DSA of liquid crystal block copolymers for integrated circuit patterning

Abstract

Disclosed is a block copolymer which is an AB diblock copolymer having a first block A of structure (I) and a second block B of structure (II) wherein R and Ri are independently selected from C-1 to C-4 alkyl groups wherein the mol% range of the repeating units of structure (I) is about 35 mol% to about 94 mol% and the mol% range of the repeating units of structure (II) is about 6 mol% to about 65 mol%, r2 is selected from C-1 to C-11 alkyl groups, L is C-5 to C-12 linear alkylene groups, and R3 is selected from C-3 to C-8 linear alkyl groups, R'is H or C-3 to C-8 linear alkyl groups, where the block copolymer has a polydispersity of from 1 to about 1.31. Also described are compositions of such block copolymers in solvents and their use in DSA treatments. # imgabs0 #

Description

Technical Field

[0001] The disclosed and claimed subject matter relates to block copolymers having liquid crystal pendants and compositions of such block copolymers in organic spin-cast films; and processes for forming directed self-assembly block copolymer films using such compositions on substrates. Background Art

[0002] In the last few decades, many efforts have been made to further increase the miniaturization, cost, speed, power consumption, and functionality of the silicon-based integrated circuit industry (IC). Great progress has been made in increasing the number of transistors in each CPU, and current microprocessors contain up to four billion transistors per small unit area. To build these types of processors, a series of operations need to be implemented; the processing steps include lithography, etching, and deposition. Lithography is a key step in the manufacture of transistors and resistors. The main factor affecting the resolution of the resulting structure is the illumination wavelength used in lithography. The smaller the wavelength, the higher the possible resolution and the smaller the pitch size. Currently, 193 nm is the smallest illumination wavelength introduced into ICs, and it can provide a ~80 nm pitch; however, the current industrial goal is to achieve a single nanometer pitch size in the same unit area.

[0003] To avoid investment in new equipment and materials, multiple patterning lithography techniques have been introduced, and a pitch of ~40 nm has been achieved. However, multiple patterning comes at the cost of increased steps, defects, cost, processing time, tools, fab space, consumable materials, and the number of personnel.

[0004] In conventional lithography methods, ultraviolet (UV) radiation can be used to expose 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 enable dry development using conventional integrated circuit (IC) plasma processing. In positive photoresists, the UV radiation transmitted through the mask causes a photochemical reaction in the photoresist to remove the exposed areas using a developer solution or by conventional IC plasma processing. In contrast, in negative photoresists, the UV radiation transmitted through the mask causes the areas exposed to the radiation to be more difficult to remove using a developer solution or by conventional IC plasma processing. Integrated circuit features (such as gates, vias, or interconnects) are then etched into the substrate or the layered substrate, and the remaining photoresist is removed. When using conventional lithography exposure methods, the feature sizes of integrated circuit features are limited. Due to limitations related to aberration, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture, it is difficult to further reduce the pattern size using radiation exposure. Directed self-assembly is a promising method that has been receiving much attention for overcoming some of the drawbacks of conventional lithography as outlined above. Directed self-assembly of block copolymers is a method that can be used to generate increasingly smaller patterned features for manufacturing microelectronic devices, where critical dimensions (CDs) of features on the order of nanometers can be achieved. The directed self-assembly method is desirable for expanding the resolution capabilities of micro-lithography etching techniques. The need for large-scale integration has led to continuous shrinking of circuit sizes and features in devices. In the past, the ultimate resolution of features has depended on the wavelength of light used to expose the photoresist, which has its own limitations. The most recent technology using shorter wavelength light to achieve that pitch is extreme ultraviolet lithography (EUV), which can theoretically achieve a maximum pitch resolution of ~13.5 nm. However, this technology has a high defect rate, which is incompatible with industrial expectations. Specific defects of EUV can be summarized as mask defects and are a combination of substrate, multilayer blank, and absorber patterning defects. Additionally, this technology is especially costly, and only 53 machines in the world are capable of production. Direct assembly techniques (such as graphoepitaxy and chemoepitaxy using block copolymer imaging) are highly desirable techniques for enhancing resolution and at the same time reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or enable even higher resolution and CD control in methods using EUV, electron beam, deep UV, or immersion lithography.

[0005] Directed self-assembly (DSA) of block copolymer (BCP) lithography is an additional alternative or supplement to conventional lithography, which differs from the above methods in that it involves a combination of bottom-up and top-down methods. The template generated using lithography\EUV technology (top-down method) is spin-coated with BCP, which then undergoes phase separation at an extremely high single-nanometer resolution (bottom-up) under the influence of the guiding pattern (template). Subsequently, one block is selectively etched, and the desired pitch pattern is obtained based on the size of that block.

[0006] A block copolymer (BCP) consists of at least two different homopolymers connected by covalent bonds. Under certain conditions, the BCP self-assembles into a nanostructure pattern with a vertical lamellar microstructure. This allows for selective etching of one block down to the substrate, such that the remaining block repeats with a constant single-nanometer pitch. The advantages of DSA using BCP stem from the fact that it is a bottom-up technology, where the pattern is determined by material properties rather than equipment. These advantages are low defects, high efficiency, and low cost.

[0007] The directed self-assembly block copolymer includes a block of etch-resistant copolymer units and a block of highly etchable copolymer units, which produce regions with an extremely high density pattern when coated, aligned, and etched on a substrate. The directed self-assembly block copolymer includes a block of etch-resistant copolymer units and a block of highly etchable copolymer units, which produce regions with an extremely high density pattern when coated, aligned, and etched on a substrate.

[0008] To achieve the upright lamellar microstructure required for patterning by selective etching, the control of three BCP parameters is crucial: the molecular weight (M n ), the chemical interaction (χ) between the blocks, and the volume ratio (f) of the blocks.

[0009] The applications of various block copolymers with low Chi in semiconductor patterning have been described and claimed, such as PS-PMMA, PS-PLA, PS-PVP, etc.

[0010] The ability of BCP to phase separate depends on the Flory Huggins interaction parameter (χ). PS-b-PMMA (poly(styrene-block-methyl methacrylate)) is the most promising candidate for directed self-assembly (DSA) applications. However, due to the low interaction parameter (χ) between PS and PMMA, the minimum half-pitch of PS-b-PMMA is limited to about 10 nm. To further miniaturize features, it is highly desirable for block copolymers to have a larger interaction parameter (higher chi) between the two blocks.

[0011] In particular, the directed self-assembly of block copolymers is a method that can be used to generate extremely small patterned features for manufacturing microelectronic devices, where critical dimensions (CDs) of features in the range of 10 nm to 50 nm can typically be achieved on the order of about the nanoscale. It is challenging to achieve feature sizes below 10 nm using conventional methods of directed self-assembly of block copolymers. Directed self-assembly methods (such as those based on block copolymer graphoepitaxy and chemoepitaxy) are desired to extend the resolution capabilities of lithography techniques.

[0012] These techniques can be used to enhance conventional lithography techniques because they enable the generation of patterns with higher resolution and / or improved CD control for EUV, electron beam, 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 high-resolution patterns.

[0013] Known examples of block copolymers suitable for directed self-assembly are those that are capable of microphase separation and include blocks that are resistant to plasma etching and rich in carbon (such as styrene or containing some other elements, such as Si, Ge, and Ti) and blocks that are highly plasma etchable or removable, which 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 are capable of forming highly etchable blocks, such as methyl methacrylate. The plasma etching gases used in the etching process to define the self-assembled pattern are typically those used in the process of manufacturing integrated circuits (ICs). In this way, extremely fine patterns can be produced on a typical IC substrate compared to conventional lithography techniques, thereby achieving pattern multiplication.

[0014] In the graphoepitaxy-directed self-assembly method, the block copolymer self-organizes on a substrate that has been pre-patterned using conventional lithography (such as ultraviolet, deep UV, electron beam, and EUV exposure sources) to form topographical features, such as line / space (L / S) or contact hole (CH) patterns. In an example of an L / S directed self-assembly array, the block copolymer can form self-aligned lamellar regions with a sub-lithographic pitch in the trenches between the pre-pattern sidewalls, thereby enhancing the pattern resolution by subdividing the space between the topographical lines into finer patterns. Similarly, features such as contact holes can be made denser by using graphoepitaxy, where a suitable block copolymer self-arranges within an array of pre-patterned holes or pre-patterned pillars defined by conventional lithography, thereby forming a denser array of etchable regions and etch-resistant domains, which produce a denser array of contact holes upon etching. Additionally, the block copolymer can form a single and smaller etchable domain at the center of a pre-patterned hole of appropriate size and provide potential shrinkage and correction of the holes in the pre-pattern. Thus, graphoepitaxy has the potential to provide pattern correction and pattern multiplication.

[0015] In chemical epitaxy (chemical epitaxy method) DSA methods, the self-assembly of block copolymers is carried out on surfaces with different chemical affinities but without topography or with very slight topography to direct the self-assembly process. For example, lithography (UV, deep UV, electron beam, EUV) and nanofabrication processes can be used to create chemically pre-patterned surfaces with different chemical affinities in on-line and space (L / S) patterns. These regions can exhibit minimal to no topographical differences, but do exhibit surface chemical patterns to direct the self-assembly of block copolymer domains. This technique allows for the precise placement of these block copolymer domains with a spatial frequency higher than that of the pre-pattern. After plasma or wet etching treatment, the aligned block copolymer domain pattern can subsequently be transferred into the underlying substrate. Additionally, chemical epitaxy has the advantage that block copolymer self-assembly can correct for variations in surface chemistry, size, and roughness of the underlying chemical pattern to yield improved line edge roughness and CD control in the final self-assembled block copolymer domain pattern. Other types of patterns (such as contact hole (CH) arrays) can also be generated or corrected using the chemical epitaxy method.

[0016] For lithographic applications, an orientation of block copolymer domains perpendicular to the substrate is desired. For conventional block copolymers (e.g., PS-b-PMMA) 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 a non-preferential or neutral material grafted or crosslinked at the polymer-substrate interface and thermally annealing it. Due to the larger differences in the interaction parameters between the domains of block copolymers with higher Chi, it is important to control the BCP-air and BCP-substrate interactions. Many orientation control strategies for generating vertically oriented BCP domains have been implemented using BCPs with higher Chi. For example, solvent vapor annealing has been used for orientation control of polystyrene-b-poly(ethylene oxide) (PS-b-PEO), polystyrene-b-poly(dimethylsiloxane) (PS-b-PDMS), polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP), poly(lactic acid)-b-poly(trimethylsilylstyrene) PLA-b-PTMSS, and PDMS-b-PHOST. The introduction of solvent vapor chambers and the kinetics of solvent vapor annealing can complicate the DSA process. Alternatively, a combination of neutral bottom and topcoat materials has been applied to PS-b-P2VP, PS-b-PTMSS, and PLA-b-PTMSS to achieve vertical orientation of the polymer domains. However, the additional topcoat material can increase the process cost and complexity. Therefore, there is a need for a BCP system with higher Chi that uses only thermal annealing without a topcoat on a range of preferential and non-preferential substrates. A key factor that has allowed for proper vertical orientation of block copolymer domains even for high Chi polymers in the past is the nature of the interaction between the different domains and the substrate on which they are coated. Specifically, the surface must not favor either of the domains (otherwise the domains will not orient in the vertical direction during self-assembly), and it needs to remain neutral with respect to its interaction with the two domains. To prepare such a neutral surface, polymer brushes can be grafted onto the surface of a silicon or silica (SiOx) substrate to form a neutral layer on the surface, which allows the block copolymer to orient its domains perpendicular to the substrate surface during self-assembly or directed self-assembly. More specifically, these neutral layers are layers on the substrate or treated substrate surface that have no affinity for either of the block segments of the block copolymer used in directed self-assembly. In the graphoepitaxy method of directed self-assembly of block copolymers, the neutral layer is useful because it can properly position or orient the block polymer segments for directed self-assembly, which results in proper placement of the etch-resistant block polymer segments and highly etchable block polymer segments relative to the substrate.For example, in a surface containing lines and space features defined by conventional radiation lithography, the neutral layer can orient the block segments such that the block segments are oriented perpendicular to the substrate surface, as related to the length between the lines defined by conventional lithography, depending on the length of the block segments in the block copolymer. This orientation is desirable for pattern correction and pattern multiplication. If the substrate interacts too strongly with one of the block segments, this will cause it to lie flat on the surface to maximize the contact surface between that segment and the substrate; such a surface will disrupt the desired vertical alignment that can be used for pattern correction or pattern multiplication based on features generated by conventional lithography. Modifying selected small regions or pinning the substrate to strongly interact with one block of the block copolymer and keeping the remaining surface coated with the neutral layer can be used to align the domains of the block copolymer in the desired direction, and this is the basis for the pinning chemical epitaxy method or the lithographic epitaxy method for pattern multiplication. However, the requirement for the neutral layer on the treated substrate requires additional processing steps. Therefore, there is a need for novel block copolymers that can perform self-assembly and directed self-assembly on treated substrates without a neutral layer, as this reduces the number of steps required for DSA processing to increase the throughput of IC manufacturing. Description of the Drawings

[0017] Figure 1 AFM image of the self-assembled film after annealing for EX.1.

[0018] Figure 2 AFM image of the self-assembled film after annealing for EX.5.

[0019] Figure 3 AFM image of the self-assembled film after annealing for EX.9.

[0020] Figure 4 AFM image of the self-assembled film after annealing for EX.15.

[0021] Figure 5 AFM image of the self-assembled film after annealing for EX.16.

[0022] Figure 6 : Chart of L0 vs. Mn for the lamellar block copolymer in Table 1 after coating and annealing on bare SiO or SiN;

[0023] Figure 7 AFM image of the self-assembled film after annealing for COMP.EX.1.

[0024] Figure 8 AFM image of the self-assembled film after annealing for COMP.EX.2.

[0025] Figure 9: DSA of block copolymer EX.1 on a graphoepitaxy substrate with trench / plateau dimensions of 40 / 40, 60 / 60, 80 / 80, 100 / 100 nm from left to right.

[0026] Figure 10 : Partial DSA on a chemoepitaxy substrate EX.15.

[0027] Figure 11 : DSA on chemoepitaxy substrates EX15 at low and high AFM magnifications.

[0028] Figure 12 : Comparison of plasma etching rates of PMMA, P[MA-C6-azobutyl], and P[MA-C11-azobutyl].

[0029] Figure 13 Continuous film of the annealed film pre-etched for EX.11.

[0030] Figure 14 Continuous film of the annealed film after plasma etching for EX.11.

[0031] Figure 15 AFM of the fingerprint self-assembled film of PMMA-b-P[MAC6 azobutyl], from left to right are EX.17, EX.18, EX.19, and at the bottom is EX.20, on SiN at 1 wt.% 190 °C for 1 hr; 1 um x 1 um scan.

[0032] Figure 16 AFM of graphoepitaxy of PMMA-b-P[MAC6 azobutyl] (EX.17, Mn 35 kDa) with L0 of 23 nm, on 80 nm trenches / plateaus in SiOx at 1 wt.% 190 °C for 1 hr.

[0033] Figure 17 AFM of graphoepitaxy of PMMA-b-P[MAC6 azobutyl] (EX.17, Mn 35 kDa) with L0 of 23 nm, on xPMMA with a pitch of 90 nm and a width of 26 nm at 1 wt.% 190 °C for 1 hr.

[0034] Figure 18 AFM of graphoepitaxy of PMMA-b-P[MAC6 azobutyl] (EX.17, Mn 35 kDa) with L0 of 23 nm, on xPMMA with a pitch of 112 nm and a width of 26 nm at 1 wt.% 190 °C for 1 hr. Summary of the Invention

[0035] The disclosed and claimed subject matter relates to liquid crystal-based block copolymers (LC-BCPs) for semiconductor patterning having a high Flory-Huggins interaction parameter (χ) (also known as Chi). Under certain conditions, the LC-BCPs described herein can directly generate a perpendicular lamellar structure on a Si substrate. Without the need for a neutral layer (NLD) or a surface coating, the LC-BCPs have the advantage of being able to easily align with a defect-free structure. Additionally, the high interaction parameter (χ) enables the formation of small and large pitch and thicker ordered copolymer films, which makes the etching process easier and ensures meeting industrial requirements.

[0036] The problem to be solved is the need to pattern integrated circuits with single-nanometer feature pitches by a method with low defects and without excessive steps, fab space, materials, tools, processing time, cost, etc. Since multiple patterning and EUV lithography do not meet these requirements, a new method is needed as an alternative or supplement.

[0037] Some low-(χ) BCPs (e.g., PS-PMMA) have been implemented to supplement multiple patterning and EUV by DSA, yet there remains a set of problems:

[0038] Typically, a neutral layer (underlayer) or a surface coating is required to obtain upright lamellae for commercial (non-liquid crystal) BCPs. However, this neutral layer not only becomes an additional processing step and material but also finally increases the defects in pattern transfer during the etching step. The ideal polymer for DSA does not require the use of a neutral layer.

[0039] Due to the low segmental heterogenicity causing phase separation only at higher molecular weights, low-χ BCPs are limited in the minimum pitch they can achieve. The ideal polymer for DSA would have a higher segmental heterogenicity between the blocks (χ) and thus be able to phase separate at low molecular weights, providing a lower pitch.

[0040] Novel block copolymers having pendant liquid crystal (LC) moieties are disclosed herein, which can achieve nanoscale pitches without using a neutral layer and have the potential to achieve single-digit nanoscale pitches. Such materials can be used as a supplement to conventional patterning lithographies for these types of pitches without using a neutral layer and the processing time and steps for generating the neutral layer, and without the increased defects brought about by these additional steps.

[0041] Working examples showing synthetic methods for the synthesis of novel LC-BCP polymers, where the polymer has the structure PMMA-b-P[MA-Cx-azobutyl] (x = 6, 8, 11); which is defined as follows: (PMMA = poly(methyl methacrylate) block segment; P[MA-Cx-azobutyl] = methacrylate (MA) block segment linked to an LC moiety (Cx-azobutyl); Cx = alkylene spacer between the MA carboxylate oxygen and the azobutyl moiety, where there are x carbon atoms in the chain connecting the MA and the azobutyl moiety; azobutyl moiety = (E)-4-((4-butylphenyl)diazenyl)phenoxy, which is linked to the other end of the Cx linking group).

[0042] These working synthetic examples involve methods for industrially-appropriate anionic polymerization. These novel block copolymer structures require the presence of hydrophobic end groups (LC capping groups) in the LC pendant moiety, which are straight-chain alkyl groups having 3 to 8 carbons (C-3 to C-8) (e.g., butyl in the working examples).

[0043] Without the use of an underlying layer and end group checks, these novel block copolymers are capable of producing annealed films on self-assembled patterns of substrates having pitches in the range of 17 - 73 nm.

[0044] In addition, the working examples are capable of influencing the DSA lithographic patterning of polymer films and can also influence their chemical patterning on pre-patterned substrates.

[0045] As demonstrated by experiments done with homopolymers, the experiments on the working examples show good etch selectivity between the PMMA and P[MA-Cx-azobutyl] blocks, and this is also the case when etching the self-assembled films of the novel block copolymers on SiOx substrates.

[0046] The fundamental methods for these novel block copolymer structures described herein, which are suitable for DSA on substrates without the use of a neutral layer, can also be complemented by predictive examples, which are a natural extension of the working examples.

[0047] · The synthetic methods for the polymerization of the working examples PMMA-b-P[MA-Cx-azobutyl] (x = 6, 8, 11) can use x = 3, 5, 7, 9, 10, 12, and 13, as well as LC capping groups other than butyl (C-4) (also referred to as C-3, C-5 to C-8), thereby influencing the standing lamellae of the polymer having pitches as small as 5 nm without the use of a neutral underlying layer. Based on the initial results using PMMA-b- and based on the initial results of the working examples, multi-pitch DSA using this predictive example is expected.

[0048] · It is expected that DSA processing using these novel polymer structures will have particularly low defects because there is no need for a neutral layer, which reduces the number of steps for, e.g., graphoepitaxy or chemoepitaxy as shown by the working examples, because there is no need for the processing to introduce a neutral layer, and this in turn improves the throughput of IC manufacturing using this process.

[0049] Specifically, the novel polymer structure is an AB block copolymer comprising a first block A of structure (I) and a second block B of structure (II), where R and R1 are each independently selected from C1 to C4 alkyl, n is the number of repeating units in structure (I), m is the number of repeating units in structure (II), and based on the total molar amount of the repeating units of structures (I) and (II), the molar % of the repeating units of structure (I) ranges from about 35 mol% to about 94 mol%, and the molar % of the repeating units of structure (II) ranges from about 6 mol% to about 65 mol%, and the sum of the molar % of the repeating units of structures (I) and (II) equals 100 mol%.

[0050] In addition, in this polymer, R2 is selected from C1 to C11 alkyl, L is a C5 to C12 straight-chain alkylene, and R3 is selected from C3 to C8 straight-chain alkyl, and R' is H or C3 to C8 straight-chain alkyl, and further wherein the block copolymer has a polydispersity of 1 to about 1.31.

[0051]

[0052] Another aspect of the disclosed and claimed subject matter is a composition comprising the block copolymer and an organic spin-casting solvent.

[0053] Another aspect of the disclosed and claimed subject matter is a process of using the composition and / or the block copolymer for self-assembly and directed self-assembly lithography processing. Detailed Description

[0054] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not restrictive of the claimed subject matter. In this application, the use of the singular form includes the plural form, the words "a" or "an" mean "at least one", and the use of "or" means "and / or", unless specifically stated otherwise. Additionally, the use of the term "including" and other forms such as "includes" and "included" is not restrictive. Further, terms such as "element" or "component" cover both elements and components that include a single unit and those that include more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive, unless otherwise indicated. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the foregoing elements, including the use of a single element.

[0055] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are hereby expressly incorporated by reference in their entirety for any purpose. In the event that one or more of the incorporated references and similar materials define a term in a manner that is inconsistent with the definition of that term in this application, this application shall control.

[0056] 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 as set forth below can be substituted or unsubstituted. The term "alkyl" refers to a moiety having from C-1 to C-8 carbon atoms. It should be understood that due to structural reasons, straight-chain alkyls start from C-1, branched-chain alkyls and cyclic alkyls start from C-3, and polycyclic alkyls start from C-5. Further, it should be understood that moieties derived from the alkyls set forth below (e.g., alkyloxy (alkoxy)) have the same carbon number range, unless otherwise indicated. The C-1 to C-4 alkyl nomenclature applies to the same criteria. If the length of the alkyl specified is different from that set forth above, the alkyl definitions set forth above still apply with respect to all types of alkyl moieties as set forth above, and the structural considerations regarding the minimum carbon number of a given type of alkyl still apply.

[0057] An alkyloxy (also known as an alkoxy) refers to an alkyl group (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.) attached via an oxygen (-O-) moiety. As elaborated below, these alkoxy moieties may be substituted or unsubstituted. The criteria for establishing the alkyl nature in C-1 to C-8 alkyloxies or in C-1 to C-4 alkyloxies are the same as those previously used to elaborate the alkyl moiety.

[0058] Halogenated or halo refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0059] Haloalkyl refers to a straight-chain, cyclic, or branched saturated alkyl as defined above, where at least one hydrogen is replaced by a halo group selected from the group consisting of F, Cl, Br, I, or a mixture of these groups (if there is more than one halo moiety). Fluoroalkyl is a specific subgroup of this moiety.

[0060] Unless otherwise indicated, the term "alkylene" refers to a hydrocarbon group that can be straight-chain, branched, or cyclic and has two or more attachment points (e.g., having two attachment points: methylene, ethylene, 1,2-isopropylidene, 1,4-cyclohexylene, etc.; having three attachment points: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.). Here again, when a possible carbon range is specified (e.g., C-1 to C-20), as a non-limiting example, this range encompasses straight-chain alkylene starting from C-1, but only branched alkylene or cycloalkylene starting from C-3. As elaborated below, these alkylene moieties may be substituted or unsubstituted. The term straight-chain alkylene refers to a straight-chain alkylene moiety having two attachment points and is unsubstituted unless otherwise specifically provided. For example, when R' is H, L as elaborated herein is an unsubstituted straight-chain alkylene of C-5 to C-12; however, when R' is a C-3 to C-8 straight-chain alkyl, then L is a straight-chain alkylene having an R' straight-chain alkyl substituent.

[0061] The term "aryl" or "aromatic group" refers to a class of groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, terphenyl, etc. This aryl can be further substituted by any suitable substituent, e.g., the above-mentioned alkyl, alkoxy, acyl, or aryl.

[0062] Unless otherwise indicated in the text, the term "substituted" when referring to aryl, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, fused aromatic ring, arene, heteroarene means one of these moieties which also contains one or more substituents selected from the group consisting of unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkoxyaryl (alkyl - O - aryl -), dialkoxyaryl ((alkyl - O -)2 - aryl), haloaryl, alkoxy, alkylaryl, haloalkyl, halo, hydroxy, cyano, nitro, acetyl, alkylcarbonyl, formyl, vinyl (CH2=CH-), phenylvinyl (Ph - CH=CH-), arylvinyl (aryl - CH=CH) and substituents including a vinylene arylene moiety (e.g., Ar(-CH=CH - Ar -) z , where z is 1 - 3. Non - limiting examples of certain substituted aryl and substituted arylethyl substituents are shown below, where represents the point of attachment:

[0063]

[0064] The polymers of the present invention

[0065] One aspect of the disclosed and claimed subject matter is a block copolymer which is an AB diblock copolymer having a first block A of structure (I) and a second block B of structure (II), where R and R1 are each independently selected from C1 - C4 alkyl, n is the number of repeating units in structure (I), m is the number of repeating units in structure (II), and based on the total moles of the repeating units of structures (I) and (II), the mole % of the repeating units of structure (I) ranges from about 35 mole % to about 94 mole %, and the mole % of the repeating units of structure (II) ranges from about 6 mole % to about 65 mole %, and the sum of the mole % of the repeating units of structures (I) and (II) equals 100 mole %.

[0066] Additionally, R2 is selected from C1 - C11 alkyl, L is a C5 - C12 straight - chain alkylene, and R3 is selected from C3 - C8 straight - chain alkyl, and R' is H or a C3 - C8 straight - chain alkyl, and further, where the block copolymer has a polydispersity of 1 to about 1.31.

[0067] In another aspect of these embodiments, R2 is selected from C1 - C10 alkyl. In another aspect of these embodiments, R2 is C1 - C9 alkyl. In another aspect of these embodiments, R2 is C1 - C8 alkyl.

[0068]

[0069] In one aspect of the disclosed and claimed subject matter, the block copolymer is a block copolymer wherein R' is H. In another aspect, the block copolymer is a block copolymer wherein R' is a C-3 to C-8 straight chain alkyl group.

[0070] In one aspect of the disclosed and claimed subject matter, the block copolymer as described herein is prepared via anionic or RAFT polymerization.

[0071] In another aspect of this embodiment, the block copolymer as described herein is prepared via anionic polymerization.

[0072] In one aspect, the copolymer is substantially free of metal contaminants such as aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, and titanium, where each of these metals is present at a level of less than 2.5 ppb in a solution of these polymers in PGMEA. In one aspect of the disclosed and claimed subject matter, the respective levels of calcium, copper, potassium, sodium, and lithium are each less than 0.4 ppb.

[0073] In another aspect of the disclosed and claimed subject matter, the block copolymer has a polydispersity in the range of 1 to about 1.13. In another aspect of this embodiment, the polydispersity range is 1 to about 1.10. However, in another aspect of this embodiment, the polydispersity range is 1 to about 1.05. However, in another aspect of this embodiment, the polydispersity range is 1 to about 1.02. In yet another aspect of this embodiment, the polydispersity range is 1 to about 1.01.

[0074] In another aspect of the disclosed and claimed subject matter, the block copolymer has an M n (number average molecular weight) in the range of about 8 kilodaltons (kDa) to about 200 kDa. In another aspect of this embodiment, M n is in the range of about 8 kDa to about 120 kDa. In another aspect of this embodiment, M n is in the range of about 20 kDa to about 170 kDa. However, in another aspect of this embodiment, it is in the range of about 37 kDa to about 108 kDa. In another aspect of this embodiment, when the polymer is prepared via RAFT polymerization, its preferred range is about 8 kDa to about 40 kDa.

[0075] In another aspect of this embodiment, it has an M n in the range of about 8 kDa to about 25 kDa.

[0076] In another aspect of the disclosed and claimed subject matter, the block copolymer prepared by RAFT polymerization has structure (III), where Rr1 is a C-1 to C-8 alkyl group, Rr2 is a C-1 to C-8 alkyl group, and Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C-1 to C-8 alkyl group or an aryl moiety, and Rr3 is an unsubstituted or substituted aryl moiety. In one aspect of this embodiment, R' is H. In another aspect of these embodiments, R' is a C-3 to C-8 straight-chain alkyl group. In another aspect of these embodiments, R is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R is a methyl group. In another aspect of these embodiments, R1 is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R1 is a methyl group. In another aspect of these embodiments, R2 is a C-1 to C-10 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-9 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-8 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-7 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-6 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-5 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-4 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-3 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R2 is a methyl group.

[0077] In one aspect of the disclosed and claimed subject matter, the block copolymer of structure (III) has structure (IIIa).

[0078] In another aspect of the disclosed and claimed subject matter, the block copolymer of structure (III) or (IIIa) has structure (IIIa-1).

[0079] In a more specific aspect of structures (III) and (IIIa), R' is hydrogen, and the block copolymer of the invention described herein is a block copolymer where L is an unsubstituted C-5 to C-12 straight-chain alkylene group and has the more specific structures (III-1), (IIIa-2), and (IIIa-3).

[0080] In one aspect of structures (III), (IIIa), (III-1), (IIIa-2) and (IIIa-3), R3 is C-3 to C-8 alkyl. In another aspect, R3 is 1-propyl. In another aspect, R3 is 1-butyl. In another aspect, R3 is 1-pentyl. In another aspect, R3 is 1-hexyl. In another aspect, R3 is 1-heptyl. In another aspect, R3 is 1-octyl. In another aspect of these embodiments, L is a C-5 straight-chain alkylene. In another aspect of these embodiments, L is a C-6 straight-chain alkylene. In another aspect of these embodiments, L is a C-7 straight-chain alkylene. In another aspect of these embodiments, L is a C-8 straight-chain alkylene. In another aspect of these embodiments, L is a C-9 straight-chain alkylene. In another aspect of these embodiments, L is a C-10 straight-chain alkylene. In another aspect of these embodiments, L is a C-11 straight-chain alkylene. In another aspect of these embodiments, L is a C-12 straight-chain alkylene. In another aspect of these embodiments, Rr3 is unsubstituted aryl. In another aspect of these embodiments, Rr3 is substituted aryl. In another aspect of these embodiments, Rr2 is methyl and Rr1 is butyl. In another more specific aspect of structures (III) and (IIIa), R' is H. In another more specific aspect of structures (III) and (IIIa), R' is C-3 to C-8 straight-chain alkyl.

[0081] In more particular aspects of structures (III) and (IIIa), which have structures (IIIb) or (IIIc) respectively, n' and n" are integers each independently in the range from 0 to 11 and further wherein the sum of n' and n" is in the range from 4 to 11. A more specific aspect of this embodiment is structure (IIIc-1). In another aspect of these embodiments, n' is 0 and n" is 4. In another aspect of these embodiments, n' is 0 and n" is 5. In another aspect of these embodiments, n' is 0 and n" is 6. In another aspect of these embodiments, n' is 0 and n" is 7. In another aspect of these embodiments, n' is 0 and n" is 8. In another aspect of these embodiments, n' is 0 and n" is 9. In another aspect of these embodiments, n' is 0 and n" is 10. In another aspect of these embodiments, n' is 0 and n" is 11. In another aspect of these embodiments, n' is 1 and n" is 3. In another aspect of these embodiments, n' is 1 and n" is 4. In another aspect of these embodiments, n' is 1 and n" is 5. In another aspect of these embodiments, n' is 1 and n" is 6. In another aspect of these embodiments, n' is 1 and n" is 7. In another aspect of these embodiments, n' is 1 and n" is 8. In another aspect of these embodiments, n' is 1 and n" is 9. In another aspect of these embodiments, n' is 1 and n" is 10. In another aspect of these embodiments, n' is 2 and n" is 2. In another aspect of these embodiments, n' is 2 and n" is 3. In another aspect of these embodiments, n' is 2 and n" is 4. In another aspect of these embodiments, n' is 2 and n" is 5. In another aspect of these embodiments, n' is 2 and n" is 6. In another aspect of these embodiments, n' is 2 and n" is 7. In another aspect of these embodiments, n' is 2 and n" is 8. In another aspect of these embodiments, n' is 2 and n" is 9. In another aspect of these embodiments, n' is 3 and n" is 1. In another aspect of these embodiments, n' is 3 and n" is 2. In another aspect of these embodiments, n' is 3 and n" is 3. In another aspect of these embodiments, n' is 3 and n" is 4. In another aspect of these embodiments, n' is 3 and n" is 5. In another aspect of these embodiments, n' is 3 and n" is 6. In another aspect of these embodiments, n' is 3 and n" is 7. In another aspect of these embodiments, n' is 3 and n" is 8. In another aspect of these embodiments, n' is 4 and n" is 0. In another aspect of these embodiments, n' is 4 and n" is 1. In another aspect of these embodiments, n' is 4 and n" is 2. In another aspect of these embodiments, n' is 4 and n" is 3. n' is 4 and n" is 4.In another aspect of these embodiments, n' is 4 and n'' is 5. In another aspect of these embodiments, n' is 4 and n'' is 6. In another aspect of these embodiments, n' is 4 and n'' is 7. In another aspect of these embodiments, n' is 5 and n'' is 0. In another aspect of these embodiments, n' is 5 and n'' is 1. In another aspect of these embodiments, n' is 5 and n'' is 2. In another aspect of these embodiments, n' is 5 and n'' is 3. In another aspect of these embodiments, n' is 5 and n'' is 4. In another aspect of these embodiments, n' is 5 and n'' is 5. In another aspect of these embodiments, n' is 5 and n'' is 6. In another aspect of these embodiments, n' is 6 and n'' is 0. In another aspect of these embodiments, n' is 6 and n'' is 1. In another aspect of these embodiments, n' is 6 and n'' is 2. In another aspect of these embodiments, n' is 6 and n'' is 3. In another aspect of these embodiments, n' is 6 and n'' is 4. In another aspect of these embodiments, n' is 6 and n'' is 5. In another aspect of these embodiments, n' is 7 and n'' is 0. n' is 7 and n'' is 1. In another aspect of these embodiments, n' is 7 and n'' is 2. In another aspect of these embodiments, n' is 7 and n'' is 3. In another aspect of these embodiments, n' is 7 and n'' is 4. n' is 8 and n'' is 0. In another aspect of these embodiments, n' is 8 and n'' is 1. In another aspect of these embodiments, n' is 8 and n'' is 2. In another aspect of these embodiments, n' is 8 and n'' is 3. In another aspect of these embodiments, n' is 9 and n'' is 0. In another aspect of these embodiments, n' is 9 and n'' is 1. In another aspect of these embodiments, n' is 9 and n'' is 2. In another aspect of these embodiments, n' is 10 and n'' is 0. In another aspect of these embodiments, n' is 10 and n'' is 1. In another aspect of these embodiments, n' is 11 and n'' is 0. In another aspect of these embodiments, R3 is C-3 to C-8 alkyl. In another aspect, R3 is 1-propyl. In another aspect, R3 is 1-butyl. In another aspect, R3 is 1-pentyl. In another aspect, R3 is 1-hexyl. In another aspect, R3 is 1-heptyl. In another aspect, R3 is 1-octyl. In another aspect of these embodiments, L is a C-5 straight-chain alkylene. In another aspect of these embodiments, L is a C-6 straight-chain alkylene. In another aspect of these embodiments, L is a C-7 straight-chain alkylene. In another aspect of these embodiments, L is a C-8 straight-chain alkylene. In another aspect of these embodiments, L is a C-9 straight-chain alkylene. In another aspect of these embodiments, L is a C-10 straight-chain alkylene.In another aspect of these embodiments, L is a C-11 straight-chain alkylene group. In another aspect of these embodiments, L is a C-12 straight-chain alkylene group. In another aspect of these embodiments, Rr3 is an unsubstituted aryl group. In another aspect of these embodiments, Rr3 is a substituted aryl group. In another aspect of these embodiments, Rr2 is methyl and Rr1 is butyl.

[0082] In another aspect of the disclosed and claimed subject matter, the block copolymer is prepared by RAFT polymerization, the -S-(C═S)-Rr3 end group is removed and replaced by hydrogen, and has the structure (III’), (IIIa’), (IIIa-1’), (III-1’), (IIIa-2’), (IIIa-3’), (IIIb’), (IIIc’), or (IIIc-1’).

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] In another aspect of the disclosed and claimed subject matter, the block copolymer is prepared by anionic polymerization. In one aspect of this embodiment, it has the structure (IV), wherein R eis a C-1 to C-8 alkyl group, and Rm and Rm1 are each independently selected from H, a C-1 to C-8 alkyl group, and a C-1 to C-8 alkoxy group. In another aspect of this embodiment, R is a C-1 to C-2 alkyl group. In another aspect of this embodiment, R is methyl. In another aspect of this embodiment, R1 is a C-1 to C-2 alkyl group. In another aspect of this embodiment, R1 is methyl. In another aspect of this embodiment, R2 is a C-1 to C-10 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-9 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-8 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-7 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-6 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-5 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-4 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-3 alkyl group. In another aspect of this embodiment, R2 is a C-1 to C-2 alkyl group. In one aspect of this embodiment, R' is H. In another aspect of this embodiment, R' is a C-3 to C-8 straight-chain alkyl group. In another aspect of these embodiments, R is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R is methyl. In another aspect of these embodiments, R1 is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R1 is methyl. In another aspect of these embodiments, R2 is a C-1 to C-4 alkyl group. In another aspect of these embodiments, R2 is a C-1 to C-2 alkyl group. In another aspect of these embodiments, R2 is methyl. In another aspect of these embodiments, R3 is a C-3 to C-7 straight-chain alkyl group. In another aspect of these embodiments, R3 is a C-3 to C-6 straight-chain alkyl group. In another aspect of these embodiments, R3 is a C-3 to C-5 straight-chain alkyl group. In another aspect of these embodiments, R3 is n-butyl. In another aspect of these embodiments, L is a C-5 straight-chain alkylene group. In another aspect of these embodiments, L is a C-6 straight-chain alkylene group. In another aspect of these embodiments, L is a C-7 straight-chain alkylene group. In another aspect of these embodiments, L is a C-8 straight-chain alkylene group. In another aspect of these embodiments, L is a C-9 straight-chain alkylene group. In another aspect of these embodiments, L is a C-10 straight-chain alkylene group. In another aspect of these embodiments, L is a C-11 straight-chain alkylene group. In another aspect of these embodiments, L is a C-12 straight-chain alkylene group.

[0089] In another aspect of these embodiments, the block copolymer has a specific structure (IVa) or (IVa-1). In one aspect of these embodiments, R' is H and L is an unsubstituted C-5 to C-12 alkylene group, and the polymer prepared by anionic polymerization has a corresponding structure (IV'), (IVa'), or (IVa-1'). In one aspect of these embodiments, R3 is a C-3 to C-8 alkyl group. In another aspect of these embodiments, R3 is 1-propyl. In another aspect of these embodiments, R3 is 1-butyl. In another aspect of these embodiments, R3 is 1-pentyl. In another aspect of these embodiments, R3 is 1-hexyl. In another aspect of these embodiments, where R3 is 1-heptyl. In another aspect of these embodiments, R3 is 1-octyl. In another aspect of these embodiments, L is a C-5 straight-chain alkylene group. In another aspect of these embodiments, L is a C-6 straight-chain alkylene group. In another aspect of these embodiments, L is a C-7 straight-chain alkylene group. In another aspect of these embodiments, L is a C-8 straight-chain alkylene group. In another aspect of these embodiments, L is a C-9 straight-chain alkylene group. In another aspect of these embodiments, L is a C-10 straight-chain alkylene group. In another aspect of these embodiments, L is a C-11 straight-chain alkylene group. In another aspect of these embodiments, L is a C-12 straight-chain alkylene group.

[0090] In another aspect of the block copolymers of structures (IV), (IVa), and (IVa-1), R' is a C-3 to C-8 straight-chain alkyl group. In one aspect, R' is a C-4 to C-8 straight-chain alkyl group. In another aspect, R' is a C-4 to C-8 straight-chain alkyl group. In another aspect, R' is a C-5 to C-8 straight-chain alkyl group. In another aspect, R' is a C-5 to C-8 straight-chain alkyl group. In another aspect, R' is a C-6 to C-8 straight-chain alkyl group. In another aspect, R' is a C-7 to C-8 straight-chain alkyl group. In another aspect, R' is a C-7 straight-chain alkyl group. In another aspect, R' is a C-8 straight-chain alkyl group.

[0091] In one aspect of this embodiment, the block copolymer of structure (IV) has a more specific structure (IVb) or (IVc), where n' and n" are integers ranging independently from 0 to 11 and further where the sum of n' and n" ranges from 4 to 11. In a more detailed aspect of these structures, they have structures (IVb) or (VIc) respectively, where n' and n" are integers ranging independently from 0 to 11 and further the sum of n' and n" ranges from 4 to 11. A more specific aspect of this embodiment is structure (IVc-1). In another aspect of these embodiments, n' is 0 and n" is 4. In another aspect of these embodiments, n' is 0 and n" is 5. In another aspect of these embodiments, n' is 0 and n" is 6. In another aspect of these embodiments, n' is 0 and n" is 7. In another aspect of these embodiments, n' is 0 and n" is 8. In another aspect of these embodiments, n' is 0 and n" is 9. In another aspect of these embodiments, n' is 0 and n" is 10. In another aspect of these embodiments, n' is 0 and n" is 11. In another aspect of these embodiments, n' is 1 and n" is 3. In another aspect of these embodiments, n' is 1 and n" is 4. In another aspect of these embodiments, n' is 1 and n" is 5. In another aspect of these embodiments, n' is 1 and n" is 6. In another aspect of these embodiments, n' is 1 and n" is 7. In another aspect of these embodiments, n' is 1 and n" is 8. In another aspect of these embodiments, n' is 1 and n" is 9. In another aspect of these embodiments, n' is 1 and n" is 10. In another aspect of these embodiments, n' is 2 and n" is 2. In another aspect of these embodiments, n' is 2 and n" is 3. In another aspect of these embodiments, n' is 2 and n" is 4. In another aspect of these embodiments, n' is 2 and n" is 5. In another aspect of these embodiments, n' is 2 and n" is 6. In another aspect of these embodiments, n' is 2 and n" is 7. In another aspect of these embodiments, n' is 2 and n" is 8. In another aspect of these embodiments, n' is 2 and n" is 9. In another aspect of these embodiments, n' is 3 and n" is 1. In another aspect of these embodiments, n' is 3 and n" is 2. In another aspect of these embodiments, n' is 3 and n" is 3. In another aspect of these embodiments, n' is 3 and n" is 4. In another aspect of these embodiments, n' is 3 and n" is 5. In another aspect of these embodiments, n' is 3 and n" is 6. In another aspect of these embodiments, n' is 3 and n" is 7. In another aspect of these embodiments, n' is 3 and n" is 8. In another aspect of these embodiments, n' is 4 and n" is 0. In another aspect of these embodiments, n' is 4 and n" is 1.In another aspect of these embodiments, n' is 4 and n'' is 2. In another aspect of these embodiments, n' is 4 and n'' is 3. n' is 4 and n'' is 4. In another aspect of these embodiments, n' is 4 and n'' is 5. In another aspect of these embodiments, n' is 4 and n'' is 6. In another aspect of these embodiments, n' is 4 and n'' is 7. In another aspect of these embodiments, n' is 5 and n'' is 0. In another aspect of these embodiments, n' is 5 and n'' is 1. In another aspect of these embodiments, n' is 5 and n'' is 2. In another aspect of these embodiments, n' is 5 and n'' is 3. In another aspect of these embodiments, n' is 5 and n'' is 4. In another aspect of these embodiments, n' is 5 and n'' is 5. In another aspect of these embodiments, n' is 5 and n'' is 6. In another aspect of these embodiments, n' is 6 and n'' is 0. In another aspect of these embodiments, n' is 6 and n'' is 1. In another aspect of these embodiments, n' is 6 and n'' is 2. In another aspect of these embodiments, n' is 6 and n'' is 3. In another aspect of these embodiments, n' is 6 and n'' is 4. In another aspect of these embodiments, n' is 6 and n'' is 5. In another aspect of these embodiments, n' is 7 and n'' is 0. n' is 7 and n'' is 1. In another aspect of these embodiments, n' is 7 and n'' is 2. In another aspect of these embodiments, n' is 7 and n'' is 3. In another aspect of these embodiments, n' is 7 and n'' is 4. n' is 8 and n'' is 0. In another aspect of these embodiments, n' is 8 and n'' is 1. In another aspect of these embodiments, n' is 8 and n'' is 2. In another aspect of these embodiments, n' is 8 and n'' is 3. In another aspect of these embodiments, n' is 9 and n'' is 0. In another aspect of these embodiments, n' is 9 and n'' is 1. In another aspect of these embodiments, n' is 9 and n'' is 2. In another aspect of these embodiments, n' is 10 and n'' is 0. In another aspect of these embodiments, n' is 10 and n'' is 1. In another aspect of these embodiments, n' is 11 and n'' is 0.

[0092] In another aspect of embodiments in which the block copolymer has structure (IV), (IVa), (IVa-1), (IV’), (IVa’), (IVa-1’), (IVb), (IVc) or (IVc-1), R3 is a C-3 to C-7 straight-chain alkyl group. In another aspect of these embodiments, R3 is a C-3 to C-7 straight-chain alkyl group. In another aspect of these embodiments, R3 is a C-3 to C-6 straight-chain alkyl group. In another aspect of these embodiments, R3 is a C-3 to C-5 straight-chain alkyl group. In another aspect of these embodiments, R3 is a n-butyl group. In another aspect of these embodiments, L is a C-5 straight-chain alkylene group. Wherein L is a C-6 straight-chain alkylene group. In another aspect of these embodiments, L is a C-7 straight-chain alkylene group. In another aspect of these embodiments, L is a C-8 straight-chain alkylene group. In another aspect of these embodiments, L is a C-9 straight-chain alkylene group. In another aspect of these embodiments, L is a C-10 straight-chain alkylene group. In another aspect of these embodiments, L is a C-11 straight-chain alkylene group. In another aspect of these embodiments, L is a C-12 straight-chain alkylene group. In another aspect of these embodiments, Rm and Rm1 are H.

[0093]

[0094]

[0095]

[0096] The composition of the present invention

[0097] Another aspect of the disclosed and claimed subject matter is a composition that includes any of the inventive block copolymers described herein and an organic spin-casting solvent. Another aspect of the disclosed and claimed subject matter is a composition that includes any of the inventive block copolymers prepared by RAFT polymerization described herein and an organic spin-casting solvent. Another aspect of the disclosed and claimed subject matter is a composition that includes any of the inventive block copolymers prepared by anionic polymerization described herein and an organic spin-casting solvent.

[0098] Another aspect of the present invention is a novel composition, wherein the concentration of the novel polymer ranges from about 0.2 wt.% to about 2 wt.%, based on the total weight of the composition (including the organic spin-casting solvent). In another aspect, the range is from about 0.5 wt.% to about 2 wt.%.

[0099] Another aspect of the disclosed and claimed subject matter is a composition of any of the block copolymers of the invention described herein and an organic spin casting solvent, the block copolymer having the structure (III), (IIIa), (IIIa-1), (III-1), (IIIa-2), (IIIa-3), (IIIb), (IIIc), (IIIc-1), (III’), (IIIa’), (IIIa-1’), (III-1’), (IIIa-2’), (IIIa-3’), (IIIb’), (IIIc’), or (IIIc-1’). In one aspect of this embodiment, the block copolymer has the general structure (III). In another aspect, it has the structure (IIIa). In another aspect, it has the structure (IIIa-1). In another aspect, it has the structure (III-1). In another aspect, it has the structure (IIIa-2). In another aspect, it has the structure (IIIa-3). In another aspect, it has the structure (IIIb). In another aspect, it has the structure (IIIc). In another aspect, it has the structure (IIIc-1). In another aspect, it has the structure (III’). In another aspect, it has the structure (IIIa’). In another aspect, it has the structure (IIIa-1’). In another aspect, it has the structure (III-1’). In another aspect, it has the structure (IIIa-2’). In another aspect, it has the structure (IIIa-3’). In another aspect, it has the structure (IIIb’). In another aspect, it has the structure (IIIc’). In another aspect, it has the structure (IIIc-1’).

[0100] Another aspect of the disclosed and claimed subject matter is a composition of any of the block copolymers of the invention described herein and an organic spin casting solvent, the block copolymer having the structure (IV), (IVa), (IVa-1), (IV’), (IVa’), (IVa-1’), (IVb), (IVc), or (IVc-1). In one aspect of this embodiment, it has the general structure (IV). In another embodiment, it has the more specific structure (IVa). In another aspect, it has the structure (IVa-1). In another aspect, it has the structure (IV’). In another aspect, it has the structure (IVa’). In another aspect, it has the structure (IVa-1’). In another aspect, it has the structure (IVb). In another aspect, it has the structure (IVc). In another aspect, it has the structure (IVc-1).

[0101] In the above-described embodiments of the novel composition, the organic spin-casting solvent is an organic spin-casting solvent that can dissolve the novel polymer and any other additional optional components mentioned above. This organic spin-casting solvent can be a single solvent or a mixed solvent. Suitable solvents are organic solvents, which can include, for example, glycol ether derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether or diethylene glycol dimethyl ether; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate or propylene glycol monomethyl ether acetate (PGMEA); carboxylic acid esters such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylic acid esters of dicarboxylic acids such as diethyl oxalate and diethyl malonate; dicarboxylic acid esters of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylic acid esters such as methyl lactate, ethyl lactate (EL), ethyl glycolate and ethyl 3-hydroxypropionate; keto esters such as methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketol 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, aromatic solvents such as naphtha, xylene, 1,2,4-trimethylbenzene, di-isopropylnaphthalene, phenylxyleneethane, chlorobenzene, 1,2-dichlorobenzene, toluene or anisole and mixtures thereof. In one aspect of this embodiment, the organic spin-casting solvent is selected from 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) and mixtures thereof; in one aspect of this embodiment, it is PGMEA, and in another aspect, it is a mixture of PGMEA and PGME. In another aspect of this embodiment, the organic spin-casting solvent is selected from aromatic solvents such as naphtha, xylene, 1,2,4-trimethylbenzene, di-isopropylnaphthalene, phenylxyleneethane, chlorobenzene, 1,2-dichlorobenzene, toluene or anisole and mixtures thereof; in one aspect of this embodiment, the solvent is toluene.

[0102] In addition to the polymer and the solvent, the novel composition may also contain a surfactant as an additive to facilitate coating.

[0103] Method of using the composition of the present invention.

[0104] Another aspect of the disclosed and claimed subject matter is a method of vertically orienting a first block copolymer domain and a second block copolymer domain on an unpatterned substrate using a block copolymer layer having a periodicity of L0, the method comprising the steps of:

[0105] a) forming a coating of any of the copolymers described herein on the unpatterned substrate using a composition of the block copolymer in an organic spin-casting solvent, wherein the coating is not a neutral layer, using the composition of the copolymer in an organic spin-casting solvent,

[0106] b) annealing the layer of the block copolymer to produce a non-zero positive integer number of first block copolymer domains and second block copolymer domains vertically oriented on the unpatterned substrate.

[0107] In another aspect of this method, the unpatterned substrate is selected from silicon (Si), silicon dioxide (SiOx), silicon nitride (SiN), silicon oxynitride (SiON). In one aspect of this method, the unpatterned substrate is silicon. In another aspect of this method, the unpatterned substrate is silicon dioxide. In another aspect of this method, the unpatterned substrate is silicon nitride. In another aspect of this method, the unpatterned substrate is silicon oxynitride.

[0108] In another aspect of this method, the block copolymer has structure (III) or more specifically structure (IIIa), (IIIa-1), (III-1), (IIIa-2), (IIIa-3), (IIIb), (IIIc), (IIIc-1), (III’), (IIIa’), (IIIa-1’), (III-1’), (IIIa-2’), (IIIa-3’), (IIIb’), (IIIc’) or (IIIc-1’).

[0109] In another aspect of this method, the block copolymer has structure (IV) or more specifically structure (IVa), (IVa-1), (IV’), (IVa’), (IVa-1’), (IVb), (IVc) or (IVc-1).

[0110] Another aspect of the disclosed and claimed subject matter is a method of vertically orienting a first block copolymer domain and a second block copolymer domain on a first patterned substrate (wherein the topographical height of the pattern on the substrate is at least 0.7 times L0) and aligning the domains with the pattern using a coating comprising a block copolymer having a periodicity of L0, wherein additionally the bottom of the patterned substrate defined by the topography is not a neutral layer surface, the method comprising the steps of:

[0111] a-1) A composition using the block copolymer in an organic spin-casting solvent to form a coating of any of the block copolymers described herein on the first patterned substrate, wherein the average thickness of the block copolymer coating is less than the topographical height of the first patterned substrate, and wherein the block copolymer layer is laterally defined by the topography; and,

[0112] b-1) Annealing the block copolymer layer to generate a first block copolymer domain and a second block copolymer domain, which are vertically oriented and confined within the recessed region on the first patterned substrate.

[0113] In another aspect of this method, the patterned substrate comprises a pattern of a crosslinked polar polymer on a silicon, silicon dioxide, silicon nitride, or silicon oxynitride substrate.

[0114] In one aspect of this method, the pattern is on silicon. In another aspect of this method, the pattern is on silicon dioxide. In another aspect of this method, the pattern is on silicon nitride. In another aspect of this method, the pattern is on silicon oxynitride.

[0115] In another aspect of this method, the block copolymer has structure (III) or more specifically structure ((IIIa), (IIIa-1), (III-1), (IIIa-2), (IIIa-3), (IIIb), (IIIc), (IIIc-1), (III’), (IIIa’), (IIIa-1’), (III-1’), (IIIa-2’), (IIIa-3’), (IIIb’), (IIIc’) or (IIIc-1’).

[0116] In another aspect of this method, the block copolymer has structure (IV) or more specifically structure (IVa), (IVa-1), (IV’), (IVa’), (IVa-1’), (IVb), (IVc) or (IVc-1).

[0117] In one aspect of the method, the pattern is a pattern of crosslinked alkyl acrylate or alkyl methacrylate; in a specific embodiment of this aspect, the pattern is one of the patterns of crosslinked poly(methyl methacrylate). An example of a suitable crosslinked poly(methyl methacrylate) is set forth in Proc. SPIE 9051, Advances in Patterning Materials and Processes XXXI, 90510K (March 27, 2014); doi:10.1117 / 12.2048179. More specifically, for this method, a patterned layer of suitable poly(methyl methacrylate) can be obtained from a copolymer layer of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate (WO15044215), and the copolymer layer can be thermally crosslinked or crosslinked using a thermal free radical generator to produce crosslinked poly(methyl methacrylate) (X-PMMA). This X-PMMA can then be patterned by overcoating with a photoresist (such as AIM5484 JSR iArF photoresist), patterning the photoresist using radiation such as argon fluoride radiation, and then developing the exposed photoresist film. This forms a patterned photoresist covering the X-PMMA, which can be used as an etch mask to selectively etch away portions of the X-PMMA layer. The etching process can use a chemical etchant or alternatively a plasma such as oxygen plasma. After the etching pattern transfer, the remaining patterned photoresist is stripped using a chemical stripper such as MS6800 from Fujifilm to form patterned X-PMMA. In one aspect of the method, the pattern of the crosslinked polar polymer is formed by patterning a copolymer coating of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate using UV radiation.

[0118] In another aspect of the method, the pattern is a line and space (L / S) pattern.

[0119] Another aspect of the disclosed and claimed subject matter is a method of vertically orienting and aligning a first block copolymer domain and a second block copolymer domain having a periodicity of L0 on a second patterned substrate (the topographical pattern of the substrate has a topographical height and pitch P1 greater than 0.7 times L0, where the pitch P1 is a non-zero positive integer multiplied by L0), wherein additionally the bottom of the patterned substrate defined by the topography is not a neutral layer surface, and the method comprises the following steps:

[0120] a-2) Using a composition of the block copolymer in an organic spin-casting solvent, forming a coating of any of the block copolymers as described herein on the second patterned substrate, wherein the thickness of the block copolymer coating is greater than the topographical height of the second patterned substrate; and,

[0121] b-2) Anneal the block copolymer layer to generate a non-zero positive integer number of vertically oriented first block copolymer domains and second block copolymer domains on the second patterned substrate and align them with the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern.

[0122] In another aspect of this method, the patterned substrate comprises a pattern of a crosslinked polar polymer on a silicon, silica, silicon nitride, or silicon oxynitride substrate. As elaborated in the previous method, a pattern of a suitable polar polymer can be obtained.

[0123] In one aspect of this method, the pattern is on silicon. In another aspect of this method, the pattern is on silica. In another aspect of this method, the pattern is on silicon nitride. In another aspect of this method, the pattern is on silicon oxynitride.

[0124] In another aspect of this method, the block copolymer has structure (III) or more specifically structure (IIIa), (IIIb), or (IIIc).

[0125] In another aspect of this method, the block copolymer has structure (IV) or more specifically structure (IVa).

[0126] In one aspect of this method, the pattern is a pattern of crosslinked alkyl acrylate or alkyl methacrylate; as elaborated above, in a specific embodiment of this aspect, the pattern of the crosslinked polar polymer is formed by patterning a coating of X-PMMA using UV radiation. In one aspect of this method, the pattern of the crosslinked polar polymer is formed by patterning a coating of a copolymer of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate using UV radiation. In one aspect of this embodiment, X-PMMA is a copolymer of methyl methacrylate and vinyl ether.

[0127] In another aspect of this method, the pattern is a line and space (L / S) pattern.

[0128] Another aspect of the disclosed and claimed subject matter is a method of vertically orienting and aligning first block copolymer domains and second block copolymer domains on a substrate having a surface chemistry prepattern, wherein the prepattern does not include a neutral layer region and has a pitch P2, where the pitch P2 is a non-zero positive integer times L0, the method comprising the steps of:

[0129] a-3) Using a composition of the block copolymer in an organic spin-casting solvent, form a coating of one of the block copolymers as elaborated herein on the substrate having a surface chemistry prepattern; and,

[0130] b-3) Anneal the block copolymer layer to generate vertically oriented first and second block copolymer domains aligned with the substrate with the surface chemical pre-pattern having a pitch P2.

[0131] In another aspect of this method, the surface chemical pre-pattern includes cross-linked polar polymer regions and regions of silicon, silicon dioxide, silicon nitride, or silicon oxynitride. In another aspect of this method, the patterned substrate includes a pattern of cross-linked polar polymer on a silicon, silicon dioxide, silicon nitride, or silicon oxynitride substrate.

[0132] In one aspect of this method, the pattern is on silicon. In another aspect of this method, the pattern is on silicon dioxide. In another aspect of this method, the pattern is on silicon nitride. In another aspect of this method, the pattern is on silicon oxynitride.

[0133] In another aspect of this method, the surface chemical pre-pattern is formed by patterning a coating of a methyl methacrylate and 2-(vinyloxy)ethyl methacrylate copolymer on the substrate using UV radiation.

[0134] In another aspect of this method, the block copolymer has structure (III) or more specifically structure (IIIa), (IIIa-1), (III-1), (IIIa-2), (IIIa-3), (IIIb), (IIIc), (IIIc-1), (III’), (IIIa’), (IIIa-1’), (III-1’), (IIIa-2’), (IIIa-3’), (IIIb’), (IIIc’), or (IIIc-1’).

[0135] In another aspect of this method, the block copolymer has structure (IV) or more specifically structure (IVa), (IVa-1), (IV’), (IVa’), (IVa-1’), (IVb), (IVc), or (IVc-1).

[0136] In one aspect of this method, the surface chemical pre-pattern includes a polar brush region, which consists of a grafted monolayer of a polar pinning polymer. In one aspect of this embodiment, the polar pinning polymer is an alkyl methacrylate having a grafted end group. In one aspect of this embodiment, the alkyl methacrylate having a grafted end group is an alkyl methacrylate having a narrow polydispersity in the range of 1 to about 1.15. In another aspect of this embodiment, the narrow polydispersity alkyl methacrylate having a grafted end group is methyl methacrylate. In another aspect of this method, the chemical pre-pattern derived from the polar pinning polymer has a thickness in the range of about 3 nm to about 13 nm. In another aspect, this chemical pre-pattern has a thickness of about 3.5 nm to about 12.0 nm. In another aspect, it has a thickness of about 4.0 nm to about 11 nm. In another aspect, it has a thickness of about 4.5 nm to about 10 nm. In another aspect, it has a thickness of about 4.5 nm to about 9 nm. In another aspect, it has a thickness of about 4.5 nm to about 8 nm. In another aspect of this method, the surface chemical pre-pattern is a patterned polar brush, which is formed by first grafting a polar brush layer on a substrate using a poly(methyl methacrylate) polymer functionalized with a hydroxyl group at one of the polymer chains, then forming the chemical, and then selectively etching it away using an overlying patterned photoresist as an etching barrier and stripping the photoresist.

[0137] In another aspect of this method, the surface chemical pre-pattern includes a non-polar brush region consisting of a grafted monolayer of a non-polar pinning polymer. In one aspect of this embodiment, the non-polar pinning polymer is a styrene polymer having a grafted end group. This grafted end group is reactive with a substrate (such as SiOx, SiN or SiON) and can thus form a surface functionalized with styrene brushes. In one aspect of this embodiment, the styrene having a grafted end group is a styrene having a narrow polydispersity in the range of 1 to about 1.15. In another aspect of this embodiment, the narrow polydispersity styrene polymer having a grafted end group is polystyrene. Examples of suitable grafted end groups are alcohol end groups or benzyl alcohol end groups.

[0138] Examples

[0139] Reference will now be made to more specific embodiments of the present invention and experimental results supporting such embodiments. Examples will be given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0140] Those skilled in the art will appreciate that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the description provided by the following embodiments, is intended to cover modifications and variations of the disclosed subject matter within the scope of any claims and their equivalents.

[0141] Although the disclosed and claimed subject matter has been described and illustrated in some detail, it should be understood that the invention is given by way of example only, and that those skilled in the art may make various changes in the order of conditions and steps without departing from the spirit and scope of the disclosed and claimed subject matter.

[0142] Chemicals

[0143] Unless otherwise indicated, all chemicals were purchased from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103) and used as received. 4-(4-Butylphenylazo)phenol was obtained from TCI. 6-Bromohexan-1-ol was obtained from Combi-Blocks. Stabilizer-free THF was obtained from Acros. w = 6% sec-BuLi in cyclohexane was obtained from Albemarle. Methyl methacrylate (MMA) was used after filtration through basic alumina. The LC monomers were synthesized as described below. The 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)).

[0144] Instruments.

[0145] Spin coating of the polymer solution was done on an Ossila Spin Coater 3.0. Annealing was done on an IKA C-MAG HS 7 controlled hotplate. Scanning electron microscope (SEM) pictures were obtained using a Magellan ultra-high resolution scanning electron microscope 400L. Atomic force microscope (AFM) pictures were obtained on a Bruker Dimension Icon XR scanning probe microscope. GISAXS analysis of the self-assembled and annealed block copolymer films for obtaining L0 data was done on a home-built system located at Hamburg University, which consists of the following components: Incoatec IµS high-brightness x-ray source, Quazar Montel multilayer mirror, Scatex scatterless collimating pinhole, Rayonix SA 165 CCD-detector. Measurement conditions: 0.154 nm wavelength, 700 µm beam diameter at the sample, 1.6 m sample-detector distance for SAXS, completely evacuated beam path (except for the sample area), 3600 s accumulation time per sample, 0.2-degree angle of incidence for GISAXS. VASE ellipsometry measurements were obtained using a J.A. Woollam alpha SE ellipsometer and Complete Ease software. Plasma oxygen etching experiments were done using a Diener Pico Plasma Asher. The plasma etching conditions for etching the block copolymer films were power = 100 watts (W.). Gel permeation chromatography was done using GPC-MALS for absolute Mn measurement. The system contains an Agilent degasser G7122A, pump G7110B, autosampler G7129A, column oven MCT G7116A, and detectors VWD G7114A, Wyatt Dawn 8 MALS, Whatt Optilab RI. 10 mg of a 30 kDa polystyrene standard was dissolved in 2 mL of THF. 1H NMR spectra were recorded on a Bruker Advance 500 MHz spectrometer.

[0146] Working monomer synthesis example: Synthesis method of the liquid crystal monomer MA-Cx-azobutyl (MA-Cx-azobutyl (x-(4-((4-butylphenyl)diazenyl)phenoxy)alkyl (Cx alkyl 6, 8, 11) methacrylate).

[0147] As described below, the MA-Cx-azobutyl monomers (Cx alkyl 6, 8, 11) were prepared by the reaction shown in Scheme 1:

[0148]

[0149] - Scheme 1 Synthesis of MA-Cx-azobutyl monomers

[0150] The following description relates to the case of C6, where n = 6:

[0151] 6-(4-((4-butylphenyl)diazenyl)phenoxy)hexan-1-ol

[0152] In a three-necked round-bottom flask equipped with a mechanical stirrer, a condenser, and nitrogen inlet and outlet, 4-((4-butylphenyl)diazenyl)phenol (0.5 mol, 127.16 g, 1 equivalent) was dissolved in isopropanol (1.6 L). Potassium carbonate (0.75 mol, 103.65 g, 1.25 equivalents) and potassium iodide (60 mmol, 9.96 g, 1 equivalent) were added to the clear solution. Then, 6-bromohexan-1-ol (0.625 mol, 82 mL, 1.25 equivalents) was introduced, and the mixture was refluxed with stirring overnight. The mixture was cooled to 50 °C room temperature and filtered to remove salts. Then the filtrate was concentrated and the resulting solid was further purified by recrystallization from heptane:isopropanol (1:1) to obtain 139 g of the product (yield: 78.4%).

[0153] Under an argon atmosphere, 6-(4-(p-tolyldiazenyl)phenoxy)hexan-1-ol (0.2 mol, 70.9 g, 1 equivalent) was dissolved in anhydrous dichloromethane (DCM) (1.8 L). Then, methacrylic acid (0.46 mol, 39.6 g, 2.3 equivalents) and 4-(dimethylamino)pyridine (DMAP) (0.06 mol, 7.33 g, 0.3 equivalents) were added, and the mixture was cooled to 0 °C using an ice bath. N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (0.5 mol, 77.6 g, 2.5 equivalents) was added slowly and the reaction mixture was slowly warmed to room temperature and stirred overnight. The solvent was removed under reduced pressure and the crude product was purified via a silica gel column to obtain 65 g of the azo monomer as a yellow solid (yield: 77%).

[0154] Working polymerization example: Synthesis method of PMMA-b-P[MA-Cx-azobutyl] poly(MA-C6-azobutyl (poly((E)-x-(4-((4-butylphenyl)diazenyl)phenoxy)alkyl (Cx alkyl 6, 8, 11) (x = 6, 8, 11))

[0155] The LC-BCPs synthesized by RAFT and anionic polymerization have the following repeating unit structures: PMMA-b-P[MA-Cx-azobutyl], poly(MA-C6-azobutyl (poly((E)-x-(4-((4-butylphenyl)diazenyl)phenoxy)alkyl (Cx alkyl 6, 8, 11), where x = 6, 8, 11, and as schematically shown, the detailed end groups are not shown and only the chemical structures of the A and B repeating units are shown, as in the following structures (V-1), (V-2), and (V-3).

[0156]

[0157] RAFT polymerization method (- Schemes 2 & 3):

[0158] The polymer synthesis procedure for all examples starts with the polymerization of the first block PMMA. Methyl methacrylate (MMA) monomer (49.942 mmol) was filtered through basic alumina. The amount of the chain transfer agent (CTA) used in the preparation of the block copolymer was selected to produce the desired Mn; (in these cases, 1-cyano-1-methylethyl dithiobenzoate was used). Specifically, the amount of AIBN was selected to be proportional to the CTA (CTA:AIBN is about 1:3), for example, the range of AIBN used for the PMMA block in the polymerization examples is 0.04 to 0.19 mmol; and the range for the second block copolymerization is 0.01 to 0.07 mmol. Therefore, the millimole amount of AIBN was pumped under vacuum into a sealed glass ampoule (the AIBN determines the M of the polymer as reported in Table 1 n ), and then argon or nitrogen was introduced. MMA and anisole were added. The container was stirred at 70 °C overnight. Then the solution was cooled to room temperature and the polymer was precipitated with 3x of the anti-solvent (methanol), and then filtered through a Buchner funnel. It was dissolved in anisole or toluene and precipitated in methanol, followed by filtration, and this process was repeated two more times. Finally, the filtered polymer was dried in a vacuum oven at 40 - 50 °C.

[0159] Table 1 Millimole amounts of AIBN for different block copolymers

[0160]

[0161]

[0162]

[0163] - Scheme 2 Synthesize novel block copolymers by RAFT polymerization.

[0164] The second block is typically added in the following manner. The above-mentioned second monomer (MA-Cx-azobutyl), AIBN, and PMMA homopolymer are pumped into a sealed glass ampoule under vacuum, and then argon or nitrogen is introduced. Degassed anisole is added via a syringe. This mixture in the reaction vessel is stirred overnight at 70 °C. Then the solution is cooled to room temperature and the same precipitation procedure as used for the homopolymer above is repeated. Table 1 gives an overview of the properties of the polymers prepared in this way. As shown in Table 1, the relative ratio of the two repeating units reflects the molar ratio of MMA and MA-Cx-azobutyl employed.

[0165]

[0166] - Scheme 3 synthesizes novel block copolymers by RAFT polymerization.

[0167] Anionic polymerization method (- Scheme 4):

[0168] The precursor is prepared in the following manner. The MMA monomer (103.280 mmol) is filtered on alumina and stored in a refrigerator with molecular sieves. The anionic carrier 1,1-diphenylethylene (DPE) is prepared in the same way. The MA-Cx-azobutyl monomer is dissolved in toluene and stirred with calcium hydride for 3 hours, and then filtered on alumina.

[0169] Each monomer is transferred to an ampoule, degassed, and flushed with argon three times. As shown in Table 1, the proportion of the corresponding repeating unit reflects the molar ratio of the amount of the MA-Cx-azobutyl monomer used to the amount of MMA. The reaction apparatus containing LiCl is heated under vacuum and then cooled to room temperature. Under argon, THF (free of inhibitor) is introduced into the reaction apparatus and then cooled to -78 °C. The initiator (sec-BuLi) is added until it turns yellow indicating anhydrous, and then the apparatus is returned to room temperature. Then the apparatus is cooled to -78 °C again and sec-BuLi (e.g., 0.2 mmol) is added via a syringe and stirred for 5 min. (As shown in Table 1, the molar number of sec-BuLi to the molar number of the monomer determines the M of the polymer n .) DPE (the volume of DPE is predicted by the volume of sec-BuLi) is added and stirred for 5 min. Then the MMA monomer ampoule is opened to the apparatus and introduced into the apparatus at a rate of 1 drop / second. When it is completed, the second monomer ampoule is opened to the apparatus and introduced into the apparatus in the same way. Stirring is started for 3 hours. Then, 3 mL of degassed methanol is introduced to terminate the reaction and it is left at room temperature overnight. The final product is precipitated into methanol, filtered, and dried in a vacuum oven.

[0170]

[0171] - Scheme 4 synthesizes novel block copolymers via anionic polymerization

[0172] Table 2a gives an overview of different novel block copolymers obtained by RAFT polymerization or anionic polymerization, which polymerization uses the general synthetic schemes outlined above, but with two different monomers having different loadings to achieve the indicated ratios of these monomers in these block copolymers and with different initiator dosages to achieve different M n values. Table 2b more specifically gives an overview of the anionic PMMA-b-P[MAC6 azobutyl] polymer data of the polymers using high Chi DSA.

[0173] Table 2a Polymers with different C-chain lengths and M n obtained by RAFT and anionic polymerization (confirmed by SAXS to be lamellar)

[0174]

[0175]

[0176] Table 2b Polymers with high Chi obtained via anionic LC BCB

[0177]

[0178] Comparative Examples: Synthetic methods for PMMA-b-P[MA-C6-azo-R] (R = methoxy, cyano)

[0179] The LC-BCPs for COMP EX.1 and COMP EX.2 (Table 3) were synthesized by RAFT polymerization and have the following structure: PMMA-b-P[MA-C6-azo-R], where R = methoxy, cyano, which is in the same manner as EX.1, except that the monomer containing LC is a monomer with a methoxy or cyano end group instead of a n-butyl end group. When the LC end group is methoxy or cyano, Structures (VI-1) and (VI-2) show the structures of these comparative block copolymers respectively.

[0180]

[0181] Table 3 RAFT synthesis of PMMA-b-P[MA-C6-azo-methoxy] and PMMA-b-P[MA-C6-azo-cyano]

[0182]

[0183] Working examples of upright lamellar fingerprints of polymers without using an underlying layer

[0184] It was observed that the polymers of the working examples in Table 1 could form upright thin films on silica (SiOx) and (SiN) substrates without an underlying layer.

[0185] Membrane preparation method:

[0186] Dissolve the polymer in toluene or PGMEA at a wt.% value of 0.5% to 2.5%. Spin-cast 100 μL of this solution on a sulfuric acid-treated SiOx or untreated SiN substrate at 3000 rpm for 30 sec. Anneal the membrane for 10 min - 4 hr between 150 °C and 250 °C. It was observed that all formulations containing the novel block copolymer treated in this way formed a fingerprint pattern, which indicates the vertical orientation of the polymer block domains during the annealing process. As an example, AFM images of this self-assembly are shown in Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 , which are the fingerprint patterns obtained after annealing the copolymer films of EX.1, EX.5, EX.9, EX.15, EX.16 respectively. However, all block copolymers EX.1 to EX.16 were inspected for patterns in this way by AFM, and these images were used to find L0 obtained by GI-SAXS measurement or from the fast Fourier transform (FFT) of the AFM images, and are shown in Table 4. The block copolymer pitch range achieved during annealing on SiO or SiN is 17 - 73 nm. Figure 5 The graph in n shows the dependence of L0 on M of block copolymers EX.1 to EX.16.

[0187] In addition, fingerprint patterns can be obtained by spin-coating 1 wt.% solutions of the polymers of EX.17, 18, 19 and 20 (Table 2b) on SiN and baking for 1 hour ( Figure 15 ). The processing solvents used to obtain these fingerprint patterns are anisole, xylene and cyclopentanone, however, PGMEA and toluene can also be used. Figure 15 Liquid crystal block copolymers of EX.17, 18 and 19 are shown from left to right, which give good fingerprint patterns indicating vertical orientation during the annealing process. The liquid crystal block copolymer of EX.20 using the same processing conditions, although it is clearly a cylindrical BCP, the resulting AFM image is consistent with the high Chi of this system and has a center-to-center distance of 19 nm ( Figure 15 bottom).

[0188] Table 4 Examples of upright lamellar fingerprints of polymers with each C-chain length

[0189]

[0190]

[0191] Figure 1 The figures in n show the dependence of L0 on the M of the block copolymer.

[0192] In contrast, when Comparative Examples COMP EX.1 and COMP EX.2 are formulated and annealed on SiO or SiN in the same manner as EX.1 to 16, they self-assemble block copolymer domains with a perpendicular orientation relative to these substrates. Table 5 summarizes the results obtained using these comparative copolymers. Figure 6 and Figure 7 show comparative block copolymers with methoxy or cyano LC end groups as observed by SEM, respectively.

[0193] Table 5 COMP EX.1 and COMP EX.2 annealed on the substrate

[0194] Polymer AFM image <![CDATA[L0(nm,SAXS)]]> Substrate COMP.Ex.1 See Figure 7 No layered structure was observed SiN COMP Ex.2 See Figure 8 Laid layered structure SiOx

[0195] It is observed from this experiment that the LC end groups have a significant effect on the interaction between the LC block and the substrate interface, thus achieving an upright lamellar structure fingerprint. AFM data shows that when the LC end groups are hydrophilic (such as cyano and methoxy), no upright lamellae are seen and one block has a preferential interaction with the substrate. However, when the LC end groups are hydrophobic (such as butyl), an upright lamellar structure can be observed. This means that the interactions of the PMMA block and the LC block with the substrate are equal.

[0196] Working examples of polymer DSA on a pre-patterned substrate by lithographic epitaxy

[0197] The lithographic epitaxy substrate is fabricated by electron beam lithography. The substrate is characterized by platforms and trenches in Si, where the platform / trench has dimensions of 40 / 40, 60 / 60, 80 / 80, and 100 / 100 nm width (line / space, L / S) and a trench depth of ~25 nm. After sulfuric acid treatment, spin coating and annealing of the polymer solution are carried out on the flat substrate. DSA is observed in the trenches. Figure 9 Shows AFM (Atomic Force Microscopy) pictures obtained from DSA of the EX.1 block copolymer on the above lithographic epitaxy substrate, with trench / platform dimensions of 40 / 40, 60 / 60, 80 / 80, 100 / 100 nm from left to right.

[0198] Figure 16AFM of the graphoepitaxy obtained from PMMA-b-P[MAC6 azobutyl] with 23 nm L0 (EX.17, Mn 35 kDa) on 80 nm trenches / platforms in SiOx at 1 wt.% at 190 °C for 1 hr. These show an effective L0 of 20.8 nm. These were obtained by spin-coating a 0.45 - 1.2 wt.% solution on a topographical substrate of trenches / platforms in silica, where the trench width:platform width was 1:1 and the widths were 40, 60, 80, and 100 nm. After annealing at 190 °C for 1 hour, the BCP was observed to align in the trenches and also on the platforms at higher wt.%. The effective L0 observed was 20.8 nm, but the L0 observed in the corresponding fingerprint pattern ( Figure 15 ) was 23 nm.

[0199] DSA working examples of novel block copolymers EX.1 to 16 on chemically epitaxially prepatterned substrates

[0200] It was observed that partial chemically epitaxial DSA could be obtained from the novel block copolymers of EX 1 to 13 by annealing these copolymers on thin guiding chemically epitaxial stripes of crosslinked PMMA with a 90 nm pitch and 36 nm width on SiN. Figure 10 Show AFM pictures obtained when EX.15 was annealed by this guiding chemical epitaxy on SiN. This AFM picture shows the trans prepattern pitch of the DSA of the annealed film of the block copolymer of EX.15, which could maintain a significant distance before the onset of misalignment.

[0201] When annealed, the film of block copolymer EX.15 self-assembled on chemically epitaxial patterns of crosslinked PMMA with a 96 nm pitch and 31 nm width of crosslinked PMMA on guiding stripes, where these guiding stripes had a thickness of 4.8 nm. Chemically epitaxial DSA alignment was observed without any misalignment and had a 2-fold gain corresponding to the above GISAXS L0 data. Figure 11 Show SEM pictures of this chemically epitaxial directed self-assembly of the annealed film of this polymer at low and high AFM magnifications.

[0202] In addition, Figure 17 、 18 Show AFM images of the chemical epitaxy of PMMA-b-P[MAC6 azobutyl] with 23 nm L0 (EX.17, M n 35 kDa). For these pictures, this block copolymer was coated at 1 - 1.2% on different chemical prepatterns of crosslinked PMMA and then annealed at 190 °C for one hour. Specifically, Figure 17DSA on crosslinked PMMA (3.9L0) with a pitch of 90 nm and a width of 26 nm, and Figure 18 DSA on xPMMA (4.9L0) with a pitch of 112 nm and a width of 26 nm. These show a 4x and 5x pitch gain respectively. Additionally, it can also be observed that the DSA has a guiding strip width (W) of W = 1 - 1.4L0.

[0203] Working examples of the etching selectivity of polymers

[0204] Homopolymers of PMMA (polymethyl methacrylate), P[MA-C6-azobutyl] (poly((E)-methyl 6-(4-((4-butylphenyl)diazenyl)phenoxy)hexyl acrylate)), and P[MA-C11-azobutyl] (poly((E)-methyl 11-(4-((4-butylphenyl)diazenyl)phenoxy)undecyl acrylate)) were deposited as films and exposed to plasma oxygen etching. The etching rate of each homopolymer was measured by VASE ellipsometry and showed differences in the etching rate between the liquid crystal homopolymer and PMMA by a factor of 2 ( Figure 12 ).

[0205] SEM imaging of LC-BCP before or after oxygen plasma etching of the annealed self-assembled films of block copolymers EX.1 to 16 showed relative removal with respect to the etched liquid crystal block PMMA. Figure 13 Showing the continuous film of the self-assembled block copolymer EX.11 after annealing. Figure 14 Showing the post-etching of the same film, where the self-assembled PMMA block domains were removed more selectively than the methacrylate block domains with pendant LC parts.

[0206] Predictive synthesis example group 1: Synthesis method of PMMA-b-P[MA-Cx-azobutyl] (x = 3 - 12) polymerization

[0207] As in EX.1 to EX.16 with spacer chain lengths of C-6, C-8, and C-11, other copolymers of PMMA-b-P[MA-Cx-azobutyl] (x = 3 - 12) having other chain lengths L (in the range of C-3 to C-12) in structure (II) can be synthesized in a similar manner, where the monomers corresponding to the C-chain lengths are the same as those of the polymers in EX.1 to 16.

[0208] Predictive self-assembly example group 2: Standing lamellar fingerprints of the copolymers of the present invention with a pitch as small as 5 nm, without using an underlying layer

[0209] Predictive Example 1 Copolymers of PMMA-b-P[MA-Cx-azobutyl] (x = 3 - 12) are expected to form upright lamellar fingerprints without using an underlying layer. The polymers of EX.1 to EX.16 show that polymers with an M of 21 kDa n can achieve a pitch as low as 17 nm. Since this polymer is a high-χ material, even these novel polymers with low Mn can undergo phase separation. This enables particularly low pitches to be achieved. It is predicted that these polymers can be synthesized at M n < 21 kDa and can provide an L0 as low as 5 nm.

[0210] Predictive Etching Example Group 3: Etching Selectivity of the Copolymers of the Present Invention

[0211] Predictive Example Group 1 Polymers of PMMA-b-P[MA-Cx-azobutyl] (x = 3 - 12) are expected to show etching selectivity between the block containing pendant liquid crystal groups and the poly(methyl methacrylate) (PMMA) block, which is similar to that observed in the etching experiments of the Figure 12 homopolymers and Figure 6 and 7 the etching experiments of the self-assembled films of the block copolymers for EX.11 shown in Figure 12 comparing the C6 and C11 homopolymers with the PMMA homopolymer.

[0212] Predictive Etching Multi-Pitch Example Group 4: Multi-Pitch DSA Using the Copolymers of the Present Invention

[0213] The block copolymers of EX.1 to 16 show the potential for multi-pitch DSA, where the same polymer can be compressed and stretched to produce different pitches depending on the size of the pre-pattern. For example, 2 rows of the same polymer are repeated in both 60 nm trenches and 80 nm trenches, indicating a certain degree of flexibility. It is predicted that the polymer has an expansion (stretching) ability of up to 70% from its natural period. It is also predicted that when the LC capping group (R3) in Structure (II) increases from C-4 to, for example, C-7 and C-8, this can also contribute to the ability of the block copolymer to expand and compress, resulting in a wider ability for multi-pitch directed self-assembly. This copolymer can be prepared in the same manner as the capped C-4 block copolymers of EX.1 to 16.

[0214] Predictive Example Group 5 for Defect Reduction: Using the Polymer in DSA Pattern Transfer Has Low Defects

[0215] Based on the working examples of these block copolymers of the present invention, it is expected that these copolymers will have particularly low defects (e.g., dislocations) in the actual pattern transfer applied to integrated circuits in the future. This is because a neutral layer is usually required in DSA to ultimately increase defects during and after the etching process. Since these block copolymers of the present invention do not require the use of a neutral layer, these block copolymers of the present invention should result in low defects.

[0216] Predictive examples for reducing defects: Synthesis and use of polymers where R’ is a C-3 to C-8 straight-chain alkyl

[0217] The working examples described above demonstrate the potential of multi-pitch DSA, where the same polymer can be compressed and stretched to produce different pitches depending on the size of the pre-pattern. For example, two rows of the same polymer are repeated in both 60 nm trenches and 80 nm trenches, indicating a certain degree of flexibility. We predict that the natural period of the polymer has an expansion (stretching) ability of up to 70%. Additionally, it is predicted that a subgroup of polymers with liquid crystal side chains or liquid crystal end groups having C = 3-8 and preferably C-7 to C-8 can contribute to the ability of the polymer to expand and compress. The following are predictive examples of specific examples of how to prepare such materials.

[0218] This predictive example gives specific examples of how variants of these block copolymers of the present invention can be prepared, where the copolymer has a branched C-3 to C-8 alkyl group (also referred to as R’ C-3 to C-8). Specific examples of C-8 branched MA-C6-azobutyl repeating units and MMA repeating units can be prepared, showing the synthesis of the precursor, methacrylate monomer, and its subsequent polymerization. Other C-X branched MA-Cx-azoalkyl (also referred to as R’-straight-chain alkyl branched group when X = C-5 to C-8; also referred to as L straight-chain alkylene C-5 to 12 when x = 5 to 12; and also referred to as R3 = C-3 to C-8 straight-chain alkyl when Cx’ = 3 to 8) - precursors, monomers, and block copolymers can be prepared in a similar manner. Scheme 5 shows the synthesis scheme for the precursor and C-8 branched MA-C6-azobutyl repeating units. These other C-X branched MA-Cx-azobutyl can be prepared in a similar manner.

[0219] Anionic polymerization of branched alkyl PMMA-b-[MA-C6 azobutyl]

[0220] Predictive synthesis steps 1 (- Scheme 5) of 2-(4-bromobutyl)-decane-1-ol

[0221] Decanal (TCI, 10.30 mol, 1609 g, 1.2 equiv) was reacted with 1,4-dibromobutane (TCI, 8.58 mol, 1853 g, 1 equiv) in 4N NaOH solution (7 L) in the presence of a water-soluble calix[n]arene catalyst (TAC4M catalyst, 0.013 equiv). After the reaction, the water-soluble reaction mixture was extracted with dichloromethane, the organic layer was washed with water and dried using a desiccant (e.g., molecular sieve of anhydrous MgSO4), the dichloromethane was removed, and the crude product was purified by column chromatography or recrystallization to give 2-(4-bromobutyl)decanal in an expected yield of about 8% (200 g), which was expected to have a melting point of 60.7 °C. This reaction procedure was adapted from Adv. Synth. Catal. 2002, 344, 370 to 378.

[0222]

[0223] - Scheme 5 Synthesis of 2-(4-bromobutyl)decan-1-ol

[0224] Predictive synthesis step 2 of 2-(4-bromobutyl)decan-1-ol (- Scheme 6)

[0225] The carbonyl group on 2-(4-bromobutyl)decanal from step 1 was reduced with NaBH4 in methanol to produce an alcohol precursor for the following monomer synthesis. 2-(4-Bromobutyl)decanal (0.69 mol, 200 g, 1 equiv) was dissolved in methanol (360 mL) and cooled to 0 °C; then NaBH4 (0.69 mol, 26.1 g, 1 equiv) was added portionwise with vigorous stirring. After the addition of NaBH4 was complete, the solution was heated to 40 °C overnight. After the reaction, methanol was removed using a rotary evaporator and the residue was dissolved in dichloromethane, the organic layer was washed with water and dried using a desiccant (e.g., molecular sieve of anhydrous MgSO4), the dichloromethane was removed, and the crude product was purified by column chromatography to give 2-(4-bromobutyl)decan-1-ol in an expected yield of about 160 g (~80% yield), which was expected to have a melting point of 79.4 °C and an expected 13C NMR in ppm as shown in Scheme 6.

[0226]

[0227] - Scheme 6 Synthesis of 2-(4-bromobutyl)decan-1-ol

[0228] Predictive synthesis of the branched C-8 branched MA-C6 azobutyl monomer ((E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate) is shown below: (- Scheme 7)

[0229] In a three-necked round-bottom flask equipped with a mechanical stirrer, a condenser, and nitrogen inlet and outlet, 4-((4-butylphenyl)diazenyl)phenol (0.5 mol, 127.16 g, 1 equivalent) was dissolved in isopropanol (1.6 L). Potassium carbonate (0.75 mol, 103.65 g, 1.25 equivalents) and potassium iodide (60 mmol, 9.96 g, 1 equivalent) were added to the clear solution. Then, 2-(4-bromobutyl)-dec-1-ol (0.625 mol, 183.31 g, 1.25 equivalents) was introduced, and the mixture was stirred overnight under reflux. The mixture was cooled to room temperature and filtered to remove salts. Then the filtrate was concentrated and the solid was further purified by recrystallization from heptane:isopropanol (1:1) to obtain the (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)dec-1-ol (MW: 466.71) product with an expected yield of 233.35 g (if 100% yield).

[0230] Under an argon atmosphere, (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)dec-1-ol (0.2 mol, 93.3 g, 1 equivalent) was dissolved in anhydrous dichloromethane (1.8 L). Then, methacrylic acid (0.46 mol, 39.6 g, 2.3 equivalents) and 4-(dimethylamino)pyridine (0.06 mol, 7.33 g, 0.3 equivalents) were added, and the mixture was cooled to 0 °C with an ice bath. N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (0.5 mol, 77.6 g, 2.5 equivalents) was added slowly and the reaction mixture was slowly warmed to room temperature and stirred overnight. The solvent was removed under reduced pressure and the crude product was purified via a silica gel column to yield 106.95 g of the solid (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate (if 100% yield) (MW 534.79). Figure 7 Show the predicted C-13 NMR spectrum of the final product in ppm.

[0231]

[0232] - Scheme 7 Synthesis of (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate

[0233] Anionic polymerization of (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate with methyl methacrylate:

[0234] The methyl methacrylate (MMA) monomer (103.280 mmol) was filtered over alumina and stored in the refrigerator using molecular sieves. The anion carrier 1,1-diphenylethylene (DPE) was prepared in the same manner. Before filtering over alumina, the branched MA-C6-azobutyl monomer E)-decyl 2-(4-((4-butylphenyl)diazenyl)phenoxy)butyl methacrylate was dissolved in toluene and stirred with calcium hydride for 3 h.

[0235] Each monomer was transferred to an ampoule, degassed, and flushed three times with argon. The molar ratio of the branched MA-C6-azobutyl monomer employed to MMA was in the range of 85%:15% to 15%:85%. The reaction apparatus containing LiCl was heated under vacuum and then cooled to room temperature. Under argon, THF (inhibitor-free) was introduced into the reaction apparatus and then cooled to -78 °C. The initiator (sec-BuLi) was added until a yellow color indicating anhydrous conditions appeared, after which the apparatus was returned to room temperature. Then the apparatus was cooled again to -78 °C and sec-BuLi (e.g., 0.2 mmol) was added via syringe and stirred for 5 min. The molar number of sec-BuLi relative to the molar number of monomers determines the M of the polymer n . DPE was added (the volume of DPE can be predicted from the volume of sec-BuLi) and stirred for 5 min. Then the MMA monomer ampoule was connected to the apparatus and introduced at a rate of 1 drop / sec. When complete, the second monomer ampoule was connected to the apparatus and introduced in the same manner. Stirring was started for 3 h. Then, 3 mL of degassed methanol was introduced to terminate the reaction and it was left at room temperature overnight. The final product was precipitated in methanol, filtered, and dried in a vacuum oven.

[0236] Predictive synthesis of the branched (C3)MA-C6 azobutyl monomer (E)-9-(4-((4-butylphenyl)diazenyl)phenoxy)nonan-4-yl methacrylate) (- Scheme 8)

[0237] In a three-necked round-bottom flask equipped with a mechanical stirrer, a condenser, and nitrogen inlet and outlet, 4-((4-butylphenyl)diazenyl)phenol (0.5 mol, 127.16 g, 1 equivalent) was dissolved in isopropanol (1.6 L). Potassium carbonate (0.75 mol, 103.65 g, 1.25 equivalents) and potassium iodide (60 mmol, 9.96 g, 1 equivalent) were added to the clear solution. Then, 9-bromononan-4-ol (0.625 mol, 139.5 g, 1.25 equivalents, purchased from Aurora Building Blocks 4) was introduced, and the mixture was stirred overnight under reflux. The mixture was cooled to room temperature and filtered to remove salts. Then the filtrate was concentrated and the solid was further purified by recrystallization from heptane:isopropanol (1:1) to give 232 g of the product of this material (assuming: 100% yield), where the material had predicted C-13 NMR of 14.1 ppm (CH3 in butyl), 22.3 pm (CH2 in butyl), 33.4 pm (CH2 in butyl), 35.4 ppm (CH2 in butyl), 144.8 ppm (quaternary aromatic C attached to butyl), 129.7 (aromatic CH in the aromatic moiety attached to butyl), 122.8 (aromatic CH in the aromatic moiety attached to butyl), 149.9 (quaternary aromatic C of the N=N moiety in the aromatic group having an OH functional group), 145.3 ppm (quaternary aromatic C of the N=N moiety in the aromatic group having an OH functional group), 124.4 pm (aromatic CH in the aromatic group having an OH functional group), 116.2 ppm (aromatic CH in the aromatic group having an OH functional group), and 160.7 ppm (quaternary aromatic C attached to OH). Scheme 8 shows the predicted C-13 NMR peaks in ppm of the final product.

[0238]

[0239] - Scheme 8 Synthesis of 9-(4-((4-butylphenyl)diazenyl)phenoxy)nonan-4-yl (E)-methacrylate

[0240] (E)-Anionic polymerization of 9-(4-((4-butylphenyl)diazenyl)phenoxy)non-4-yl methacrylate with methyl methacrylate

[0241] This anionic polymerization was carried out as described above for the copolymerization of methyl methacrylate with (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate, where the latter reactant was replaced with an equimolar amount of (E)-9-(4-((4-butylphenyl)diazenyl)phenoxy)non-4-yl methacrylate.

[0242] The foregoing description is primarily intended for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described with reference to exemplary embodiments, those skilled in the art will understand that various other changes, omissions, and additions in form and detail may be made to the invention without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A block copolymer which is an AB diblock copolymer having a first block A with structure (I) and a second block B with structure (II), wherein R and R1 are each independently selected from C1 to C4 alkyl groups, n is the number of repeating units in structure (I), m is the number of repeating units in structure (II), and based on the total molar amount of the repeating units of structures (I) and (II), the molar % of the repeating units of structure (I) ranges from about 35 mol% to about 94 mol%, and the molar % of the repeating units of structure (II) ranges from about 6 mol% to about 65 mol%, and the sum of the molar % of the repeating units of structures (I) and (II) is equal to 100 mol%; R2 is selected from C1 to C11 alkyl groups, L is a C5 to C12 straight-chain alkylene group, R3 is selected from C3 to C8 straight-chain alkyl groups, and R' is H or a C3 to C8 straight-chain alkyl group, and further wherein the block copolymer has a polydispersity of from 1 to about 1.31; 2. The block copolymer according to claim 1, wherein the block copolymer has a polydispersity of from about 1 to about 1.

13.

3. The block copolymer according to claim 1 or 2, wherein the block copolymer has a polydispersity of from 1 to about 1.

10.

4. The block copolymer according to any one of claims 1 to 3, wherein the block copolymer has a polydispersity of from 1 to about 1.

05.

5. The block copolymer according to any one of claims 1 to 4, wherein the block copolymer has a polydispersity of from 1 to about 1.

02.

6. The block copolymer according to any one of claims 1 to 5, wherein the block copolymer has a polydispersity of from 1 to about 1.

01.

7. A block copolymer according to any one of claims 1 to 6, wherein the block copolymer has an M in the range of about 20 kDa to about 170 kDa n .

8. A block copolymer according to any one of claims 1 to 7, wherein the block copolymer has an M in the range of about 8 kDa to about 120 kDa n .

9. A block copolymer according to any one of claims 1 to 7, wherein the block copolymer has an M in the range of about 8 kDa to about 25 kDa n .

10. The block copolymer according to any one of claims 1 to 9, wherein the block copolymer is a block copolymer in which R' is H.

11. The block copolymer according to any one of claims 1 to 9, wherein the block copolymer is a block copolymer in which R' is a C3 to C8 straight-chain alkyl group.

12. The block copolymer according to any one of claims 1 to 11, which is a block copolymer prepared by RAFT polymerization.

13. The block copolymer according to any one of claims 1 to 12, which has structure (III), wherein Rr1 is a C1 to C8 alkyl group, Rr2 is a C1 to C8 alkyl group, and Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), wherein Ri is a C1 to C8 alkyl group or an aryl moiety, and Rr3 is an unsubstituted or substituted aryl moiety; 14. The block copolymer according to claim 13, wherein R' is H.

15. The block copolymer according to claim 13, wherein R' is a C3 to C8 straight-chain alkyl group.

16. The block copolymer according to any one of claims 1 to 15, wherein R is a C1 to C2 alkyl group.

17. The block copolymer according to any one of claims 1 to 16, wherein R is a methyl group.

18. The block copolymer according to any one of claims 1 to 17, wherein R1 is a C1 to C2 alkyl group.

19. The block copolymer according to any one of claims 1 to 18, wherein R1 is methyl.

20. The block copolymer according to any one of claims 1 to 19, wherein R2 is a C-1 to C-4 alkyl group.

21. The block copolymer according to any one of claims 1 to 20, wherein R2 is a C-1 to C-2 alkyl group.

22. The block copolymer according to any one of claims 1 to 21, wherein R2 is methyl.

23. The block copolymer according to any one of claims 1 to 22, wherein the block copolymer has the structure (IIIa):

24. The block copolymer according to claim 23, wherein R3 is a C-3 to C-8 alkyl group.

25. The block copolymer according to claim 23 or 24, wherein R3 is 1-propyl.

26. The block copolymer according to claim 23 or 24, wherein R3 is 1-butyl.

27. The block copolymer according to claim 23 or 24, wherein R3 is 1-pentyl.

28. The block copolymer according to claim 23 or 24, wherein R3 is 1-hexyl.

29. The block copolymer according to claim 23 or 24, wherein R3 is 1-heptyl.

30. The block copolymer according to claim 23 or 24, wherein R3 is 1-octyl.

31. The block copolymer according to any one of claims 23 to 30, wherein L is a C-5 straight-chain alkylene group.

32. The block copolymer according to any one of claims 23 to 30, wherein L is a C-6 straight-chain alkylene group or a C-7 straight-chain alkylene group.

33. The block copolymer according to any one of claims 23 to 30, wherein L is a C-8 straight-chain alkylene group.

34. The block copolymer according to any one of claims 23 to 30, wherein L is a C-9 straight-chain alkylene group.

35. The block copolymer according to any one of claims 23 to 30, wherein L is a C-10 straight-chain alkylene group.

36. The block copolymer according to any one of claims 23 to 30, wherein L is a C-11 straight-chain alkylene group.

37. The block copolymer according to any one of claims 23 to 30, wherein L is a C-12 straight-chain alkylene group.

38. The block copolymer according to any one of claims 23 to 30, wherein Rr3 is an unsubstituted aryl group.

39. The block copolymer according to any one of claims 23 to 30, wherein Rr3 is a substituted aryl group.

40. The block copolymer according to any one of claims 23 to 39, wherein Rr2 is methyl and Rr1 is butyl.

41. The block copolymer according to any one of claims 23 to 40, wherein the block copolymer is a block copolymer in which R' is H.

42. The block copolymer according to any one of claims 23 to 40, wherein the block copolymer is a block copolymer in which R' is a C-3 to C-8 straight-chain alkyl group.

43. The block copolymer according to claim 42, wherein the block copolymer is one of the structures (IIIb), wherein n' and n'' are integers independently ranging from 0 to 11 and further wherein the sum of n' and n'' ranges from 4 to 11 44. The block copolymer according to claim 43, which has the structure (IIIc):

45. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 4.

46. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 5.

47. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 6.

48. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 7.

49. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 8.

50. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 9.

51. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 10.

52. The block copolymer according to claims 43 to 44, wherein n' is 0 and n" is 11.

53. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 3.

54. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 4.

55. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 5.

56. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 6.

57. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 7.

58. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 8.

59. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 9.

60. The block copolymer according to claims 43 to 44, wherein n' is 1 and n" is 10.

61. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 2.

62. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 3.

63. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 4.

64. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 5.

65. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 6.

66. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 7.

67. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 8.

68. The block copolymer according to claims 43 to 44, wherein n' is 2 and n" is 9.

69. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 1.

70. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 2.

71. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 3.

72. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 4.

73. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 5.

74. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 6.

75. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 7.

76. The block copolymer according to claims 43 to 44, wherein n' is 3 and n" is 8.

77. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 0.

78. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 1.

79. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 2.

80. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 3.

81. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 4.

82. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 5.

83. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 6.

84. The block copolymer according to claims 43 to 44, wherein n' is 4 and n" is 7.

85. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 0.

86. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 1.

87. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 2.

88. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 3.

89. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 4.

90. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 5.

91. The block copolymer according to claims 43 to 44, wherein n' is 5 and n" is 6.

92. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 0.

93. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 1.

94. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 2.

95. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 3.

96. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 4.

97. The block copolymer according to claims 43 to 44, wherein n' is 6 and n" is 5.

98. The block copolymer according to claims 43 to 44, wherein n' is 7 and n" is 0.

99. The block copolymer according to claims 43 to 44, wherein n' is 7 and n" is 1.

100. The block copolymer according to claims 43 to 44, wherein n' is 7 and n" is 2.

101. The block copolymer according to claims 43 to 44, wherein n' is 7 and n" is 3.

102. The block copolymer according to claims 43 to 44, wherein n' is 7 and n" is 4.

103. The block copolymer according to claims 43 to 44, wherein n' is 8 and n" is 0.

104. The block copolymer according to claims 43 to 44, wherein n' is 8 and n'' is 1.

105. The block copolymer according to claims 43 to 44, wherein n' is 8 and n'' is 2.

106. The block copolymer according to claims 43 to 44, wherein n' is 8 and n'' is 3.

107. The block copolymer according to claims 43 to 44, wherein n' is 9 and n'' is 0.

108. The block copolymer according to claims 43 to 44, wherein n' is 9 and n'' is 1.

109. The block copolymer according to claims 43 to 44, wherein n' is 9 and n'' is 2.

110. The block copolymer according to claims 43 to 44, wherein n' is 10 and n'' is 0.

111. The block copolymer according to claims 43 to 44, wherein n' is 10 and n'' is 1.

112. The block copolymer according to claims 43 to 44, wherein n' is 11 and n'' is 0.

113. The block copolymer according to any one of claims 1 to 11, which is prepared by anionic polymerization.

114. A block copolymer according to any one of claims 1 to 11 and 113, having structure (IV), wherein R e is a C1 to C8 alkyl group, and Rm and Rm1 are each independently selected from H, a C1 to C8 alkyl group, and a C1 to C8 alkoxy group; 115. The block copolymer according to claim 114, wherein R' is H.

116. The block copolymer according to claim 114, wherein R' is a C-3 to C-8 linear alkyl group.

117. The block copolymer according to any one of claims 1 to 11, 115 and 116, wherein R is a C-1 to C-2 alkyl group.

118. The block copolymer according to any one of claims 1 to 11 and 115 to 117, wherein R is methyl.

119. The block copolymer according to any one of claims 1 to 11 and 115 to 118, wherein R1 is a C-1 to C-2 alkyl group.

120. The block copolymer according to any one of claims 1 to 11 and 115 to 119, wherein R1 is methyl.

121. The block copolymer according to any one of claims 1 to 11 and 115 to 120, wherein R2 is a C-1 to C-4 alkyl group.

122. The block copolymer according to any one of claims 1 to 11 and 115 to 121, wherein R2 is a C-1 to C-2 alkyl group.

123. The block copolymer according to any one of claims 1 to 11 and 115 to 122, wherein R2 is methyl.

124. The block copolymer according to any one of claims 1 to 11 and 115 to 123, wherein R3 is a C-3 to C-7 linear alkyl group.

125. The block copolymer according to any one of claims 1 to 11 and 115 to 124, wherein R3 is a C-3 to C-6 linear alkyl group.

126. The block copolymer according to any one of claims 1 to 11 and 115 to 125, wherein R3 is a C-3 to C-5 linear alkyl group.

127. The block copolymer according to any one of claims 1 to 11 and 115 to 126, wherein R3 is n-butyl.

128. The block copolymer according to any one of claims 1 to 11 and 115 to 127, wherein L is a C-5 linear alkylene group.

129. A block copolymer according to any one of claims 1 to 11 and 115 to 128, wherein L is a C-6 straight-chain alkylene group.

130. A block copolymer according to any one of claims 1 to 11 and 115 to 129, wherein L is a C-7 straight-chain alkylene group.

131. A block copolymer according to any one of claims 1 to 11 and 115 to 130, wherein L is a C-8 straight-chain alkylene group.

132. A block copolymer according to any one of claims 1 to 11 and 115 to 131, wherein L is a C-9 straight-chain alkylene group.

133. A block copolymer according to any one of claims 1 to 11 and 115 to 132, wherein L is a C-10 straight-chain alkylene group.

134. A block copolymer according to any one of claims 1 to 11 and 115 to 133, wherein L is a C-11 straight-chain alkylene group.

135. A block copolymer according to any one of claims 1 to 11 and 115 to 134, wherein L is a C-12 straight-chain alkylene group.

136. A block copolymer according to any one of claims 1 to 11 and 115 to 135, which has the structure (IVa), 137. The block copolymer according to claim 136, wherein R3 is a C-3 to C-8 alkyl group.

138. The block copolymer according to claim 136 or 137, wherein R3 is 1-propyl.

139. The block copolymer according to claim 136 or 137, wherein R3 is 1-butyl.

140. The block copolymer according to claim 136 or 137, wherein R3 is 1-pentyl.

141. The block copolymer according to claim 136 or 137, wherein R3 is 1-hexyl.

142. The block copolymer according to claim 136 or 137, wherein R3 is 1-heptyl.

143. The block copolymer according to claim 136 or 137, wherein R3 is 1-octyl.

144. The block copolymer according to any one of claims 136 to 143, wherein L is a C-5 straight-chain alkylene group.

145. The block copolymer according to any one of claims 136 to 143, wherein L is a C-6 straight-chain alkylene group or a C-7 straight-chain alkylene group.

146. The block copolymer according to any one of claims 136 to 143, wherein L is a C-8 straight-chain alkylene group.

147. The block copolymer according to any one of claims 136 to 143, wherein L is a C-9 straight-chain alkylene group.

148. The block copolymer according to any one of claims 136 to 143, wherein L is a C-10 straight-chain alkylene group.

149. The block copolymer according to any one of claims 136 to 143, wherein L is a C-11 straight-chain alkylene group.

150. The block copolymer according to any one of claims 136 to 143, wherein L is a C-12 straight-chain alkylene group.

151. The block copolymer according to any one of claims 136 to 150, wherein Rm and Rm1 are H.

152. The block copolymer according to any one of claims 136 to 150, wherein the block copolymer is a block copolymer in which R' is H.

153. A block copolymer according to any one of claims 136 to 150, wherein the block copolymer is a block copolymer in which R' is a C-3 to C-8 straight-chain alkyl group.

154. The block copolymer according to claim 153, wherein the block copolymer is one of structures (IVb), where n' and n'' are independently integers ranging from 0 to 11 and further where the sum of n' and n'' ranges from 4 to 11.

155. The block copolymer according to claim 153 or 154, wherein the block copolymer is one of structures (IVc).

156. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 4.

157. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 5.

158. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 6.

159. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 7.

160. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 8.

161. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 9.

162. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 10.

163. The block copolymer according to claim 154 or 155, wherein n' is 0 and n'' is 11.

164. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 3.

165. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 4.

166. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 5.

167. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 6.

168. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 7.

169. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 8.

170. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 9.

171. The block copolymer according to claim 154 or 155, wherein n' is 1 and n'' is 10.

172. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 2.

173. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 3.

174. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 4.

175. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 5.

176. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 6.

177. The block copolymer according to claim 154 or 155, wherein n' is 2 and n'' is 7. The block copolymer according to claim 154 or 155, wherein n' is 2 and n" is 8. The block copolymer according to claim 154 or 155, wherein n' is 2 and n" is 9. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 1. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 2. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 3. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 4. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 5. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 6. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 7. The block copolymer according to claim 154 or 155, wherein n' is 3 and n" is 8. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 0. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 1. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 2. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 3. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 4. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 5. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 6. The block copolymer according to claim 154 or 155, wherein n' is 4 and n" is 7. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 0. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 1. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 2. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 3. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 4. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 5. The block copolymer according to claim 154 or 155, wherein n' is 5 and n" is 6. The block copolymer according to claim 154 or 155, wherein n' is 6 and n" is 0. The block copolymer according to claim 154 or 155, wherein n' is 6 and n" is 1. The block copolymer according to claim 154 or 155, wherein n' is 6 and n'' is 2. The block copolymer according to claim 154 or 155, wherein n' is 6 and n'' is 3. The block copolymer according to claim 154 or 155, wherein n' is 6 and n'' is 4. The block copolymer according to claim 154 or 155, wherein n' is 6 and n'' is 5. The block copolymer according to claim 154 or 155, wherein n' is 7 and n'' is 0. The block copolymer according to claim 154 or 155, wherein n' is 7 and n'' is 1. The block copolymer according to claim 154 or 155, wherein n' is 7 and n'' is 2. The block copolymer according to claim 154 or 155, wherein n' is 7 and n'' is 3. The block copolymer according to claim 154 or 155, wherein n' is 7 and n'' is 4. The block copolymer according to claim 154 or 155, wherein n' is 8 and n'' is 0. The block copolymer according to claim 154 or 155, wherein n' is 8 and n'' is 1. The block copolymer according to claim 154 or 155, wherein n' is 8 and n'' is 2. The block copolymer according to claim 154 or 155, wherein n' is 8 and n'' is 3. The block copolymer according to claim 154 or 155, wherein n' is 9 and n'' is 0. The block copolymer according to claim 154 or 155, wherein n' is 9 and n'' is 1. The block copolymer according to claim 154 or 155, wherein n' is 9 and n'' is 2. The block copolymer according to claim 154 or 155, wherein n' is 10 and n'' is 0. The block copolymer according to claim 154 or 155, wherein n' is 10 and n'' is 1. The block copolymer according to claim 154 or 155, wherein n' is 11 and n'' is 0.

224. A composition comprising the block copolymer according to any one of claims 1 to 223 and an organic spin-casting solvent.

225. A composition comprising the block copolymer according to claims 1 to 112 prepared by RAFT polymerization and an organic spin-casting solvent.

226. A composition comprising the block copolymer according to claims 1 to 11 and 113 to 223 prepared by anionic polymerization and an organic spin-casting solvent.

227. The composition according to any one of claims 224 to 226, wherein the concentration of the block copolymer ranges from about 0.2 wt.% to about 2.0 wt.%.

228. The composition according to any one of claims 224 to 226, wherein the organic spin-casting solvent comprises at least one solvent selected from the group consisting of glycol ether derivatives, glycol ether ester derivatives, carboxylic acid esters, dicarboxylic esters of dicarboxylic acids, dicarboxylic esters of diols, hydroxycarboxylic esters, ketones, alkoxycarboxylic esters (such as methyl 3-methoxypropionate), ketoesters, ketoethers; ketoalcohol derivatives; ketals, acetals, lactones, amide derivatives, and aromatic solvents.

229. The composition according to any one of claims 224 to 228, wherein the organic spin-casting solvent comprises at least one solvent selected from the group consisting of 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, diethylene glycol dimethyl ether, ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, n-butyl acetate, amyl acetate; diethyl oxalate, diethyl malonate, ethylene glycol diacetate, propylene glycol diacetate; methyl lactate, ethyl lactate (EL), ethyl glycolate, ethyl 3-hydroxypropionate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl ethoxypropionate, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, 2-heptanone, methyl ether of diacetone alcohol, acetone alcohol, diacetone alcohol, 1,3-dioxolane, diethoxypropane, butyrolactone, dimethylacetamide, dimethylformamide, anisole, toluene, and mixtures thereof.

230. The composition according to any one of claims 224 to 229, wherein the organic spin-casting solvent is PGMEA.

231. The composition according to any one of claims 224 to 230, wherein the organic spin-casting solvent is toluene.

232. A method of vertically orienting a first block copolymer domain and a second block copolymer domain above an unpatterned substrate using a layer of a block copolymer having L0 periodicity, the method comprising the steps of: a) forming a block copolymer coating on the unpatterned substrate, which is not a neutral layer, using the composition according to any one of claims 224 to 231; and b) annealing the layer of the block copolymer to generate a non-zero positive integer number of first block copolymer domains and second block copolymer domains that are vertically oriented on the unpatterned substrate.

233. The method according to claim 232, wherein the unpatterned substrate is selected from silicon, silicon dioxide, silicon nitride, and silicon oxynitride.

234. A method of vertically orienting a first block copolymer domain and a second block copolymer domain above a first patterned substrate using a coating comprising a block copolymer having L0 periodicity and aligning the domains with the pattern, wherein the height of the topography of the pattern on the substrate is at least 0.7 times L0, the method comprising the following steps: a-1) Form a coating of the block copolymer on the first patterned substrate using a composition according to any one of claims 224 to 231, wherein an average thickness of the coating of the block copolymer is less than a height of the topography of the first patterned substrate, and wherein the block copolymer layer is laterally confined by the topography; and b-1) Anneal the block copolymer layer to generate first block copolymer domains and second block copolymer domains that are vertically oriented and confined within the recessed regions on the first patterned substrate.

235. The method according to claim 234, wherein the patterned substrate comprises a pattern of a crosslinked polar polymer on a silicon, silicon dioxide, silicon nitride, or silicon oxynitride substrate.

236. The method according to claim 235, wherein the pattern of the crosslinked polar polymer is formed by patterning a copolymer coating of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate using UV radiation.

237. The method according to any one of claims 234 to 236, wherein the pattern is a line and space (L / S) pattern.

238. A method for vertically orienting first block copolymer domains and second block copolymer domains having a periodicity of L0 and aligning the domains with a pattern on a second patterned substrate comprising a topographical pattern having a topography height and a pitch P1 greater than 0.7 times L0, wherein the pitch P1 is a non-zero positive integer multiplied by L0, and wherein a bottom of the patterned substrate defined by the topography is not a neutral layer surface, the method comprising the steps of: a-2) Form a coating of the block copolymer on the second patterned substrate using a composition according to any one of claims 224 to 231, wherein a thickness of the coating of the block copolymer is greater than the height of the topography of the second patterned substrate; and b-2) Anneal the block copolymer layer to generate a non-zero positive integer number of first block copolymer domains and second block copolymer domains that are vertically oriented on the second patterned substrate and align them with the second patterned substrate, wherein a sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern.

239. The method according to claim 238, wherein the patterned substrate comprises a pattern of a crosslinked polar polymer on a silicon, silicon dioxide, silicon nitride, or silicon oxynitride substrate.

240. The method according to claim 239, wherein the pattern of the crosslinked polar polymer is formed by patterning a copolymer coating of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate using UV radiation.

241. The method according to any one of claims 238 to 240, wherein the pattern is a line and space (L / S) pattern.

242. A method for vertically orienting first block copolymer domains and second block copolymer domains and aligning the domains above a substrate having a surface chemical prepattern that does not include a neutral layer region and has a pitch P2, wherein the pitch P2 is a non-zero positive integer multiplied by L0, the method comprising the steps of: a-3) Forming a coating of the block copolymer on the substrate having the surface chemical pre-pattern using the composition according to any one of claims 224 to 231; and b-3) Annealing the block copolymer layer to generate vertically oriented first and second block copolymer domains aligned with the substrate including the surface chemical pre-pattern having a pitch P2.

243. The method according to claim 242, wherein the surface chemical pre-pattern includes polar regions and regions of silicon, silicon dioxide, silicon nitride, or silicon oxynitride.

244. The method according to claim 242 or 243, wherein the surface chemical pre-pattern is formed by patterning a copolymer coating of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate using UV radiation.

245. The method according to claim 242 or 243, wherein the surface chemical pre-pattern is a patterned polar brush formed by first grafting a polar brush layer on the substrate using a poly(methyl methacrylate) polymer functionalized with a hydroxyl group at one polymer chain, then forming the chemical, and then selectively etching it away using an overlying patterned photoresist as an etching barrier and stripping the photoresist.

246. Use of a block copolymer according to any one of claims 1 to 223 or a composition according to any one of claims 224 to 231 for self-assembly and directed self-assembly lithography processes.

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