DSA of liquid crystal block copolymers for integrated circuit patterning

Abstract

A block copolymer is disclosed, the block copolymer being an AB diblock copolymer having a first block A of Structure (I) and a second block B of Structure (II), wherein R and R1 are independently selected from C1-C4 alkyl, the mole percent of repeating units of Structure (I) ranges from about 35 mole percent to about 94 mole percent, and the mole percent of repeating units of Structure (II) ranges from about 6 mole percent to about 65 mole percent, R2 is selected from C1-C11 alkyl, L is a C5-C12 linear alkylene, and R3 is selected from C3-C8 linear alkyl, R' is H or a C3-C8 linear alkyl, and the block copolymer has a polydispersity of 1 to about 1.31. Compositions of the block copolymer in solvents and their use in DSA processing are also disclosed. TIFF2025536621000039.tif117170

Description

[Technical Field]

[0001] The disclosed and claimed invention relates to block copolymers having liquid crystalline pendant groups, and compositions thereof in organic-based spin-cast films, and methods of using these compositions to form directed self-assembled block copolymer films on substrates. [Background technology]

[0002] In recent decades, much effort has been made to further improve the miniaturization, cost, speed, power consumption, and versatility of silicon-based integrated circuit (IC) technologies. Significant progress has been made to increase the number of transistors per CPU, with current microprocessors containing up to 4 billion transistors per small unit area. Building these types of processors involves a series of process steps, including photolithography, etching, and deposition. Photolithography is a key step in transistor and resistor fabrication. The primary factor affecting the resolution of the resulting structures is the wavelength of illumination used during photolithography. The shorter the wavelength, the higher the possible resolution and the smaller the pitch size. Currently, 193 nm is the smallest illumination wavelength that has been implemented in ICs, which provides a pitch of approximately 80 nm; however, the current industry target is to achieve pitch sizes in the single-digit nanometer range for the same unit area.

[0003] To avoid investment in new equipment and materials, multiple patterning photolithography techniques have been introduced to achieve pitches of approximately 40 nm, but multiple patterning comes at the expense of increased number of steps, defects, cost, process time, tools, fab space, consumable materials, and manpower.

[0004] Conventional lithography approaches can use ultraviolet (UV) radiation to expose a photoresist coated on a substrate or layer of substrate through a mask. Positive- or negative-tone photoresists are useful, and they can also contain refractory elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive-tone photoresists, UV radiation passing through a mask causes a photochemical reaction in the photoresist, rendering the exposed areas removable with a developer solution or by conventional IC plasma processing. Conversely, in negative-tone photoresists, UV radiation passing through a mask renders the exposed areas less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features, such as gates, vias, or interconnects, are then etched into the substrate or layer of substrate, and the remaining photoresist is removed. Using conventional lithography exposure processes, there are limitations to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Directed self-assembly is a promising approach that has attracted interest for addressing some of the shortcomings of conventional lithography techniques outlined above. Directed self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the fabrication of microelectronic devices, achieving feature critical dimensions (CDs) on the nanoscale. Directed self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques. Due to the need for large-scale integration, device circuit dimensions and features have been continually reduced. In the past, the final resolution of features has depended on the wavelength of light used to expose the photoresist, which has its own limitations. A recent technology for achieving desired pitches using shorter wavelength light is extreme ultraviolet lithography (EUV), which theoretically could achieve a maximum pitch resolution of approximately 13.5 nm. However, this technique has a high defect rate, which is not in line with industrial expectations.EUV-specific defects are generally referred to as mask defects, which are a combination of substrate, multilayer blank, and absorber patterning defects. Additionally, this particular technique is expensive, with only 53 machines worldwide capable of manufacturing it. Guided assembly techniques, such as graphoepitaxy and chemoepitaxy using block copolymer imaging, are highly desirable techniques used to enhance resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or to enable even higher resolution and CD control in approaches using EUV, e-beam, deep UV, or immersion lithography.

[0005] Directed self-assembly (DSA) of block copolymer (BCP) lithography is an additional alternative or complementary method to conventional lithography, differing from the above methods in that it involves a combination of bottom-up and top-down techniques. A template formed using photolithography / EUV techniques (top-down technique) is spin-coated with BCP, which is then phase-separated with very high resolution (single-digit nanometer order) under the influence of a guide pattern (template) (bottom-up technique). One block is then selectively etched to obtain the desired pitch pattern, depending on the size of the block.

[0006] Block copolymers (BCPs) consist of at least two different homopolymers linked by covalent bonds. Under certain conditions, BCPs self-assemble into nanodomain patterns with vertical lamellar mesostructures. In this case, one block can be selectively etched down to the substrate, resulting in the remaining blocks repeating at a constant pitch in the single-digit nanometer range. The advantage of DSA using BCPs comes from the fact that it is a bottom-up technique in which the pattern is determined by the material properties rather than the device. These advantages include fewer defects, higher efficiency, and lower cost.

[0007] Directed self-assembly block copolymers comprise blocks of etch-resistant copolymer units and blocks of highly etchable copolymer units, which when coated, aligned, and etched onto a substrate, provide regions of very dense patterns. Directed self-assembly block copolymers comprise blocks of etch-resistant copolymer units and blocks of highly etchable copolymer units, which when coated, aligned, and etched onto a substrate, provide regions of very dense patterns.

[0008] To achieve the upright lamellar mesostructure required for patterning by selective etching, three BCP parameters, namely, molecular weight (M n ), the chemical interaction between the blocks (χ), and the volume ratio of the blocks (f) are important.

[0009] Various block copolymers with low chi, such as PS-PMMA, PS-PLA, PS-PVP, etc., have been disclosed and claimed for their use in semiconductor patterning.

[0010] The ability of BCPs to undergo phase separation 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, the minimum half pitch of PS-b-PMMA is limited to approximately 10 nm due to the low interaction parameter (χ) between PS and PMMA. To enable further feature miniaturization, block copolymers with a larger interaction parameter (larger χ) between the two blocks are highly desirable.

[0011] Specifically, directed self-assembly of block copolymers is a useful method for generating very small patterned features for the fabrication of microelectronic devices, and such methods can achieve feature critical dimensions (CDs) on the nanoscale, typically ranging from 10 nm to 50 nm. Using conventional strategies for directed self-assembly of block copolymers, it is difficult to achieve feature sizes below 10 nm. Directed self-assembly methods, such as those based on graphoepitaxy and chemical epitaxy of block copolymers, are desirable for extending the resolution capabilities of lithography techniques.

[0012] These techniques can be used to enhance conventional lithography techniques by enabling the generation of patterns at higher resolution and / or improving CD control for EUV, e-beam, deep UV, or immersion lithography. Directed self-assembly block copolymers contain blocks of etch-resistant polymer units and blocks of highly etchable polymer units, which, when coated, aligned, and etched onto a substrate, provide regions of high-resolution patterns.

[0013] Known examples of block copolymers suitable for directed self-assembly include those capable of microphase separation and containing a carbon-rich block (e.g., containing styrene or some other element such as Si, Ge, and Ti) that is resistant to plasma etching and a highly plasma-etchable or removable block, allowing for high-resolution pattern definition. An example of a highly etchable block can contain a monomer, such as methyl methacrylate, that is oxygen-rich and free of refractory elements and can form a highly etchable block. The plasma etching gases used in the etching process that defines the self-assembly pattern are typically those used in methods for manufacturing integrated circuits (ICs). In this way, much finer patterns can be produced on typical IC substrates compared to conventional lithography techniques, thereby achieving pattern multiplication.

[0014] In graphoepitaxy-guided self-assembly, block copolymers self-assemble on substrates that have been prepatterned using conventional lithography (e.g., ultraviolet, deep UV, e-beam, and EUV exposure sources) to form topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-guided self-assembly array, the block copolymers can form self-aligned lamellar regions with sublithographic pitch in the trenches between the sidewalls of the prepattern, thereby enhancing pattern resolution by dividing the spaces in the trenches between the topographical lines into finer patterns. Similarly, features such as contact holes can be produced more densely using graphoepitaxy, where suitable block copolymers align themselves by guided self-assembly within prepatterned hole or prepatterned post arrays defined by conventional lithography, forming a denser array of etchable and etch-resistant domains that, when etched, give a denser array of contact holes. In addition, block copolymers can form a single smaller etchable domain in the center of a prepattern hole of appropriate dimensions, offering potential shrinkage and correction of the hole in the prepattern. As a result, graphoepitaxy has the potential to offer both pattern correction and pattern multiplication.

[0015] In chemical epitaxy (chemoepitaxy) DSA, block copolymer self-assembly occurs on surfaces that contain regions of different chemical affinity but little or no topography to guide the self-assembly process. For example, chemical prepatterns can be created using lithography (UV, deep UV, e-beam, EUV) and nanofabrication processes to create surfaces with different chemical affinities in line-and-space (L / S) patterns. These regions may have little or no topographical differences, but provide a surface chemical pattern that guides the self-assembly of block copolymer domains. This technique allows for precise positioning of these block copolymer domains with spatial frequencies greater than those of the prepattern. The aligned block copolymer domains can then be pattern-transferred into the underlying substrate after plasma or wet etching processes. In addition, chemical epitaxy has the advantage that block copolymer self-assembly can modify variations in the surface chemistry, dimensions, and roughness of the underlying chemical pattern, thus providing 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 modified using chemo-epitaxy.

[0016] For lithography applications, alignment of block copolymer domains perpendicular to the substrate is desirable. For conventional block copolymers such as PS-b-PMMA, where both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermally annealing the block copolymer on a layer of non-preferential or neutral material grafted or crosslinked to the polymer-substrate interface. Due to the relatively large difference in interaction parameters between domains of high-Chi block copolymers, it is important to control both the BCP-air and BCP-substrate interactions. Many alignment control strategies for producing perpendicularly aligned BCP domains have been implemented using high-Chi BCPs. For example, solvent vapor annealing has been used to control the orientation of polystyrene-b-polyethylene oxide (PS-b-PEO), polystyrene-b-polydimethylsiloxane (PS-b-PDMS), polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP), polylactide-b-poly(trimethylsilylstyrene), PLA-b-PTMSS, and PDMS-b-PHOST. The introduction of a solvent vapor chamber and kinetics in the solvent vapor annealing method can complicate the DSA fabrication process. Instead, a combination of a neutral underlayer and a topcoat material has been applied to PS-b-P2VP, PS-b-PTMSS, and PLA-b-PTMSS to achieve perpendicular orientation of the polymer domains. However, the additional topcoat material can increase process costs and complexity. Therefore, there is a need to provide a topcoat-free, high-chi BCP system that uses simple thermal annealing on a range of preferred and non-preferential substrates. Even in the case of high-K polymers, one crucial factor in the past for enabling proper perpendicular orientation of the block copolymer domains is the nature of the interactions between these different domains and the substrate on which they are coated. Specifically, the surface must not favor either one of these domains, since otherwise they would not orient perpendicularly during self-assembly; therefore, it must be neutral in its interactions with the two domains.To provide such a neutral surface, grafting of polymer brushes onto the surface of a silicon or silicon dioxide (SiOx) substrate can be used to form neutral layers on the substrate surface that allow block copolymers to orient their domains perpendicular to the substrate surface during self-assembly or directed self-assembly. More specifically, these neutral layers are layers on the substrate or surfaces of treated substrates that have no affinity for any of the block segments of the block copolymers used in directed self-assembly. In graphoepitaxy methods of directed self-assembly of block copolymers, neutral layers are useful because they allow for proper placement or orientation of the block copolymer segments for directed self-assembly, resulting in the proper placement of etch-resistant and highly etchable block copolymer segments relative to the substrate. For example, on a surface containing line-and-space features defined by conventional radiation lithography, a neutral layer can orient the block segments so that they are perpendicular to the surface of the substrate. This orientation is ideal for both pattern modification and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, this segment will lie flat on the surface, maximizing the contact area between the segment and the substrate; such a surface would disrupt the desired perpendicular alignment that can be used to achieve either pattern modification or pattern multiplication based on the features generated by conventional lithography. Modifying or pinning selected small regions of the substrate so that they interact strongly with one block of the block copolymer, while leaving the rest of the substrate coated with a neutral layer, can be useful for aligning the domains of the block copolymer in a desired direction, and this is the basis for pinned chemoepitaxy or graphoepitaxy used for pattern multiplication. However, the need for a neutral layer on the treated substrate requires an additional process step.Therefore, there is a need for novel block copolymers that can self-assemble and direct self-assembly on treated substrates in the absence of a neutral layer, which would reduce the number of steps required in DSA processing and increase the throughput of IC manufacturing. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is an AFM photograph of the self-assembled monolayer of Example 1 after annealing. [Figure 2] FIG. 2 is an AFM photograph of the self-assembled monolayer of Example 5 after annealing. [Figure 3] FIG. 3 is an AFM photograph of the self-assembled monolayer of Example 9 after annealing. [Figure 4] FIG. 4 is an AFM photograph of the self-assembled monolayer of Example 15 after annealing. [Figure 5] FIG. 5 is an AFM photograph of the self-assembled monolayer of FIG. 16 after annealing. [Figure 6] FIG. 6 is a graph of L vs. Mn for the lamellar block copolymers of Table 1 after coating and annealing on bare SiO or SiN. [Figure 7] FIG. 7 is an AFM photograph of the self-assembled monolayer of Comparative Example 1 after annealing. [Figure 8] FIG. 8 is an AFM photograph of the self-assembled monolayer of Comparative Example 2 after annealing. [Figure 9] FIG. 9 is a DSA of Block Copolymer Example 1 on graphoepitaxy substrates with trench / plateau dimensions of 40 / 40, 60 / 60, 80 / 80, and 100 / 100 nm from left to right. [Figure 10] FIG. 10 is a partial DSA on a chemo-epitaxy substrate (Example 15). [Figure 11] FIG. 11 shows DSA on a chemo-epitaxy substrate at low and high AFM magnification (Example 15). [Figure 12] FIG. 12 is a comparison of plasma etch rates for PMMA, P[MA-C6-azobutyl], and P[MA-C11-azobutyl]. [Figure 13]FIG. 13 is a continuous film of the annealed film of Pre-etch Example 11. [Figure 14] FIG. 14 is a continuous film of the annealed film of Example 11 after plasma etching. [Figure 15] Figure 15 shows AFM of fingerprint self-assembled films of PMMA-bP[MA C6 Azobutyl] (from left to right: Example 17, Example 18, Example 19, and bottom: Example 20, 1 wt %, 190°C, 1 hour, on SiN; 1 um x 1 um scan). [Figure 16] Figure 16 is an AFM of graphoepitaxy of PMMA-bP[MA C6 azobutyl] (Example 17, Mn 35 kDa) with L0 of 23 nm (1 wt%, 190 °C, 1 h, on 80 nm trench / plateau in SiOx). [Figure 17] Figure 17 is an AFM of chemoepitaxy of PMMA-bP[MA C6 azobutyl] (Example 17, Mn 35 kDa) with L0 of 23 nm (1 wt%, 190 °C, 1 h, pitch 90 nm, width 26 nm on xPMMA). [Figure 18] Figure 18 is an AFM of chemoepitaxy of PMMA-bP[MA C6 azobutyl] (Example 17, Mn 35 kDa) with L0 of 23 nm (1 wt%, 190 °C, 1 h, pitch 112 nm, width 26 nm on xPMMA). [Prior art documents] [Patent documents]

[0018] [Patent Document 1] WO15044215 [Non-patent literature]

[0019] [Non-Patent Document 1] Proc.SPIE 9051,Advances in Patterning Materials and Processes XXXI,90510K(27 March 2014);doi:10.1117 / 12.2048179 [Non-patent document 2] David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization”, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005) [Non-patent document 3] Adv.Synth.Catal.2002,344,370-378 Summary of the Invention

[0020] The disclosed and claimed invention relates to liquid crystal-based block copolymers (LC-BCPs) with a high Flory-Huggins interaction parameter (χ) (also known as "chi") for semiconductor patterning. Under certain conditions, the LC-BCPs described herein produce vertical lamellar structures directly on Si substrates. LC-BCPs have the advantage of being easily alignable into defect-free structures without the need for a neutral layer (NLD) or topcoat. Furthermore, the high interaction parameter (χ) enables the formation of small and large pitches and relatively thick ordered copolymer films, which leads to a simpler etching process and promises to meet industrial demands.

[0021] The problem to be solved is the desire to pattern integrated circuits with single-digit nanometer feature pitches with low defectivity and by methods that do not require extra steps, fab space, materials, tools, process time, costs, etc. Because multiple patterning and EUV lithography do not meet these requirements, new methods are needed as alternatives or complements.

[0022] Although some low-χ BCPs (e.g., PS-PMMA) have been used to complement multiple patterning by DSA and EUV, a series of problems remain. To obtain upright lamellae with commercial (non-liquid crystal) BCPs, a neutral layer (underlayer) or topcoat is generally required. However, this neutral layer, besides ultimately being an extra process step and material, increases pattern transfer defects during the etching step. An ideal polymer for DSA would not require the use of a neutral layer.

[0023] Low χ BCPs are limited in the minimum pitch they can achieve because the low dissimilarity of their blocks results in phase separation only at relatively high molecular weights. An ideal polymer for DSA would be one that has relatively high dissimilarity between each block (χ) and therefore can undergo phase separation at low molecular weights, providing a relatively small pitch.

[0024] Disclosed herein are novel block copolymers with suspended liquid crystal (LC) moieties that can potentially achieve single-digit nanometer-sized pitches without the use of neutral layers. Such materials can be used as a complement to conventional patterning lithography to obtain these types of pitches without the use of neutral layers and, accordingly, without the processing time and steps required to form such neutral layers and the increased defects that these extra steps would impart.

[0025] An example of a synthetic method for the synthesis of a novel LC-BCP polymerization is demonstrated, where the polymer has the structure PMMA-bP[MA-Cx-azobutyl] (x = 6, 8, 11), where the polymer is defined as follows: (PMMA = poly(methyl methacrylate) block segment; P[MA-Cx-azobutyl] = methacrylate (MA) block segment with LC moieties (Cx-azobutyl) attached; Cx = alkylene spacer between the MA carboxylate oxygen and the azobutyl moiety, where x is a carbon in the chain connecting MA and the azobutyl moiety; azobutyl moiety = (E)-4-((4-butylphenyl)diazenyl)phenoxy attached to the other end of the Cx linking group.

[0026] These working synthesis examples involve commercially suitable anionic polymerization methods. These novel block copolymer structures require the inclusion of hydrophobic end groups (LC capping groups) on the LC pendant moieties that are linear alkyls containing from 3 to 8 carbon atoms (C3-C8) (e.g., butyl in the examples).

[0027] These novel block copolymers, as annealed films on substrates, are capable of producing self-assembled patterns with pitches ranging from 17 to 73 nm without the use of an underlayer.

[0028] Additionally, embodiments can provide DSA graphoepitaxy and DSA chemoepitaxy on pre-patterned substrates as polymer films.

[0029] Experiments based on the examples showed good etch selectivity between PMMA and P[MA-Cx-azobutyl] blocks, as demonstrated by experiments performed with homopolymers and when etching self-assembled films of the novel block copolymers on SiOx substrates.

[0030] The basic strategy described here for these novel block copolymer architectures suitable for use for DSA on substrates without a neutral layer is also supplemented with prophetic examples that are a natural extension of the working examples. The synthetic method used to polymerize PMMA-bP[MA-Cx-azobutyl] (x=6, 8, 11) in the examples can be used when x is 3, 5, 7, 9, 12, and 13, and with IC capping groups other than butyl (C4) (alternatively, C3, C5-C8), to yield upstanding lamellae of the polymer with pitches as small as 5 nm without the use of a neutral underlayer. Multi-pitch DSA using the prophetic examples above is expected based on the initial results with PMMA-b-. DSA processing using these novel polymer architectures is expected to have particularly low defectivity because it does not require a neutral layer, either in graphoepitaxy or chemoepitaxy, as demonstrated by the examples. Because the introduction of a neutral layer requires fabrication, this will reduce the number of steps and improve the throughput of IC manufacturing using such processes.

[0031] Specifically, the novel polymer architecture is an AB type block copolymer comprising a first block A of Structure (I) and a second block B of Structure (II), wherein R and R1 are 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 the mole percent of repeating units of Structure (I) ranges from about 35 mole percent to about 94 mole percent of the total number of moles of repeating units of Structures (I) and (II), the mole percent of repeating units of Structure (II) ranges from about 6 mole percent to about 65 mole percent of the total number of moles of repeating units of Structures (I) and (II), and the sum of the mole percent of repeating units of Structures (I) and (II) equals 100 mole percent.

[0032] Further, in this polymer, R2 is selected from C1-C11 alkyl, L is C5-C12 linear alkylene, and R3 is selected from C3-C8 linear alkyl, and R' is H or C3-C8 linear alkyl, and further, the block copolymer has a polydispersity of 1 to about 1.31.

[0033] [ka] Another aspect of the disclosed and claimed invention is a composition comprising the block copolymer and an organic spin-casting solvent.

[0034] Yet another aspect of this disclosure and claimed invention is a method of using the compositions and / or block copolymers for self-assembly and directed self-assembly lithographic processing. DETAILED DESCRIPTION OF THE INVENTION

[0035] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive with respect to the invention as claimed. As used herein, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises" and other verb forms, such as "comprises," is not limiting. Furthermore, references to "elements" or "components" include both elements and components containing one unit and elements or components containing more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. As used herein, the conjunction "and" refers to any combination of the aforementioned elements, including the use of a single element.

[0036] The section headings used herein are for organizational purposes only and should not be construed as limiting the invention described. All references or portions thereof cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials cited herein conflicts with that herein, the definition herein shall control.

[0037] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group, which can be linear or branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties can be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1 to C8 carbons. For structural reasons, it is understood that linear alkyls begin at C1, while branched and cyclic alkyls begin at C3, and polycyclic alkyls begin at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy (alkoxy), are understood to have the same carbon number range unless otherwise specified. This same rule applies to the description of C1 to C4 alkyl. Where a different alkyl group length than those above is specified, the above definition of alkyl remains valid in that it encompasses all types of alkyl moieties above, and the structural considerations above regarding the minimum carbon number of a given type of alkyl group still apply.

[0038] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkyloxy moieties may be substituted or unsubstituted as described below. The criteria for establishing the type of alkyl in a C1-C8 alkoxy or C1-C4 alkoxy are the same as those described above for the alkyl moiety.

[0039] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0040] Haloalkyl refers to a saturated linear, cyclic, or branched alkyl group, such as those described above, in which at least one of the hydrogens has been replaced by a halide selected from the group F, Cl, Br, I, or a mixture thereof if more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0041] The term "alkylene," unless otherwise specified, refers to a hydrocarbon group that can be linear, branched, or cyclic, having two or more points of attachment (e.g., methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like, having two points of attachment; 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like, having three points of attachment). Again, when specifying a range of possible carbon numbers, such as, as a non-limiting example, C1 to C20, this range includes linear alkylene beginning at C1, but specifies only branched alkylene or cycloalkylene beginning at C3. These alkylene moieties can be substituted or unsubstituted, as described below. The term linear alkylene refers to a linear alkylene moiety having two points of attachment that is unsubstituted, unless otherwise specified. For example, when R' is H, L described herein is an unsubstituted C5-C12 alkylene, but when R' is a C3-C8 linear alkyl, L is a linear alkylene with a linear alkyl substituent as R'.

[0042] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, and the like. These aryl groups may be further substituted with any of the suitable substituents described above, such as alkyl, alkoxy, acyl, or aryl groups described above.

[0043] Unless otherwise indicated herein, the term "substituted," when used in connection with aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic ring, arene, heteroarene, includes unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH), and moieties containing ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1 to 3)). Specific non-limiting examples of substituted aryl and substituted arylethenyl substituents are the following, wherein:

[0044] [ka] represents the point of attachment.

[0045] [ka] Polymers of the Invention One aspect of the disclosed and claimed invention is a block copolymer that is an AB type diblock copolymer having a first block A of Structure (I) and a second block B of Structure (II), wherein R and R1 are independently selected from C1-C4 alkyl, n is the number of repeat units in Structure (I), m is the number of repeat units in Structure (II), and the mole % of repeat units of Structure (I) ranges from about 35 mole % to about 94 mole % of the total number of moles of repeat units of Structures (I) and (II), and the mole % of repeat units of Structure (II) ranges from about 6 mole % to about 65 mole % of the total number of moles of repeat units of Structures (I) and (II), and the sum of the mole % of repeat units of Structures (I) and (II) equals 100 mole %.

[0046] Further, R2 is selected from C1-C11 alkyl, L is C5-C12 linear alkylene, and R3 is selected from C3-C8 linear alkyl, and R' is H or C3-C8 linear alkyl, and further, the block copolymer has a polydispersity of 1 to about 1.31.

[0047] 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.

[0048] [ka] In one aspect of the disclosed and claimed invention, the block copolymer is one where R' is H. In another aspect, the block copolymer is one where R' is a C3-C8 linear alkyl.

[0049] In one aspect of the disclosed and claimed invention, the block copolymers described herein are prepared by anionic or RAFT polymerization.

[0050] In another aspect of this embodiment, the block copolymers described herein are prepared by anionic polymerization.

[0051] In one aspect, the copolymers are essentially 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, wherein the concentrations of these metals in solutions of these polymers in PGMEA are individually less than 2.5 ppb. In one aspect of the disclosed and claimed invention, the individual concentrations of calcium, copper, potassium, sodium, and lithium are less than 0.4 ppb.

[0052] In another aspect of the disclosed and claimed invention, the block copolymer has a polydispersity ranging from 1 to about 1.13. In another aspect of this embodiment, the polydispersity ranges from 1 to about 1.10. In yet another aspect of this embodiment, the polydispersity ranges from 1 to about 1.05. In yet another aspect of this embodiment, the polydispersity ranges from 1 to about 1.02. In yet another aspect of this embodiment, the polydispersity ranges from 1 to about 1.01.

[0053] In another aspect of the disclosed and claimed invention, the block copolymer has an M ranging from about 8 kilodaltons (kDa) to about 200 kDa. n (number average molecular weight). In another aspect of this embodiment, M n In another aspect of this embodiment, M ranges from about 8 kDa to about 120 kDa. n ranges from about 20 kDa to about 170 kDa. In yet another aspect of this embodiment, it ranges from about 37 kDa to about 108 kDa. In another aspect of this embodiment, when the polymer is produced by RAFT polymerization, the preferred range is from about 8 kDa to about 40 kDa.

[0054] In another aspect of this embodiment, it is a polypeptide having an M ranging from about 8 kDa to about 25 kDa. n It has.

[0055] In another aspect of the disclosed and claimed invention, when the block copolymer is produced by RAFT polymerization, it has structure (III), in which Rr1 is a C1-C8 alkyl, Rr2 is a C1-C8 alkyl, and Rr is a cyano moiety (—CN) or a carbonyl alkyl moiety (—C(═O)—Ri), where Ri is a C1-C8 alkyl or 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 C3-C8 linear alkyl. In another aspect of these embodiments, R is a C1-C2 alkyl. In another aspect of these embodiments, R is methyl. In another aspect of these embodiments, R1 is a C1-C2 alkyl. In another aspect of these embodiments, R1 is methyl. In another aspect of these embodiments, R2 is a 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. In another aspect of these embodiments, R2 is C1-C7 alkyl. In another aspect of these embodiments, R2 is C1-C6 alkyl. In another aspect of these embodiments, R2 is C1-C5 alkyl. In another aspect of these embodiments, R2 is C1-C4 alkyl. In another aspect of these embodiments, R2 is C1-C3 alkyl. In another aspect of these embodiments, R2 is C1-C2 alkyl. In another aspect of these embodiments, R2 is methyl.

[0056] In one aspect of the disclosed and claimed invention, the block copolymer of structure (III) has structure (IIIa):

[0057] In another aspect of the disclosed and claimed invention, the block copolymer of structure (III) or (IIIa) has structure (IIIa-1).

[0058] In a more specific aspect of structures (III) and (IIIa), R' is hydrogen, and the block copolymers of the invention described herein are those in which L is an unsubstituted C5-C12 linear alkylene, and have the more specific structures (III-1), (IIIa-2), and (IIIa-3).

[0059] In one aspect of structures (III), (IIIa), (III-1), (IIIa-2), and (IIIa-3), R3 is a C3-C8 alkyl. In another aspect, R3 is 1-propyl. In another aspect, R3 is 1-butyl. In another aspect, R3 is 1-pentanyl. In another aspect, R3 is 1-hexanyl. In another aspect, R3 is 1-heptanyl. In another aspect, R3 is 1-octanyl. In another aspect of these embodiments, L is a C5 linear alkylene. In another aspect of these embodiments, L is a C6 linear alkylene. In another aspect of these embodiments, L is a C7 linear alkylene. In another aspect of these embodiments, L is a C8 linear alkylene. In another aspect of these embodiments, L is a C9 linear alkylene. In another aspect of these embodiments, L is a C10 linear alkylene. In another aspect of these embodiments, L is C11 linear alkylene. In another aspect of these embodiments, L is C12 linear 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 C3-C8 linear alkyl.

[0060] In one more detailed aspect of structures (III) and (IIIa), they each have structure (IIIb) or (IIIc), where n' and n" are independently integers ranging 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 (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 C3-C8 alkyl. In another aspect, R3 is 1-propyl. In another aspect, R3 is 1-butyl. In another aspect, R3 is 1-pentanyl. In another aspect, R3 is 1-hexanyl. In another aspect, R3 is 1-heptanyl. In another aspect, R3 is 1-octanyl. In another aspect of these embodiments, L is a C5 linear alkylene. In another aspect of these embodiments, L is a C6 linear alkylene. In another aspect of these embodiments, L is a C7 linear alkylene. In another aspect of these embodiments, L is a C8 linear alkylene. In another aspect of these embodiments, L is a C9 linear alkylene. In another aspect of these embodiments, L is C10 linear alkylene. In another aspect of these embodiments, L is C11 linear alkylene. In another aspect of these embodiments, L is C12 linear 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.

[0061] In another aspect of the disclosed and claimed invention, the block copolymer is prepared by RAFT polymerization, wherein the -S-(C=S)-Rr end groups are removed and replaced with hydrogen, and have the structure (III'), (IIIa'), (IIIa-1'), (III-1'), (IIIa-2'), (IIIa-3'), (IIIb'), (IIIc'), or (IIIc-1').

[0062] [ka] In another aspect of the disclosed and claimed invention, the block copolymer is prepared by anionic polymerization. In one aspect of this embodiment, it has structure (IV): eis C1-C8 alkyl, and Rm and Rm1 are independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy. In another aspect of this embodiment, R is C1-C2 alkyl. In another aspect of this embodiment, R is methyl. In another aspect of this embodiment, R1 is C1-C2 alkyl. In another aspect of this embodiment, R1 is methyl. In another aspect of this embodiment, R2 is C1-C10 alkyl. In another aspect of this embodiment, R2 is C1-C9 alkyl. In another aspect of this embodiment, R2 is C1-C8 alkyl. In another aspect of this embodiment, R2 is C1-C7 alkyl. In another aspect of this embodiment, R2 is C1-C6 alkyl. In another aspect of this embodiment, R2 is C1-C5 alkyl. In another aspect of this embodiment, R2 is C1-C4 alkyl. In another aspect of this embodiment, R2 is C1-C3 alkyl. In another aspect of this embodiment, R2 is C1-C2 alkyl. In one aspect of this embodiment, R' is H. In another aspect of this embodiment, R' is C1-C8 linear alkyl. In another aspect of these embodiments, R is C1-C2 alkyl. In another aspect of these embodiments, R is methyl. In another aspect of these embodiments, R1 is C1-C2 alkyl. In another aspect of these embodiments, R1 is methyl. In another aspect of these embodiments, R2 is C1-C4 alkyl. In another aspect of these embodiments, R2 is C1-C2 alkyl. In another aspect of these embodiments, R2 is methyl. In another aspect of these embodiments, R3 is C3-C7 linear alkyl. In another aspect of these embodiments, R3 is C3-C6 linear alkyl. In another aspect of these embodiments, R3 is C3-C5 linear alkyl. In another aspect of these embodiments, R3 is n-butyl. In another aspect of these embodiments, L is a C5 linear alkylene. In another aspect of these embodiments, L is a C6 linear alkylene. In another aspect of these embodiments, L is a C7 linear alkylene. In another aspect of these embodiments, L is a C8 linear alkylene.In another aspect of these embodiments, L is a C9 linear alkylene. In another aspect of these embodiments, L is a C10 linear alkylene. In another aspect of these embodiments, L is a C11 linear alkylene. In another aspect of these embodiments, L is a C12 linear alkylene.

[0063] In another aspect of these embodiments, the block copolymer has the more specific structure (IVa) or (IVa-1). In one aspect of these embodiments, R' is H and L is an unsubstituted C5-C12 alkylene, and the polymer produced by anionic polymerization has the corresponding structure (IV'), (IVa'), or (IVa-1'). In one aspect of these embodiments, R3 is a C3-C8 alkyl. 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-pentanyl. In another aspect of these embodiments, R3 is 1-hexanyl. In another aspect of these embodiments, R3 is 1-heptanyl. In another aspect of these embodiments, R3 is 1-octanyl. In another aspect of these embodiments, L is a C5 linear alkylene. In another aspect of these embodiments, L is a C6 linear alkylene. In another aspect of these embodiments, L is a C7 linear alkylene. In another aspect of these embodiments, L is a C8 linear alkylene. In another aspect of these embodiments, L is a C9 linear alkylene. In another aspect of these embodiments, L is a C10 linear alkylene. In another aspect of these embodiments, L is a C11 linear alkylene. In another aspect of these embodiments, L is a C12 linear alkylene.

[0064] In another aspect of the block copolymers of structures (IV), (IVa), and (IVa-1), R' is a C3-C8 linear alkyl. In one aspect, R' is a C4-C8 linear alkyl. In one aspect, R' is a C4-C8 linear alkyl. In another aspect, R' is a C5-C8 linear alkyl. In another aspect, R' is a C5-C8 linear alkyl. In another aspect, R' is a C6-C8 linear alkyl. In another aspect, R' is a C7-C8 linear alkyl. In another aspect, R' is a C7 linear alkyl. In another aspect, R' is a C8 linear alkyl. In one aspect of this embodiment, the block copolymer of structure (IV) has more specific structure (IVb) or (IVc), where n' and n" are independently integers ranging from 0 to 11, and further, the sum of n' and n" ranges from 4 to 11. In one more detailed aspect of these structures, they each have structure (IVb) or (VIc), where n' and n" are independently integers ranging 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.

[0065] In another aspect of the embodiment wherein the block copolymer has structure (IV), (IVa), (IVa-1), (IV'), (IVa'), (IVa-1'), (IVb), (IVc), or (IVc-1), R3 is C3-C7 linear alkyl. In another aspect of these embodiments, R3 is C3-C7 linear alkyl. In another aspect of these embodiments, R3 is C3-C6 linear alkyl. In another aspect of these embodiments, R3 is C3-C5 linear alkyl. In another aspect of these embodiments, R3 is n-butyl. In another aspect of these embodiments, L is C5 linear alkylene. L is C6 linear alkylene. In another aspect of these embodiments, L is C7 linear alkylene. In another aspect of these embodiments, L is C8 linear alkylene. In another aspect of these embodiments, L is C9 linear alkylene. In another aspect of these embodiments, L is C10 linear alkylene. In another aspect of these embodiments, L is C11 linear alkylene. In another aspect of these embodiments, L is C12 linear alkylene. In another aspect of these embodiments, Rm and Rm1 are H.

[0066] [ka] TIFF2025536621000012.tif234170TIFF2025536621000013.tif120170Composition of the present invention Another aspect of the disclosed and claimed invention is a composition comprising any of the block polymers of the present invention described herein and an organic spin-casting solvent. Another aspect of the disclosed and claimed invention is a composition comprising any of the block polymers of the present invention described herein prepared by RAFT polymerization and an organic spin-casting solvent. Another aspect of the disclosed and claimed invention is a composition comprising any of the block polymers of the present invention described herein prepared by anionic polymerization and an organic spin-casting solvent.

[0067] In another aspect of the invention, the concentration of the novel polymer ranges from about 0.2% to about 2% by weight of the total weight of the composition, including the organic spin-casting solvent. In another aspect, the concentration ranges from about 0.5% to about 2% by weight.

[0068] Another aspect of the disclosed and claimed invention is a composition of any one of the block copolymers of the invention described herein having 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 an organic spin-casting solvent. In one aspect of this embodiment, the block polymer has general structure (III). In another aspect, it has structure (IIIa). In another aspect, it has structure (IIIa-1). In another aspect, it has structure (IIIa-2). In another aspect, it has structure (IIIa-3). In another aspect, it has structure (IIIb). In another aspect, it has structure (IIIc). In another aspect, it has structure (IIIc-1). In another aspect, it has structure (III'). In another aspect, it has structure (IIIa'). In another aspect, it has structure (IIIa-1'). In another aspect, it has structure (III-1'). In another aspect, it has structure (IIIa-2'). In another aspect, it has structure (IIIa-3'). In another aspect, it has structure (IIIb'). In another aspect, it has structure (IIIc'). In another aspect, it has structure (IIIc-1').

[0069] Another aspect of the disclosed and claimed invention is a composition of any one of the block copolymers of the present invention described herein having structure (IV), (IVa), (IVa-1), (IV'), (IVa'), (IVa-1'), (IVb), (IVc), or (IVc-1) in an organic spin-casting solvent. In one aspect of this embodiment, it has general structure (IV). In another aspect, it has more specific structure (IVa). In another aspect, it has structure (IVa-1). In another aspect, it has structure (IV'). In another aspect, it has structure (IVa'). In another aspect, it has structure (IVa-1'). In another aspect, it has structure (IVb). In another aspect, it has structure (IVc). In another aspect, it has structure (IVc-1).

[0070] In the above aspects of the novel composition, the organic spin-casting solvent is capable of dissolving the novel polymer and any other additional optional ingredients described above. The organic spin-casting solvent may be a single solvent or a mixture of solvents.Suitable solvents are organic solvents, such as glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dibasic acids, such as diethyl oxylate and diethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; Examples of suitable solvents include alkyloxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketone alcohol derivatives such as acetol or diacetone alcohol; ketals or acetals such as 1,3-dioxalane and diethoxypropane; lactones such as butyrolactone; amide derivatives such as dimethylacetamide or dimethylformamide, aromatic solvents such as naphtha, xylene, 1,2,4-trimethylbenzene, di-isopropylnaphthalene, phenylxylylethane, 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 embodiment, 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, phenylxylylethane, chlorobenzene, 1,2-dichlorobenzene, toluene, or anisole, and mixtures thereof; in one aspect of this embodiment, the solvent is toluene.

[0071] In addition to the polymer and the solvent, the novel composition may contain a surfactant as an additive to facilitate coating.

[0072] Methods of Using the Compositions of the Invention Another aspect of the disclosed and claimed invention is a method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of block copolymer having a periodicity L, comprising the steps of: a) forming a coating layer of any one of the copolymers described herein on the unpatterned substrate, which is not a neutral layer, using a composition of the block copolymer in an organic spin-casting solvent; b) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method comprises:

[0073] In another aspect of this method, the unpatterned substrate is selected from silicon (Si), silicon dioxide (SiOx), silicon nitride (SiN), and 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.

[0074] 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').

[0075] 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).

[0076] Another aspect of the disclosed and claimed invention is a method for vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having a periodicity L, wherein a topography height of the pattern on the substrate is at least 0.7 times L, and wherein the domains are aligned with the pattern, and wherein a bottom surface of the patterned substrate defined by the topography is not a neutral layer surface, the method comprising the steps of: a-1) forming a coating layer of any one of the block copolymers described herein on the first topographic substrate using a composition of the block copolymer in an organic spin-casting solvent, wherein the average thickness of the block copolymer coating layer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; b-1) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within recessed regions; The method comprises:

[0077] 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.

[0078] 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.

[0079] 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').

[0080] 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).

[0081] In one aspect of this method, the pattern is a pattern of cross-linked alkyl acrylate or alkyl methacrylate; in one specific embodiment of this aspect, the pattern is a pattern of cross-linked poly(methyl methacrylate). One example of a suitable cross-linked poly(methyl methacrylate) is described in Proc. SPIE 9051, Advances in Patterning Materials and Processes XXXI, 90510K (27 March 2014); doi:10.1117 / 12.2048179 (Non-Patent Document 1).

[0082] More specifically, for this method, a suitable patterned layer of poly(methyl methacrylate) can be obtained from a layer of a copolymer of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate (WO 15044215), which can be crosslinked thermally or with a thermal radical generator to produce crosslinked poly(methyl methacrylate) (X-PMMA). This X-PMMA can then be patterned by overcoating it with a photoresist, such as AIM5484JSRi ArF photoresist, patterning the photoresist with radiation, such as ArF radiation, and then developing the exposed photoresist film. This forms a patterned photoresist coating the X-PMMA, which is used as an etching mask to selectively etch portions of the X-PMMA layer. This etching process can use a chemical etchant or alternatively a plasma, such as oxygen plasma. After this etching pattern transfer, the remaining patterned photoresist is stripped with a chemical stripper, such as Fujifilm MS6800, to form the patterned X-PMMA. In one aspect of this method, the pattern of 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.

[0083] In another aspect of this method, the pattern is a line and space (L / S) pattern.

[0084] Another aspect of the disclosed and claimed invention is a method of vertically orienting first and second block copolymer domains having a periodicity L on a second patterned substrate having a topographical pattern, wherein the topographical pattern has a topographical height greater than 0.7 times L and a pitch P1, where the pitch P1 is a non-zero positive integer multiplied by L, and further wherein a bottom surface of the patterned substrate defined by the topography is not a neutral layer surface, and aligning the domains with the pattern, the method comprising: a-2) forming a coating layer of any one of the block copolymers described herein on the second patterned substrate using a composition of the block copolymer in an organic spin-casting solvent, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b-2) annealing the block copolymer layer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the second patterned substrate and align them with respect to the second patterned substrate, wherein the sum of the vertically oriented domains is equal to or greater than the pitch P1 of the topographical pattern.

[0085] 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. Suitable patterns of polar polymers can be obtained as described in the prior art.

[0086] 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.

[0087] In another aspect of this method, the block copolymer has structure (III), or more specifically, structure (IIIa), (IIIb), or (IIIc).

[0088] In another aspect of this method, the block copolymer has structure (IV), or more specifically, structure (IVa).

[0089] In one aspect of this method, the pattern is a pattern of a crosslinked alkyl acrylate or alkyl methacrylate; in one specific embodiment of this aspect, the pattern of crosslinked polar polymer is formed by patterning a coating of X-PMMA with UV radiation as described above. In one aspect of this method, the pattern of crosslinked polar polymer is formed by patterning a coating of a copolymer of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate with UV radiation. In one aspect of this embodiment, X-PMMA is a copolymer of methyl methacrylate and a vinyl ether.

[0090] In another aspect of this method, the pattern is a line and space (L / S) pattern.

[0091] Another aspect of the disclosed and claimed invention is a method for vertically orienting first and second block copolymer domains on a substrate having a surface chemical pre-pattern with a pitch P2, where the pitch P2 is a non-zero positive integer multiplied by L0, and aligning these domains, the method comprising the steps of: a-3) forming a coating layer of one of the block copolymers described herein on a substrate having a surface chemical pre-pattern using a composition of the block copolymer in an organic spin-casting solvent; and b-3) annealing the block copolymer layer to produce vertically oriented first and second block copolymer domains aligned with the substrate having a surface chemical prepattern with a pitch of 2; The method includes:

[0092] In another aspect of this method, the surface chemistry pre-pattern comprises both regions of a crosslinked polar polymer and regions of silicon, silicon dioxide, silicon nitride, or silicon oxynitride. 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.

[0093] 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.

[0094] In another aspect of this method, the surface chemical prepattern is formed by patterning a coating of a copolymer of methyl methacrylate and 2-(vinyloxy)ethyl methacrylate on the substrate with UV radiation.

[0095] 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').

[0096] In another aspect of this method, the block copolymer has structure (IV), or more specifically (IVa), (IVa-1), (IV'), (IVa'), (IVa-1'), (IVb), (IVc), or (IVc-1).

[0097] In one aspect of this method, the surface chemical prepattern comprises a polar brush region consisting of a grafted monolayer of a polar pinning polymer. In one aspect of this embodiment, the polar pinning polymer is an alkyl methacrylate with a grafting end group. In one aspect of this embodiment, the alkyl methacrylate with a grafting end group has a narrow polydispersity ranging from 1 to about 1.15. In another aspect of this embodiment, the alkyl methacrylate with a grafting group having a narrow polydispersity is methyl methacrylate. In another aspect of this method, the chemical prepattern resulting from the polar pinning polymer has a thickness ranging from about 3 nm to about 13 nm, in another aspect, the chemical prepattern has a thickness from about 3.5 nm to about 12.0 nm, in another aspect, it has a thickness from about 4.0 nm to about 11 nm, in another aspect, it has a thickness from about 4.5 nm to about 10 nm, in another aspect, it has a thickness from about 4.5 nm to about 9 nm, and in another aspect, it has a thickness from about 4.5 nm to about 8 nm. In another aspect of this method, the surface chemical prepattern is a patterned polar brush formed by first grafting a polar brush layer onto a substrate using a poly(methyl methacrylate) polymer functionalized with a hydroxy group on one side of the polymer chain, then selectively etching it using an overlying patterned photoresist as an etch barrier, and removing the photoresist.

[0098] In another aspect of this method, the surface chemical prepattern comprises a nonpolar brush region consisting of a grafted monolayer of a nonpolar pinning polymer. In one aspect of this embodiment, the nonpolar pinning polymer is a styrenic polymer having grafted end groups. The grafted end groups are reactive with substrates such as SiOx, SiN, or SiON, thereby forming a styrenic brush-functionalized surface. In one aspect of this embodiment, the styrenic polymer having grafted end groups has a narrow polydispersity ranging from 1 to about 1.15. In one aspect of this embodiment, the styrenic polymer having grafted groups with a narrow polydispersity is polystyrene. One example of a suitable grafted end group is an alcohol or benzylic alcohol end group. [Example]

[0099] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0100] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0101] Although the disclosed and claimed invention has been described and illustrated with a certain degree of detail, it will be understood that this disclosure is made by way of example only and that those skilled in the art may resort to numerous variations in the conditions and order of the steps without departing from the spirit and scope of the disclosed and claimed invention.

[0102] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich (3050 Spruce Street, 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. 6 wt% Sec-BuLi in cyclohexane was obtained from Albemarle. Methyl methacrylate (MMA) was used after filtration through basic aluminum oxide. LC monomers were synthesized as described below. Chemicals used in anionic polymerization were purified as described in the literature (e.g., David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization,” Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0103] Equipment configuration Spin coating of the polymer solutions was performed using an Ossilia Spin Coater 3.0. Annealing was performed using an IKA C-MAG HS7 Control Hotplate. Scanning electron microscopy (SEM) images were obtained using a Magellan 400L ultra-high-resolution scanning electron microscope. Atomic force microscopy (AFM) images were obtained using a Bruker Dimension-Icon XR scanning probe microscope. GISAXS analysis of the self-assembled and annealed block copolymer films to obtain L0 data was performed at the University of Hamburg using a home-built system consisting of the following components: an Incoatec IμS high-brilliance x-ray source, a Quasar Montell multilayer mirror, a Scatex non-scattering pinhole collimation system, and a Rayonix SA165 CCD detector. Measurement conditions: for SAXS, wavelength 0.154 nm, beam diameter at the sample 700 μm, sample-to-detector distance 1.6 m; for GISAX, fully evacuated beam path (excluding the sample area), integration time 3600 s per sample, and angle of incidence 0.2°. VASE ellipsometry measurements were obtained using a J.A. Woollam Alpha SE ellipsometer and Complete Ease software. Plasma oxygen etching experiments were performed using a Diner Pico Plasma Asher. The plasma etching conditions used to etch the block copolymer films were power = 100 watts (W). Gel permeation chromatography (GPC) was performed using GPC-MALS for absolute molecular weight (Mn) measurements. The system was equipped with an Agilent Degasser G7122A, pump G7110B, autosampler G7129A, column oven MCT G7116A, and detector VWD G7114A, a Wyatt Dawn8 MALS, and a Watt Optilab RI. A 10 mg, 30 kDa polystyrene standard was dissolved in 2 mL of THF. H NMR spectra were obtained on a Bruker Advance 500 MHz spectrometer.

[0104] Monomer synthesis example: Synthesis of liquid crystal monomer MA-Cx-azobutyl (MZ-Cx-azobutyl(x-(4-((4-butylphenyl)diazenyl)phenoxy)alkyl (Cx alkyl 6, 8, 11) methacrylate Each MA-Cx-azobutyl monomer (Cx alkyl 6, 8, 11) was prepared by the reaction shown in Scheme 1 below.

[0105] [ka] The following explanation relates to C6, i.e., the case where n=6: 6-(4-((4-butylphenyl)diazenyl)phenoxy)hexan-1-ol 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 equiv.) was dissolved in isopropanol (1.6 L). To this clear solution, potassium carbonate (0.75 mol, 103.65 g, 1.25 equiv.) and potassium iodide (60 mmol, 9.96 g, 1 equiv.) were added. 6-Bromo-hexan-1-ol (0.625 mol, 82 mL, 1.25 equiv.) was then introduced, and the mixture was stirred under reflux overnight. The mixture was allowed to cool to room temperature at 50°C and filtered to remove salts. The filtrate was then concentrated, and the solid was further purified by recrystallization from heptane:isopropanol (1:1) to give 139 g of product (yield: 78.4%).

[0106] Under an argon atmosphere, 6-(4-(p-toluyldiazenyl)phenoxy)hexan-1-ol (0.2 mol, 70.9 g, 1 equiv.) was dissolved in anhydrous dichloromethane (DCM) (1.8 L). Then, methacrylic acid (0.46 mol, 39.6 g, 2.3 equiv.) and 4-(dimethylamino)pyridine (DMAP) (0.06 mol, 7.33 g, 0.3 equiv.) 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 equiv.) was slowly added, and the reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed under reduced pressure, and the crude product was purified by passing through a silica gel column to obtain 65 g of the azo monomer as a yellow solid (yield: 77%).

[0107] Polymerization Example: Synthesis of PMMA-bP[MA-Cx-azobutyl] Polymerization of poly(MA-C6-azobutyl(poly(m((E)-x-(4-((4-butylphenyl)azenyl)phenoxy)alkyl(Cx alkyl 6, 8, 11) (x=6, 8, 11)) The LC-BCPs synthesized by RAFT polymerization and anionic polymerization had the following repeating unit structures: PMMA-bP[MA-Cx-azobutyl], poly(MA-C6-azobutyl(poly(m((E)-x-(4-((4-butylphenyl)diazenyl)phenoxy)alkyl(Cx alkyl 6, 8, 11), x = 6, 8, 11), and are shown below in structures (V-1), (V-2), and (V-3) schematically without details of the end groups, showing only the chemical structures of the A and B repeating units.

[0108] [ka] RAFT Polymerization Method (Scheme 2 & 3): In all examples, the polymer synthesis procedure began with the polymerization of the first block, PMMA. Methyl methacrylate (MMA) monomer (49.942 mmol) was filtered through basic aluminum oxide. The chain transfer agent (CTA) used in the preparation of the block copolymer (1-cyano-1-methylethylbenzenecarbodithioate was used in these cases) was selected to provide the desired Mn. Specifically, the amount of AIBN was selected in proportion to the CTA (CTA:AIBN = approximately 1:3). For example, in this polymerization example, the range of AIBN for the PMMA block was 0.04 to 0.19 mmol; the range for the second block copolymerization was 0.01 to 0.07 mmol. Therefore, the amount of AIBN in mmol determined the Mn of the polymer, as reported in Table 1. nThe solubility of the polymer was determined and pumped into a sealed glass ampoule under vacuum, followed by the introduction of argon or nitrogen. MMA and anisole were added. The vessel was stirred overnight at 70°C. The solution was then cooled to room temperature, and the polymer was precipitated three times with an anti-solvent (methanol) and then filtered through a Buchner funnel. Dissolution in anisole or toluene and precipitation into methanol, followed by filtration, was repeated two more times. Finally, the filtered polymer was dried in a vacuum oven at 40-50°C.

[0109] [Table 1]

[0110] [ka] The second block was added in the following general manner: The second monomer (MA-Cx-azobutyl), AIBN, and the previously described PMMA homopolymer were pumped under vacuum into a sealed glass ampoule, followed by argon or nitrogen. Degassed anisole was added via syringe. The mixture in the reaction vessel was stirred overnight at 70°C. The solution was then cooled to room temperature, and the precipitation procedure was repeated as for the previously described homopolymer. Table 1 summarizes the properties of the polymers thus prepared. The relative proportions of the two repeating units shown in Table 1 reflect the molar ratios of MMA and MA-Cx-azobutyl used.

[0111] [ka] Anionic polymerization method (Scheme 4): The precursor was prepared as follows: MMA monomer (103.280 mmol) was filtered through aluminum oxide and stored in a refrigerator with molecular sieves. This sample preparation was performed with 1,1-diphenylethylene (DPE) as the anion carrier. MA-Cx-azobutyl monomer was dissolved in toluene and stirred with calcium hydride for 3 hours, then filtered through aluminum oxide.

[0112] Each monomer was transferred to an ampoule, degassed, and flushed with argon three times. The molar ratio of the amount of MA-Cx-azobutyl monomer used to MMA reflected the proportion of the corresponding repeat unit, as shown in Table 1. The reactor containing LiCl was heated under vacuum and then cooled to room temperature. Under argon, THF (without inhibitor) was introduced into the reactor, which was then cooled to -78°C. The initiator (sec-BuLi) was added until a yellow color indicated the absence of water, after which the apparatus was allowed to return to room temperature. The apparatus was then cooled again to -78°C, and sec-BuLi (e.g., 0.2 mmol) was added via syringe and stirred for 5 minutes. (The moles of sec-BuLi relative to the moles of monomer correspond to the M of the polymer, as reported in Table 1.) n was determined. ) DPE (the volume of DPE is predicted by the volume of sec-BuLi) was added and stirred for 5 minutes. Then, an MMA monomer ampoule was opened into the apparatus and introduced at a rate of 1 drop / second. Upon completion, a second monomer ampoule was opened into the apparatus and introduced in the same manner. Stirring was started for 3 hours. The reaction was then stopped by introducing 3 mL of degassed methanol, which was allowed to warm to room temperature overnight. The final product was precipitated in methanol, filtered, and dried in a vacuum oven.

[0113] [ka] Table 2a summarizes different novel block copolymers prepared by either RAFT or anionic polymerization using the general synthetic scheme outlined above, but varying the amounts of two different monomers to achieve the specified ratios of these monomers in the block copolymer, and varying the amount of initiator to achieve different Mn values. Table 2b more specifically summarizes the anionic PMMA-bP[MA C6 azobutyl] for polymers with high chi DSA.

[0114] [Table 2]

[0115] [Table 3]

[0116] Comparative Example: Synthesis of PMMA-bP[MA-C6-azo-R] (R = methoxy, cyano) The following structure: PMMA-bP[MA-C6-azo-R] (where R = methoxy, cyano) The LC-BCPs for Comparative Examples 1 and 2 (Table 3) were synthesized by RAFT polymerization similar to Example 1, except that the LC-containing monomers had methoxy or cyano end groups instead of n-butyl. Structures (VI-1) and (VI-2) show the structures of these comparative block copolymers when the LC end group is methoxy or cyano, respectively.

[0117] [ka]

[0118] [Table 4]

[0119] Example of polymeric upright lamellar fingerprinting without an underlayer The polymers from the examples in Table 1 were observed to form upright lamellae on silicon dioxide (SiOx) and (SiN) substrates (without an underlayer).

[0120] Membrane manufacturing method: The polymers were dissolved in toluene or PGMEA at weight percentages between 0.5% and 2.5%. 100 μL of the polymers were spin-coated onto sulfuric acid-treated SiOx or untreated SiN substrates at 3000 rpm for 30 seconds. The films were annealed between 150 and 250°C for 10 minutes to 4 hours. All formulations containing the novel block copolymers treated in this manner were observed to form fingerprint patterns suggesting perpendicular orientation of the polymer block domains during the annealing process. As examples, AFM photographs of the self-assembly are shown in Figures 1, 2, 3, 4, and 5 for the fingerprint patterns obtained after annealing films of the copolymers of Examples 1, 5, 9, 15, and 16, respectively. However, all block copolymers (Examples 1 through 16) were examined by AFM with this orientation pattern, and these images were used to confirm the resulting L0, measured by GI-SAXS or from fast Fourier transform (FFT) of the AFM images. The results are shown in Table 4. The range of block copolymer pitch achieved during annealing on SiO or SiN ranges from 17 to 73 nm. The graph in Figure 5 shows the M of block copolymers Examples 1 to 16. n The dependence of L0 on

[0121] Additionally, fingerprint patterns (Figure 15) can be obtained using the polymers of Examples 17, 18, 19, and 20 (Table 2b) by spin-casting 1 wt % solutions of these polymers onto SiN and baking for 1 hour. The processing solvents used to obtain these fingerprint patterns were anisole, xylene, and cyclopentanone, although PGMEA and toluene can also be used. Figure 15 shows, from left to right, that the liquid crystal block copolymers of Examples 17, 18, and 19 each gave good fingerprint patterns, suggesting perpendicular alignment during the annealing process. Using the same processing conditions, the liquid crystal block copolymer of Example 20, apparently a cylindrical BCP, gave an AFM image with a center-to-center distance of 19 nm, consistent with the high chi of this system (Figure 15, bottom).

[0122] [Table 5]

[0123] The graph in Figure 1 shows the M n The dependence of L0 on

[0124] In contrast, Comparative Examples 1 and 2, when prepared and annealed on either SiO or SiN in the same manner as Examples 1-16, self-assembled block copolymer domains with a perpendicular orientation to these substrates. Table 5 summarizes the results obtained with these comparative copolymers. Figures 6 and 7 show SEMs observed for comparative block copolymers with methoxy or cyano LC capping groups, respectively.

[0125] [Table 6]

[0126] From this experiment, it was observed that the LC end groups have a significant effect on the interaction between the LC block and the substrate interface, achieving a vertical lamellar structure fingerprint. The AFM data show that when the LC end groups are hydrophilic, such as cyano and methoxy, vertical lamellae do not form, and one block has preferential interaction with the substrate. However, when the LC end groups are hydrophobic, such as butyl, vertical lamellar structures are observed. This means that the interactions of the PMMA block and the LC block with the substrate are the same.

[0127] Examples of DSA of polymers on graphoepitaxy prepatterned substrates Graphoepitaxy substrates were fabricated by electron beam lithography. The substrates featured plateaus and trenches in Si, with plateau / trench (line / space, L / S) width dimensions of 40 / 40, 60 / 60, 80 / 80, and 100 / 100 nm, and trench depths of approximately 25 nm. After sulfuric acid treatment, spin coating of the polymer solution was performed similarly to the flat substrate, followed by annealing. DSA was observed in the trenches. Figure 9 shows AFM (atomic force microscopy) images obtained by DSA of the block copolymer of Example 1 on the above graphoepitaxy substrates with trench / plateau dimensions of 40 / 40, 60 / 60, 80 / 80, and 100 / 100 nm, from left to right.

[0128] Figure 16 shows AFM images of graphoepitaxy of PMMA-bP[MA C6 azobutyl] (Example 17, Mn 35 kDa) with an L of 23 nm obtained at 1 wt % at 190 °C for 1 h on 80 nm trenches / plateaus in SiOx. These show an effective L of 20.8 nm. These were obtained by spin-coating solutions ranging from 0.45 to 1.2 wt % on topographic substrates of trenches / plateaus in silicon oxide with a 1:1 trench width:plateau width ratio. The widths were 40, 60, 80, and 100 nm. After annealing at 190 °C for 1 h, the BCP was observed to be aligned in the trenches and, at relatively high wt %, also on the plateaus. The observed effective L was 20.8 nm, whereas the observed L in the corresponding fingerprint pattern (Figure 15) was 23 nm.

[0129] Demonstration of DSA of novel block copolymers of Examples 1-16 on chemoepitaxy patterned substrates It was observed that partial chemoepitaxy DSA could be obtained using the novel block copolymers of Examples 1-13. These were annealed on thin, guided chemoepitaxy strips of crosslinked PMMA with a pitch of 90 nm and a width of 36 nm on SiN. Figure 10 shows an AFM image obtained when Example 15 was annealed on this guided chemoepitaxy on SiN. The AFM image shows the trans-prepattern pitch for DSA of the annealed film of block copolymer Example 15, which persists for a significant distance before the onset of disorder.

[0130] When annealed self-assembly of a film of block copolymer Example 15 was performed on a chemoepitaxy pattern of crosslinked PMMA with a 96 nm pitch and 31 nm wide crosslinked PMMA guide strips (these guide strips had a thickness of 4.8 nm), a lack of disorder and a 2-fold increase in chemoepitaxy DSA alignment were observed, which corresponds to the GISAXS L data reported previously. Figure 11 shows SEM images of this chemoepitaxy-induced self-assembly of an annealed film of this polymer at low and high AFM magnification.

[0131] Additionally, Figures 17 and 18 show PMMA-bP[MA C6 azobutyl] (Example 17, M n Figure 17 shows AFM images of the chemoepitaxy of a 35 kDa (35 kDa) block copolymer. In these figures, this block copolymer was coated at 1–1.2% on various chemical prepatterns of crosslinked PMMA and then annealed at 190 °C for 1 h. Specifically, Figure 17 shows DSA on a 90 nm pitch of 26 nm wide crosslinked PMMA (3.9 L0), and Figure 18 shows DSA on a 112 nm pitch (4.9 L0) and 26 nm wide xPMMA pitch. These were demonstrations of 4x and 5x pitch multiplication, respectively. Furthermore, DSA was also observed using guide strip widths (W) ranging from 1 to 1.4 L0.

[0132] Example of polymer etch selectivity The homopolymers PMMA (polymethyl methacrylate), P[MA-C6-azobutyl] (poly((E)-6-(4-((4-butylphenyl)diazenyl)phenoxy)hexyl methacrylate)), and P[MA-C11-azobutyl] (poly((E)-11-(4-((4-butylphenyl)diazenyl)phenoxy)undecyl methacrylate)) were deposited as films and exposed to plasma oxygen etching. The etch rates of each homopolymer were measured by VASE ellipsometry, revealing a two-fold difference in etch rate between the liquid crystal homopolymers and PMMA (Figure 12).

[0133] SEM images of LC-BCP before and after oxygen plasma etching of annealed self-assembled films of block copolymer examples 1-16 showed the relative removal of PMMA to the liquid crystal blocks after etching. Figure 13 shows a continuous film of self-assembled block copolymer example 11 after annealing. Figure 14 shows the same film after etching, demonstrating that the self-assembled PMMA block domains are selectively removed over the methacrylate block domains with pendant LC moieties.

[0134] Prospective Synthesis Example Set 1: Synthesis of PMMA-bP[MA-Cx-azobutyl] (x=3-12) Polymerization Similarly to Examples 1-16 having spacer chain lengths of C6, C8, and C11, other copolymers of PMMA-bP[MA-Cx-azobutyl] (x=3-12) having other chain lengths for L in Structure (II) ranging from C3 to C12 can be similarly synthesized using monomers of the corresponding C chain lengths as was done for the polymers of Examples 1-16.

[0135] Prophetic self-assembly example set 2: Upright lamellar fingerprints of the copolymers of the present invention with pitch as small as 5 nm without an underlayer The copolymers PMMA-bP[MA-Cx-azobutyl] (x=3-12) of Prophetic Example 1 would be expected to form upright lamellar fingerprints without the use of an underlayer. The polymers of Examples 1-16 demonstrated the ability to achieve pitches as small as 17 nm for polymers with Mn of 21 kDa. Because the polymers are high-chi materials, phase separation can occur even at the low Mn of these new polymers. This allows for particularly small pitches to be achieved. These polymers have Mn values ​​of <21 kDa. n It can be synthesized in a short time and is expected to provide a low L0 of down to 5 nm.

[0136] Prophetic Etching Example Set 3: Etch Selectivity of Copolymers of the Invention The polymers PMMA-bP[MA-Cx-azobutyl] (x = 3-12) of Prophetic Example Set 1 are expected to exhibit etch selectivity between the block containing the pendant liquid crystal group and the poly(methyl methacrylate) (PMMA) block similar to that observed in the homopolymer etch experiments in Figure 12 comparing C6 and C11 homopolymers with PMMA homopolymer and in the etch experiments shown in Figures 6 and 7 for the self-assembled films of the block copolymers of Example 11.

[0137] Prophetic Etching Multipitch Example Set 4: Multipitch DSA using Copolymers of the Invention The block copolymers of Examples 1-16 demonstrate the potential for multi-pitch DSA, where the same polymer compresses and expands to form different pitches depending on the prepattern dimensions. For example, two lines of the same polymer were repeated in both 60 nm and 80 nm trenches. This suggests a degree of flexibility. The polymer is expected to expand (stretch) up to 70% from its natural period. It is also expected that lengthening the LC capping group (R3) in Structure (II) from C4 to, for example, C7 and C8, will also contribute to the block copolymer's ability to expand and compress, providing a wider range of possibilities for multi-pitch-induced self-assembly. Such copolymers can be prepared in a similar manner to the C4-capped block copolymers of Examples 1-16.

[0138] Prophetic Example Set 5 for Reduced Defectivity: Low Defectivity in DSA Pattern Transfer Using the Polymer Based on the examples of these inventive block copolymers, it is expected that they will have particularly low defectivity (e.g., dislocations) in future applications in actual pattern transfer on integrated circuits. This is because the use of a neutral layer, which is typically required for DSA, ultimately increases defectivity during and after the etching process. Because these inventive block copolymers do not require the use of a neutral layer, the inventive block copolymers will incur lower defectivity.

[0139] Prospective examples of reduced defectivity: Synthesis and use of polymers where R' is C3-C8 linear alkyl. The above examples demonstrate the potential for multi-pitch DSA, where the same polymer compresses and expands to form different pitches depending on the prepattern dimensions. For example, two lines of the same polymer were repeated in both a 60 nm trench and an 80 nm trench. This suggests a degree of flexibility. The polymer's ability to expand (stretch) up to 70% from its natural period is expected. In addition, it is expected that a subset of polymers with C=3-8, preferably C7-C8, side chains or terminal groups to such liquid crystals may contribute to the polymer's ability to expand and compress. Below is a prophetic example of how a specific example of this type of material can be fabricated.

[0140] This prophetic example provides a concrete example of how copolymers of this variant of the invention having C3-C8 branched alkyl (or, alternatively, R' = C3-C8) can be prepared. This example illustrates the synthesis of precursor methacrylate monomers for the C8-branched MA-C6-azobutyl and MMA repeat units and their subsequent polymerization. Other CX-branched MA-Cx-azoalkyl (Cx') monomers [i.e., in structure (I), X = C5-C8, i.e., R' = linear alkyl branching group; x = 5-12, i.e., L = linear alkylene C5-C12; and Cx' = 3-8, i.e., R3 = C3-C8 linear alkyl] precursors, monomers, and block copolymers can be prepared in a similar manner. Scheme 5 shows the synthetic scheme for the precursor and C8-branched MA-C6-azobutyl repeat unit. These other CX-branched MA-Cx-azobutyls can be prepared in a similar manner.

[0141] Anionic polymerization of branched alkyl PMMA-b-[MA-C6 azobutyl] Prospective synthesis of 2-(4-bromobutyl)-decan-1-ol Step 1 (Scheme 5) Decanol (TCI, 10.30 mol, 1609 g, 1.2 equiv.) is reacted with 1,4-dibromobutane (TCI, 8.58 mol, 1853 g, 1 equiv.) in 4 N NaOH solution (7 L) in the presence of a water-soluble calix[n]arene catalyst (TAC4M catalyst, 0.013 equiv.). After the reaction, the aqueous reaction mixture is extracted with methylene chloride, the organic phase is washed with water, and dried over a drying agent such as anhydrous MgSO molecular sieves to remove methylene chloride. The crude product can be purified by column chromatography or recrystallization to produce 2-(4-bromobutyl)decanal in an expected yield of approximately 8% (200 g), with a predicted melting point of 60.7 °C. This reaction procedure was adapted from Adv. Synth. Catal. 2002, 344, 370-378 (Non-Patent Document 3).

[0142] [ka] Proposed synthesis of 2-(4-bromobutyl)-decan-1-ol Step 2 (Scheme 6) The carbonyl on the 2-(4-bromobutyl)decanal from step 1 is reduced with NaBH4 in methanol to produce the alcohol precursor for the following monomer synthesis. 2-(4-Bromobutyl)decanal (0.69 mol, 200 g, 1 equiv.) is dissolved in methanol (360 mL) and cooled to 0°C; NaBH4 (0.69 mol, 26.1 g, 1 equiv.) is then added in multiple portions with vigorous stirring. After the addition of NaBH4 is complete, the solution is heated to 40°C overnight. After the reaction, the methanol is removed by rotary evaporation and the residue is dissolved in methylene chloride, the organic phase is washed with water and dried over a drying agent such as anhydrous MgSO molecular sieves to remove methylene chloride, and the crude product is purified by column chromatography to produce 2-(4-bromobutyl)decan-1-ol in an expected yield of about 160 g (about 80% yield) with a predicted melting point of 79.4 °C and the predicted C NMR (ppm) shown in Scheme 6.

[0143] [ka] A prospective synthesis of the branched C8 branched MA-C6 azobutyl monomer ((E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate) is as follows: (Scheme 7) In a three-necked round-bottom flask equipped with a mechanical stirrer, a condenser, and a nitrogen inlet and outlet, 4-((4-butylphenyl)diazenyl)phenol (0.5 mol, 127.16 g, 1 eq.) is dissolved in isopropanol (1.6 L). To this clear solution, potassium carbonate (0.75 mol, 103.65 g, 1.25 eq.) and potassium iodide (60 mmol, 9.96 g, 1 eq.) are added. 2-(4-bromobutyl)-decan-1-ol (0.625 mol, 183.31 g, 1.25 eq.) is then introduced, and the mixture is stirred under reflux overnight. The mixture is allowed to cool to room temperature and filtered to remove salts. The filtrate is then concentrated and the solid is further purified by recrystallization from heptane:isopropanol (1:1) to give the product (£)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decan-1-ol (MW: 466.71) in an expected yield of 233.35 g (assuming 100% yield).

[0144] In an argon atmosphere, (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decan-1-ol (0.2 mol, 93.3 g, 1 eq.) is dissolved in anhydrous dichloromethane (1.8 L). Methacrylic acid (0.46 mol, 39.6 g, 2.3 eq.) and 4-(dimethylamino)pyridine (0.06 mol, 7.33 g, 0.3 eq.) are then added, and the mixture is cooled to 0° C. using an ice bath. N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (0.5 mol, 77.6 g, 2.5 eq.) is slowly added, and the reaction mixture is allowed to warm slowly to room temperature and stirred overnight. The solvent is removed under reduced pressure and the crude product is purified by passing through a silica gel column to give 106.95 g (100% yield) of (£)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate as a solid (MW 534.79). Figure 7 shows the predicted C NMR spectrum (ppm) of the final product.

[0145] [ka] Anionic polymerization of (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate with methyl methacrylate: Methyl methacrylate (MMA) monomer (103.280 mmol) was filtered through aluminum oxide and stored in a refrigerator with molecular sieves. This sample preparation was performed with 1,1-diphenylethylene (DPE) as the anion carrier. (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate as the branched MA-Cx-azobutyl monomer was dissolved in toluene and stirred with calcium hydride for 3 hours, then filtered through aluminum oxide.

[0146] Each monomer is transferred to an ampoule, degassed, and flushed with argon three times. The molar ratio of branched MA-C6-azobutyl monomer used to MMA ranges from 85%:15% to 15%:85%. The reactor containing LiCl is heated under vacuum and then cooled to room temperature. Under argon, THF (without inhibitor) is introduced into the reactor, which is then cooled to -78°C. The initiator (sec-BuLi) is added until a yellow color indicates the absence of water, after which the apparatus is allowed to return to room temperature. The apparatus is then cooled again to -78°C, and sec-BuLi (e.g., 0.2 mmol) is added via syringe and stirred for 5 minutes. The number of moles of sec-BuLi relative to the number of moles of monomer is the M of the polymer. n Determine the volume of the monomer mixture. Add DPE (the volume of DPE is predicted by the volume of sec-BuLi) and stir for 5 minutes. Then, open the MMA monomer ampoule into the apparatus and introduce it at a rate of 1 drop / second. Once completed, open the second monomer ampoule into the apparatus and introduce it in the same way. Start stirring for 3 hours. After that, 3 mL of degassed methanol is introduced to stop the reaction, which is left to come to room temperature overnight. The final product is precipitated in methanol, filtered, and dried in a vacuum oven.

[0147] Prospective synthesis of branched (C3)MA-C6 azobutyl monomer) (E) 4-(4-((4-butylphenyl)diazenyl)phenoxy)nonan-4-yl methacrylate) (Scheme 8) 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 equiv.) was dissolved in isopropanol (1.6 L). To this clear solution, potassium carbonate (0.75 mol, 103.65 g, 1.25 equiv.) and potassium iodide (60 mmol, 9.96 g, 1 equiv.) were added. 9-Bromonan-4-ol (0.625 mol, 139.5 g, 1.25 equiv., available from Aurora Building Blocks) was then introduced, and the mixture was stirred under reflux overnight. The mixture was allowed to cool to room temperature and filtered to remove salts. The filtrate was then concentrated, and the solid was further purified by recrystallization from heptane:isopropanol (1:1) to reveal the following: 14.1 ppm (CH in butyl), 22.3 ppm (CH in butyl), 33.4 ppm (CH in butyl), 35.4 ppm (CH in butyl), 144.8 ppm (quaternary aromatic carbons attached to butyl), 129.7 (aromatic CH in aromatic moieties attached to butyl), 122.8 (aromatic CH in aromatic moieties attached to butyl), 149.9 ppm (quaternary aromatic carbons attached to butyl), 149.9 ppm ... This material has a predicted C NMR of 145.3 ppm (quaternary aromatic carbon bonded to N=N moieties in aromatic groups with OH functionality), 145.3 ppm (quaternary aromatic carbon bonded to N=N moieties in aromatic groups with OH functionality), 124.4 ppm (aromatic CH in aromatic groups with OH functionality), 116.2 ppm (aromatic CH in aromatic groups with OH functionality), and 160.7 ppm (quaternary aromatic carbon bonded to OH) to obtain 232 g of product (assuming a 100% yield). Scheme 8 shows the predicted C NMR spectrum (ppm) of the final product.

[0148] [ka] Anionic polymerization of (E)-9-(4-((4-butylphenyl)diazenyl)phenoxy)nonan-4-yl methacrylate with methyl methacrylate: The anionic polymerization is carried out as described above for the copolymerization of methyl methacrylate with (E)-2-(4-(4-((4-butylphenyl)diazenyl)phenoxy)butyl)decyl methacrylate, except that the latter is replaced by an equivalent amount of (E)-9-(4-((4-butylphenyl)diazenyl)phenoxy)nonan-4-yl methacrylate).

[0149] The above description is intended primarily for purposes of illustration. While the disclosed and claimed invention has been shown and described with respect to exemplary embodiments thereof, it will be understood by those skilled in the art that the above and various other changes, omissions and additions in form and detail may be made thereto without departing from the spirit and scope of the disclosed and claimed invention.

Claims

1. A block copolymer that is an AB diblock copolymer having a first block A of structure (I) and a second block B of structure (II), wherein R and R １ are independently selected from C1-C4 alkyl, n is the number of repeat units in Structure (I), m is the number of repeat units in Structure (II), and the mole percent of repeat units of Structure (I) ranges from about 35 mole percent to about 94 mole percent of the total number of moles of repeat units of Structures (I) and (II), the mole percent of repeat units of Structure (II) ranges from about 6 mole percent to about 65 mole percent of the total number of moles of repeat units of Structures (I) and (II), and the sum of the mole percent of repeat units of Structures (I) and (II) equals 100 mole percent; R ２ is selected from C1-C11 alkyl, L is C5-C12 linear alkylene, and R ３ is selected from C3-C8 linear alkyl, and R' is H or C3-C8 linear alkyl, and further, the block copolymer has a polydispersity of 1 to about 1.

31. The block copolymer. 【Chemistry 1】

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

13.

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

10.

4. 4. The block copolymer of claim 1, wherein the block copolymer has a polydispersity of from 1 to about 1.

05.

5. 5. The block copolymer of claim 1, wherein the block copolymer has a polydispersity of from 1 to about 1.

02.

6. 6. The block copolymer of claim 1, wherein the block copolymer has a polydispersity of from 1 to about 1.

01.

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

8. The block copolymer has an M ranging from about 8 kDa to about 120 kDa. ｎ The block copolymer according to any one of claims 1 to 7, having the formula:

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

10. The block copolymer of any one of claims 1 to 9, wherein R' is H.

11. 10. The block copolymer of claim 1, wherein R' is a C3 to C8 linear alkyl.

12. 12. The block copolymer according to claim 1, which is produced by RAFT polymerization.

13. having the structure (III), wherein Rr １ is C1-C8 alkyl, and Rr ２ is a C1-C8 alkyl, and Rr is a cyano moiety (—CN) or a carbonylalkyl moiety (—C(═O)—Ri), Ri is a C1-C8 alkyl or aryl moiety, and Rr ３ The block copolymer of any one of claims 1 to 12, wherein is an unsubstituted or substituted aryl moiety. 【Chemistry 2】

14. 14. The block copolymer of claim 13, wherein R' is H.

15. 14. The block copolymer of claim 13, wherein R' is a C3 to C8 linear alkyl.

16. 16. The block copolymer of claim 1, wherein R is a C1-C2 alkyl.

17. 17. The block copolymer of claim 1, wherein R is methyl.

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

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

20. R ２ 20. The block copolymer of claim 1, wherein is a C1 to C4 alkyl.

21. R ２ 21. The block copolymer of claim 1, wherein is a C1-C2 alkyl.

22. R ２ The block copolymer of any one of claims 1 to 21, wherein is methyl.

23. 23. The block copolymer of any one of claims 1 to 22, wherein the block copolymer has the structure (IIIa): 【Transformation 3】

24. R ３ 24. The block copolymer of claim 23, wherein is a C3 to C8 alkyl.

25. R ３ The block copolymer of claim 23 or 24, wherein is 1-propyl.

26. R ３ The block copolymer of claim 23 or 24, wherein is 1-butyl.

27. R ３ The block copolymer of claim 23 or 24, wherein is 1-pentanyl.

28. R ３ The block copolymer of claim 23 or 24, wherein is 1-hexanyl.

29. R ３ The block copolymer of claim 23 or 24, wherein is 1-heptanyl.

30. R ３ The block copolymer of claim 23 or 24, wherein is 1-octanyl.

31. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C5 linear alkylene.

32. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C6 linear alkylene or a C7 linear alkylene.

33. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C8 linear alkylene.

34. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C9 linear alkylene.

35. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C10 linear alkylene.

36. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C11 linear alkylene.

37. 31. The block copolymer of any one of claims 23 to 30, wherein L is a C12 linear alkylene.

38. Rr ３ The block copolymer of any one of claims 23 to 30, wherein is unsubstituted aryl.

39. Rr ３ The block copolymer of any one of claims 23 to 30, wherein is substituted aryl.

40. Rr ２ is methyl and Rr １ The block copolymer of any one of claims 23 to 39, wherein is butyl.

41. 41. The block copolymer of any one of claims 23 to 40, wherein R' is H.

42. 41. The block copolymer of any one of claims 23 to 40, wherein R' is a C3 to C8 linear alkyl.

43. 43. The block copolymer of claim 42, wherein the block copolymer is of structure (IIIb), wherein n′ and n″ are independently integers ranging from 0 to 11, and further wherein the sum of n′ and n″ ranges from 4 to 11. 【Chemistry 4】

44. 44. The block copolymer of claim 43 having the structure (IIIc): 【Transformation 5】

45. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 4.

46. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 5.

47. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 6.

48. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 7.

49. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 8.

50. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 9.

51. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 10.

52. 45. The block copolymer of claim 43 or 44, wherein n' is 0 and n'' is 11.

53. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 3.

54. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 4.

55. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 5.

56. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 6.

57. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 7.

58. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 8.

59. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 9.

60. 45. The block copolymer of claim 43 or 44, wherein n' is 1 and n'' is 10.

61. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 2.

62. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 3.

63. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 4.

64. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 5.

65. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 6.

66. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 7.

67. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 8.

68. 45. The block copolymer of claim 43 or 44, wherein n' is 2 and n'' is 9.

69. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 1.

70. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 2.

71. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 3.

72. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 4.

73. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 5.

74. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 6.

75. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 7.

76. 45. The block copolymer of claim 43 or 44, wherein n' is 3 and n'' is 8.

77. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 0.

78. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 1.

79. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 2.

80. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 3.

81. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 4.

82. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 5.

83. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 6.

84. 45. The block copolymer of claim 43 or 44, wherein n' is 4 and n'' is 7.

85. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 0.

86. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 1.

87. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 2.

88. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 3.

89. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 4.

90. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 5.

91. 45. The block copolymer of claim 43 or 44, wherein n' is 5 and n'' is 6.

92. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 0.

93. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 1.

94. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 2.

95. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 3.

96. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 4.

97. 45. The block copolymer of claim 43 or 44, wherein n' is 6 and n'' is 5.

98. 45. The block copolymer of claim 43 or 44, wherein n' is 7 and n'' is 0.

99. 45. The block copolymer of claim 43 or 44, wherein n' is 7 and n'' is 1.

100. 45. The block copolymer of claim 43 or 44, wherein n' is 7 and n'' is 2.

101. 45. The block copolymer of claim 43 or 44, wherein n' is 7 and n'' is 3.

102. 45. The block copolymer of claim 43 or 44, wherein n' is 7 and n'' is 4.

103. 45. The block copolymer of claim 43 or 44, wherein n' is 8 and n'' is 0.

104. 45. The block copolymer of claim 43 or 44, wherein n' is 8 and n'' is 1.

105. 45. The block copolymer of claim 43 or 44, wherein n' is 8 and n'' is 2.

106. 45. The block copolymer of claim 43 or 44, wherein n' is 8 and n'' is 3.

107. 45. The block copolymer of claim 43 or 44, wherein n' is 9 and n'' is 0.

108. 45. The block copolymer of claim 43 or 44, wherein n' is 9 and n'' is 1.

109. 45. The block copolymer of claim 43 or 44, wherein n' is 9 and n'' is 2.

110. 45. The block copolymer of claim 43 or 44, wherein n' is 10 and n'' is 0.

111. 45. The block copolymer of claim 43 or 44, wherein n' is 10 and n'' is 1.

112. 45. The block copolymer of claim 43 or 44, wherein n' is 11 and n'' is 0.

113. 12. The block copolymer of claim 1, which is prepared by anionic polymerization.

114. having the structure (IV), in which R ｅ is C1-C8 alkyl, and Rm and Rm １ is independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy. 【Transformation 6】

115. 115. The block copolymer of claim 114, wherein R' is H.

116. 115. The block copolymer of claim 114, wherein R' is a C3 to C8 linear alkyl.

117. 117. The block copolymer of any one of claims 1 to 11, 115 and 116, wherein R is a C1 to C2 alkyl.

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

119. R １ 119. The block copolymer of any one of claims 1 to 11 and 115 to 118, wherein is a C1 to C2 alkyl.

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

121. R ２ 121. The block copolymer of any one of claims 1 to 11 and 115 to 120, wherein is a C1 to C4 alkyl.

122. R ２ 122. The block copolymer of any one of claims 1 to 11 and 115 to 121, wherein is a C1 to C2 alkyl.

123. R ２ 123. The block copolymer of any one of claims 1 to 11 and 115 to 122, wherein is methyl.

124. R ３ 124. The block copolymer of any one of claims 1 to 11 and 115 to 123, wherein is a C3 to C7 linear alkyl.

125. R ３ 125. The block copolymer of any one of claims 1 to 11 and 115 to 124, wherein is a C3 to C6 linear alkyl.

126. R ３ 126. The block copolymer of any one of claims 1 to 11 and 115 to 125, wherein is a C3 to C5 linear alkyl.

127. R ３ 127. The block copolymer of any one of claims 1 to 11 and 115 to 126, wherein is n-butyl.

128. 128. The block copolymer of any one of claims 1 to 11 and 115 to 127, wherein L is a C5 linear alkylene.

129. 129. The block copolymer of any one of claims 1 to 11 and 115 to 128, wherein L is a C6 linear alkylene.

130. 130. The block copolymer of any one of claims 1-11 and 115-129, wherein L is a C7 linear alkylene.

131. 131. The block copolymer of any one of claims 1-11 and 115-130, wherein L is a C8 linear alkylene.

132. 132. The block copolymer of any one of claims 1 to 11 and 115 to 131, wherein L is a C9 linear alkylene.

133. 133. The block copolymer of any one of claims 1 to 11 and 115 to 132, wherein L is a C10 linear alkylene.

134. 134. The block copolymer of any one of claims 1 to 11 and 115 to 133, wherein L is a C11 linear alkylene.

135. 135. The block copolymer of any one of claims 1 to 11 and 115 to 134, wherein L is a C12 linear alkylene.

136. 136. The block copolymer of any one of claims 1-11 and 115-135, having the structure (IVa): 【Transformation 7】

137. R ３ is a C3 to C8 alkyl.

138. R ３ The block copolymer of claim 136 or 137, wherein is 1-propyl.

139. R ３ The block copolymer of claim 136 or 137, wherein is 1-butyl.

140. R ３ The block copolymer of claim 136 or 137, wherein is 1-pentanyl.

141. R ３ The block copolymer of claim 136 or 137, wherein is 1-hexanyl.

142. R ３ The block copolymer of claim 136 or 137, wherein is 1-heptanyl.

143. R ３ The block copolymer of claim 136 or 137, wherein is 1-octanyl.

144. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C5 linear alkylene.

145. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C6 linear alkylene or a C7 linear alkylene.

146. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C8 linear alkylene.

147. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C9 linear alkylene.

148. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C10 linear alkylene.

149. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C11 linear alkylene.

150. 144. The block copolymer of any one of claims 136 to 143, wherein L is a C12 linear alkylene.

151. Rm and Rm １ is H.

152. 151. The block copolymer of any one of claims 136 to 150, wherein R' is H.

153. 151. The block copolymer of any one of claims 136-150, wherein R' is a C3 to C8 linear alkyl.

154. 154. The block copolymer of claim 153, wherein the block copolymer is of structure (IVb), wherein n′ and n″ are independently integers ranging from 0 to 11, and further wherein the sum of n′ and n″ ranges from 4 to 11. 【Transformation 8】

155. 155. The block copolymer of claim 153 or 154, wherein the block copolymer is of structure (IVc): 【Chemistry 9】

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

177. 156. The block copolymer of claim 154 or 155, wherein n' is 2 and n'' is 7.

178. 156. The block copolymer of claim 154 or 155, wherein n' is 2 and n'' is 8.

179. 156. The block copolymer of claim 154 or 155, wherein n' is 2 and n'' is 9.

180. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 1.

181. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 2.

182. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 3.

183. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 4.

184. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 5.

185. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 6.

186. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 7.

187. 156. The block copolymer of claim 154 or 155, wherein n' is 3 and n'' is 8.

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

189. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 1.

190. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 2.

191. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 3.

192. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 4.

193. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 5.

194. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 6.

195. 156. The block copolymer of claim 154 or 155, wherein n' is 4 and n'' is 7.

196. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 0.

197. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 1.

198. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 2.

199. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 3.

200. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 4.

201. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 5.

202. 156. The block copolymer of claim 154 or 155, wherein n' is 5 and n'' is 6.

203. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 0.

204. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 1.

205. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 2.

206. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 3.

207. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 4.

208. 156. The block copolymer of claim 154 or 155, wherein n' is 6 and n'' is 5.

209. 156. The block copolymer of claim 154 or 155, wherein n' is 7 and n'' is 0.

210. 156. The block copolymer of claim 154 or 155, wherein n' is 7 and n'' is 1.

211. 156. The block copolymer of claim 154 or 155, wherein n' is 7 and n'' is 2.

212. 156. The block copolymer of claim 154 or 155, wherein n' is 7 and n'' is 3.

213. 156. The block copolymer of claim 154 or 155, wherein n' is 7 and n'' is 4.

214. 156. The block copolymer of claim 154 or 155, wherein n' is 8 and n'' is 0.

215. 156. The block copolymer of claim 154 or 155, wherein n' is 8 and n'' is 1.

216. 156. The block copolymer of claim 154 or 155, wherein n' is 8 and n'' is 2.

217. 156. The block copolymer of claim 154 or 155, wherein n' is 8 and n'' is 3.

218. 156. The block copolymer of claim 154 or 155, wherein n' is 9 and n'' is 0.

219. 156. The block copolymer of claim 154 or 155, wherein n' is 9 and n'' is 1.

220. 156. The block copolymer of claim 154 or 155, wherein n' is 9 and n'' is 2.

221. 156. The block copolymer of claim 154 or 155, wherein n' is 10 and n'' is 0.

222. 156. The block copolymer of claim 154 or 155, wherein n' is 10 and n'' is 1.

223. 156. The block copolymer of claim 154 or 155, wherein n' is 11 and n'' is 0.

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

225. A composition comprising a block copolymer according to any one of claims 1 to 112 prepared by RAFT polymerization, and an organic spin-casting solvent.

226. 224. A composition comprising a block copolymer according to any one of claims 1 to 11 and 113 to 223 prepared by anionic polymerization, and an organic spin-casting solvent.

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

228. 227. The composition of 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, carboxylates, dicarboxylates of dibasic acids, dicarboxylates of glycols, hydroxycarboxylates, ketones, alkyloxycarboxylic acid esters such as methyl 3-methoxypropionate, ketone esters, ketone ethers; ketone alcohol derivatives; ketals, acetals, lactones, amide derivatives, and aromatic solvents.

229. The organic spin-casting solvent is 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 oxylate, 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, diacetone alcohol methyl ether, acetol, diacetone alcohol, 1,3 dioxalane, diethoxypropane, butyrolactone, dimethylacetamide, dimethylformamide, anisole, toluene, and mixtures thereof.

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

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

232. Periodicity L ０ 1. A method for vertically orienting first and second block copolymer domains on an unpatterned substrate using a layer of a block copolymer having the following steps: a) forming a coating layer of a block copolymer on the unpatterned substrate, which is not a neutral layer, using the composition of any one of claims 224 to 231; and b) annealing the layer of block copolymer to produce vertically oriented, non-zero positive integer first and second block copolymer domains on the unpatterned substrate; The method comprising:

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

234. Periodicity L ０ and vertically orienting first and second block copolymer domains on a first patterned substrate using a coating comprising a block copolymer having ０ and a method of aligning these domains in said pattern, comprising the steps of: a-1) forming a coating layer of the block copolymer on the first topographic substrate using the composition of any one of claims 224 to 231, wherein the average thickness of the coating layer of the block copolymer is less than the height of the topography of the first topographic substrate, and the block copolymer layer is laterally confined by the topography; and b-1) annealing the block copolymer layer to produce first and second block copolymer domains that are vertically oriented on the first patterned substrate and confined within recessed regions; The method comprising:

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

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

238. A periodic L is formed on a second patterned substrate having a topographical pattern. ０ and vertically orienting the first and second block copolymer domains having a topographical pattern of L ０ The topography height and pitch P are more than 0.7 times １ and has a pitch P １ Is, L ０ and further wherein a bottom surface of the patterned substrate defined by the topography is not a neutral layer surface, and a method of aligning the domains with the pattern, comprising the steps of: a-2) forming a coating layer of a block copolymer on the second patterned substrate using the composition of any one of claims 224 to 231, wherein the thickness of the coating layer of the block copolymer is greater than the height of the topography of the second patterned substrate; and b-2) annealing the block copolymer layer to produce perpendicularly oriented, non-zero positive integer first and second block copolymer domains on the second patterned substrate and aligning them with respect to the second patterned substrate, wherein the sum of the perpendicularly oriented domains is equal to the pitch P of the topographical pattern. １ That's it, step; The method comprising:

239. 239. The method of 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. 240. The method of claim 239, wherein the pattern of 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.

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

242. Pitch P, not including the neutral layer region ２ and orienting the first and second block copolymer domains perpendicularly on a substrate having a surface chemical prepattern having a pitch P ２ Is L ０ and a method for aligning these domains, comprising the steps of: a-3) forming a coating layer of a block copolymer on a substrate having a surface chemical pre-pattern using the composition according to any one of claims 224 to 231; and b-3) Annealing the block copolymer layer to form a pitch P ２ producing aligned, vertically oriented first and second block copolymer domains on a substrate having a surface chemical pre-pattern having: The method comprising:

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

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

245. The method of claim 242 or 243, wherein the surface chemical pre-pattern is a patterned polar brush formed by first grafting a polar brush layer onto a substrate using a poly(methyl methacrylate) polymer functionalized with a hydroxy group on one of the polymer chains, then selectively etching it using an overlying patterned photoresist as an etching barrier, and then removing 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 lithographic processing.

Images