B segment and the linking group L, and is either randomly located along the B segment on some of its repeating units or is present on each of its repeating units.

28. The block copolymer of any one of claims 1 to 21, wherein oligomeric flexible tethering groups are present on the A segments or the B segments or both, said oligomeric flexible tethering groups being randomly present on some of their repeating units along their respective segments.

29. The block copolymer according to any one of claims 1 to 21, wherein oligomeric flexible tethering groups are present on the A segments or the B segments or both, these oligomeric flexible tethering groups being present on all their respective repeating units.

30. The block copolymer according to any one of claims 1 to 29, wherein the copolymer has structure (II) comprising: A styrenic block composed of randomly copolymerized styrenic repeating units of structures (STa) and (STb), wherein R1 and R2 are each selected from H or C-1 to C-4 alkyl, R5 and R6 are each selected from H or C-1 to C-4 alkyl, and an oligomeric flexible tethering group selected from an oligomeric linear alkylene tethering group, an oligomeric ether tethering group, and an oligomeric dialkylsiloxane tethering group; a linking moiety of structure (L1), wherein R7 and R8 are each selected from H, C-1 to C-4 alkyl, and are multi-tethered by an oligomeric flexible tethering group selected from an oligomeric linear alkylene tethering group, an oligomeric ether tethering group, and an oligomeric dialkylsiloxane tethering group; The 2-methylene alkanoate derived block is composed of randomly copolymerized 2-methylene alkanoate repeating units of the structures (MEAa) and (MEAb), wherein R3 and R4 are each selected from C-1 to C-4 alkyl, and R9 and R 10 each selected from C-1 to C-4 alkyl groups and multi-tethered with an oligomeric flexible tethering group selected from an oligomeric linear alkylene tethering group, an oligomeric ether tethering group, and an oligomeric dialkylsiloxane tethering group; E' is a C-1 to C-10 alkyl terminal group, E" is selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl); x and x' represent the number of repeating units of structures (STa) and (STb), respectively, in the styrenic block having a Mw of about 20,000 to about 200,000 and in the non-polar block segment, which is delimited by brackets denoted by n, y and y' represent the number of repeating units of structures (MEAa) and (MEAb), respectively, in the 2-methylene alkanoate derived block, the block having an Mw of about 20,000 to about 200,000, and in the polar block segment, which is bounded by brackets denoted by m, and further wherein at least one of structures (STa), (STb), (L1), (MEAa) and (MEAb), respectively, has R5, R6, R7, R8, R9 or R1 selected from the oligomeric flexible tethering group 10 31. The block copolymer of claim 30, wherein R5 is an oligomeric flexible tethering group, R6 is H or a C-1 to C-4 alkyl group, R7 and R8 are each selected from H and a C-1 to C-4 alkyl group, R9 and R 10 Each is selected from C-1 to C-4 alkyl groups.

32. The block copolymer of claim 30, wherein R5 and R6 are multi-tethered with oligomeric flexible tethering groups, R7 and R8 are each selected from H and C-1 to C-4 alkyl, R9 and R 10 Each is selected from C-1 to C-4 alkyl groups.

33. The block copolymer of claim 30, wherein R5 and R6 are each selected from H and C-1 to C-4 alkyl, at least one of R8 and R7 is an oligomeric flexible tethering group, and R9 and R 10 Each is selected from C-1 to C-4 alkyl groups.

34. The block copolymer of claim 33, wherein both R8 and R7 are oligomeric flexible tethering groups.

35. The block copolymer according to claim 30, wherein R5 and R6 are each selected from H and C-1 to C-4 alkyl, R8 and R7 are each selected from H and C-1 to C-4 alkyl, and R9 and R 10 At least one of the is an oligomeric flexible tethering group.

36. The block copolymer according to claim 30, wherein R9 and R 10 Both are oligomeric flexible tethering groups.

37. The block copolymer according to claim 33, wherein at least one of R5 and R6, and R9 and R 10 At least one of the is a flexible tethering group.

38. The block copolymer of claim 37, wherein both R5 and R6 and R9 and R 10 Both are flexible tether groups.

39. The block copolymer according to claim 33, wherein at least one of R5 and R6, at least one of R7 and R8, and R9 and R 10 At least one of the is a flexible tethering group.

40. The block copolymer according to claim 39, wherein R5, R6, R7, R8, R9 and R 10 It is an oligomeric flexible tethering group.

41. The block copolymer of any one of claims 33 to 40, wherein R1 and R2 are H.

42. The block copolymer of any one of claims 33 to 41, wherein R3 and R4 are C-1 to C-3 alkyl.

43. The block copolymer of any one of claims 33 to 42, wherein R3 and R4 are C-1 to C-2 alkyl groups.

44. The block copolymer of any one of claims 33 to 43, wherein R3 and R4 are methyl.

45. A block copolymer having structure (III), wherein A1 is a styrenic block copolymer segment having a T of about 50°C to about 100°C. g A2 is T g A block copolymer segment having a temperature of about -5°C to about -50°C, comprising repeating units derived from an olefin selected from the group consisting of olefins, dienes and trienes or a mixture of at least two different olefins selected from the group; B1 is a polar block copolymer segment having a T of about 50°C to about 100°C. g , comprising repeating units derived from 2-methylenealkanoic acid alkyl esters, repeating units derived from lactones, repeating units derived from ethylene oxide, repeating units derived from oxetane, or repeating units derived from cyclic carbonates; L1 is a direct bond or a linking moiety derived from 1,1-diarylethene; wherein E 3 is an alkyl group, E 4 is a group selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl), and further wherein The block copolymer has a polydispersity of 1 to about 1.09, AND 3 -A1-A2-L1-B1-E 4 (III)。 46. ​​The block copolymer of claim 45, wherein A2 has repeating units derived from an olefin.

47. The block copolymer of claim 45, wherein A2 has repeating units derived from a diene.

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

49. The block copolymer according to any one of claims 45, 47 and 48, wherein A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc) and (IIId) derived from dienes; wherein R d , R d1 , R d3 , R d4 , R e , R e1 , R e3 and R e4 each selected from H and C-1 to C-8 alkyl, and further wherein the total mole % of olefinic repeating units in the block copolymer is in the range of about 3 mole % to about 50 mole %; 50. The block copolymer according to any one of claims 45, 48 and 49, wherein A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc) and (IIId) derived from dienes; wherein R d , R d1 , R d3 and R d4 are the same and are selected from H or C-1 to C-8 alkyl, and R e , R e1 , R e3 and R e4 is selected from H or C-1 to C-8 alkyl, 51. The block copolymer of claim 45 or 46, wherein A2 comprises repeating units derived from ethylene, propylene, butene, pentene, hexene, heptene, octene, isoprene, 3-methylenepent-1-ene, 3-methylenehex-1-ene, 3,4-dimethylenehexane, 2-methyl-3-methylenepent-1-ene, 1,3-butadiene, ethylidene norbornene (2-ethylidene-5-norbornene), dicyclopentadiene, vinyl norbornene (2-vinylbicyclo[2.2.1]hept-2-ene), or chloroprene (2-chlorobut-1,3-diene), or a mixture of at least two of these.

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

53. The block copolymer of claim 45 or 46, wherein A2 is derived from a triolefin.

54. The block copolymer of claim 45, wherein A2 has repeating units derived from a mixture of at least two different olefins selected from olefins, dienes, and trienes.

55. The block copolymer according to any one of claims 45 to 51, wherein A2 further comprises styrenic repeating units.

56. The block copolymer according to any one of claims 45 to 55, wherein the polar block copolymer fragment B1 comprises repeating units derived from a lactone.

57. The block copolymer of any one of claims 45 to 55, wherein the polar block copolymer segment B1 comprises repeating units derived from alkyl 2-methylene alkanoate.

58. The block copolymer of any one of claims 45 to 57, wherein the polar block copolymer segment Bl has an Mw of about 20,000 to about 200,000, and the non-polar styrenic block segment has an Mw of 20,000 to about 200,000.

59. The block copolymer according to any one of claims 45 to 58, wherein L1 is a direct valence bond.

60. The block copolymer of any one of claims 45 to 58, wherein L1 is a linking group derived from 1,1-diarylethene.

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

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

63. The block copolymer according to any one of claims 45 to 62, wherein E 3 It is a C-1 to C-8 alkyl group.

64. A block copolymer according to any one of claims 45 to 52, 54, 55, 57, 58 or 60 having structure (IIIe) comprising The styrene block is composed of random copolymerized styrene repeating units of structures (STc) and (STc), wherein R 1a and R 2a are each selected from H or C-1 to C-4 alkyl, R 5a and R 6a are each selected from H or C-1 to C-4 alkyl, The connecting part of structure (L1), wherein R 7a and R 8a are each selected from H and C-1 to C-4 alkyl, wherein E' is a C-1 to C-20 alkyl terminal group, E" is selected from H, alkyl, carbonylalkyl (-C=O-alkyl), carbonyloxyalkyl (-C=OO-alkyl) and a terminal group derived from 2-aryl alkyl acrylate (-CH2-CH(aryl)(C(=O))-O-alkyl); x and x' represent the number of repeating units of structures (STc) and (STd), respectively, in said styrenic block having a Mw of about 20,000 to about 200,000, in the non-polar block segment, which is delimited by brackets denoted by n, y and y' represent the number of repeating units of structures (MEAc) and (MEAd), respectively, in the 2-methylene alkanoate derived block having an Mw of about 20,000 to about 200,000, in the polar block segment, bounded by brackets denoted by m, wherein R 3a and R 4a、 R 9a and R 10a each selected from C-1 to C-4 alkyl, A2 is T g A block copolymer segment having a temperature of about -5°C to about -50°C, comprising repeating units derived from an olefin selected from the group consisting of olefins, dienes and trienes or a mixture of at least two different olefins selected from the group; 65. The block copolymer according to claim 64, wherein R 1a , R 2a , R 5a , R 6a It's H.

66. according to the block copolymer described in claim 64 or 65, wherein R 7a and R 8a It's H.

67. The block copolymer according to any one of claims 64 to 66, wherein R 3a , R 4a , R 9a and R 10a It is CH3.

68. The block copolymer according to any one of claims 64 to 67, wherein A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc) and (IIId); wherein R d , R d1 , R d3 , R d4 , R e , R e1 , R e3 and R e4 each selected from H and C-1 to C-8 alkyl, and further wherein the total mole % of olefinic repeating units in the block copolymer is from about 3 mole % to about 50 mole %; 69. A block copolymer according to any one of claims 64 to 68, wherein A2 comprises a mixture of at least two different repeating units having structures (IIIa), (IIIb), (IIIc) and (IIId), wherein R d , R d1 , R d3 and R d4 are the same and are selected from H or C-1 to C-8 alkyl, and R e , R e1 , R e3 and R e4 is selected from H or C-1 to C-8 alkyl, 70. The block copolymer of any one of claims 64 to 69, wherein A2 is a block copolymer segment whose repeating units are derived from isoprene or butadiene.

71. The block copolymer of any one of claims 64 to 70, wherein the non-polar block copolymer fragment A1 has a Mw between about 20,000 and about 200,000.

72. The block copolymer of any one of claims 64 to 71, wherein E' is a C-3 to C-7 alkyl group.

73. A block copolymer according to any one of claims 64 to 71, wherein E" is H.

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

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

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

77. A method for vertically aligning first and second block copolymer domains on an unpatterned substrate using a block copolymer layer having a periodicity of L0, comprising the steps of: a) forming a block copolymer coating on the unpatterned substrate from the composition according to any one of claims 74 to 76; and b) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains that are vertically oriented on the unpatterned substrate.

78. A method for vertically aligning first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a periodicity of L0 and aligning the domains with the pattern, wherein the topography height of the pattern on the substrate is at least 0.7 times L0, the method comprising the steps of: a1) forming a coating of the composition of any one of claims 74 to 76 on the first topographical substrate, wherein the average thickness of the block copolymer coating has a thickness less than the height of the topography of the first topographical substrate, wherein the block copolymer layer is laterally confined by the topography; and b1) annealing the block copolymer layer to produce first and second block copolymer domains, the first and second block copolymer domains being vertically oriented on the first patterned substrate and confined within the recessed regions.

79. A method of vertically orienting first and second block copolymer domains having a periodicity of L0 on a second patterned substrate and aligning the domains with the pattern, the second patterned substrate having a topographic pattern having a topographic height greater than 0.7 times L0 and a pitch P1, wherein the pitch P1 is a non-zero positive integer multiplied by L0, the method comprising the steps of: a2) forming a block copolymer coating from the composition according to any one of claims 74 to 76 on the second patterned substrate, wherein the thickness of the block copolymer coating is greater than the topography height of the second patterned substrate; and b2) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the second patterned substrate and aligning them to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographic pattern.

80. A method of vertically orienting first and second block copolymer domains and aligning the domains on a substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2, wherein the pitch P2 is a non-zero positive integer multiplied by L0, the method comprising the steps of: a3) forming a block copolymer coating from the composition according to any one of claims 74 to 76 on a substrate having a surface chemical pre-pattern; and b3) annealing the block copolymer layer to produce homeotropically oriented first and second block copolymer domains aligned with the substrate, the substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2.

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

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

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

84. A method for vertically aligning first and second block copolymer domains on an unpatterned substrate using a block copolymer layer having a periodicity of L0, comprising the steps of: a4) forming a block copolymer coating on the unpatterned substrate from the composition according to any one of claims 81 to 83; and b4) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the unpatterned substrate.

85. A method for vertically aligning first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a L0 periodicity and aligning the domains with the pattern, wherein the topography height of the pattern on the substrate is at least 0.7 times the L0, the method comprising the steps of: a5) forming a coating of the composition of any one of claims 81 to 83 on the first topographical substrate, wherein the average thickness of the block copolymer coating is less than the height of the topography of the first topographical substrate, wherein the block copolymer layer is laterally confined by the topography; and b5) annealing the block copolymer layer to produce first and second block copolymer domains, the first and second block copolymer domains being vertically oriented on the first patterned substrate and confined within the recessed regions.

86. A method of vertically orienting first and second block copolymer domains having a periodicity of L0 on a second patterned substrate and aligning the domains with the pattern, the second patterned substrate having a topographic pattern having a topographic height greater than 0.7 times L0 and a pitch P1, wherein the pitch P1 is a non-zero positive integer multiplied by L0, the method comprising the steps of: a6) forming a block copolymer coating on the second patterned substrate from the composition according to any one of claims 81 to 83, wherein the thickness of the block copolymer coating is greater than the topography height of the second patterned substrate; and b6) annealing the block copolymer layer to produce a non-zero positive integer number of first and second block copolymer domains vertically oriented on the second patterned substrate and aligning them to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographic pattern.

87. A method of vertically orienting first and second block copolymer domains and aligning the domains on a substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2, wherein the pitch P2 is a non-zero positive integer multiplied by L0, the method comprising the steps of: a7) forming a block copolymer coating from the composition according to any one of claims 81 to 83 on a substrate having a surface chemical pre-pattern; and b7) annealing the block copolymer layer to produce homeotropically oriented first and second block copolymer domains aligned with the substrate, the substrate having a surface chemical pre-pattern, the surface chemical pre-pattern having a pitch P2.

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

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