method

Abstract

This is a method for forming a self-assembled film on the surface of a substrate (101). A solution containing a block copolymer and a solvent is deposited on the surface. The block copolymer is a rod-coil copolymer containing rod blocks A and coil blocks B. The surface may have one or more feature regions (103) to induce the self-assembly of the rod-coil polymer.

Description

[Background technology]

[0001] Kim et al, “Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates,” Nature volume 424, pages 411-414 (2003), discloses the self-assembly of the diblock copolymer PS-b-PMMA.

[0002] Luo and Epps, “Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication,” Macromolecules 2013, 46, 7567-7579, discloses the induced self-assembly of block copolymer thin films.

[0003] Tseng and Darling, “Block Copolymer Nanostructures for Technology”, Polymers, 2010, Vol.2 Issue 4, 470-489, disclose block copolymer nanostructures for microelectronics and photovoltaic power generation. [Overview of the Initiative]

[0004] This disclosure provides a method for forming a self-assembled film on a surface, comprising depositing a solution containing a block copolymer and a solvent onto the surface and evaporating the solvent, wherein the block copolymer is a rod-coil copolymer comprising a rod block A and a coil block B.

[0005] Optionally, rod block A has a conjugated skeleton.

[0006] Optionally, rod block A is made of vinylene, acetylene, imine, and Ar 1, and units selected from combinations thereof, each of which may be unsubstituted or substituted with one or more substituents, Ar 1 This is an arylene group or a heteroarylene group.

[0007] Optionally, rod block A is given by equation (I): [ka] It has,

[0008] In the formula, Ar 1 The group is a monocyclic group, a fused aromatic group, or a heteroaromatic group, and n is greater than 1.

[0009] Optional, Ar 1 It is either unsubstituted or substituted phenylene.

[0010] Optionally, the coil block has a skeleton that does not contain conjugated double or triple bonds.

[0011] Optionally, the coil block skeleton does not contain double or triple bonds.

[0012] Optionally, coil block B is given by equations (II) to (VII): [ka] [ka] [ka] [ka] [ka] [ka] Selected from,

[0013] In the formula, R 1 In each occurrence, is independently either H or a substituent, and m is greater than 1.

[0014] Optionally, the block copolymer includes a connecting unit that links rod block A to coil block B.

[0015] Optionally, the unit of connection is given by equation -N=CR 9 - is the imine unit, and in the formula, R 9 is either H or a substituent.

[0016] Optionally, the linking unit is a monocyclic or polycyclic group that has been optionally substituted.

[0017] Optionally, the block copolymer is selected from AB block copolymer, ABA block copolymer, and BAB block copolymer.

[0018] Optionally, the block copolymer contains fused aromatic terminal groups or heteroaromatic terminal groups comprising at least four fused aromatic rings or heteroaromatic rings.

[0019] Optionally, the surface comprises at least one feature portion for inducing the self-assembly of the block copolymer.

[0020] Optionally, at least one feature for inducing self-organization defines one or more regions of the substrate having a different surface energy from the rest of the substrate.

[0021] Optionally, the deposited block copolymer is heated to a temperature exceeding the glass transition temperature of the block copolymer.

[0022] This disclosure provides a method for patterning a substrate, comprising: providing an inductively self-assembled rod-coil block copolymer, comprising rod block A and coil block B, on the surface of the substrate; selectively removing one of rod block A and coil block B, preferably selectively removing coil block B; and patterning the substrate. The rod-coil block copolymer may be any of those described elsewhere herein.

[0023] The substrate is optionally a silicon substrate.

[0024] The disclosed technology and accompanying drawings illustrate several implementations of the disclosed technology. [Brief explanation of the drawing]

[0025] [Figure 1] This is a schematic diagram of a substrate having surface features that induce self-organization. [Figure 2] Figure 1 is a schematic diagram of the induced self-assembled layer of rod-coil block copolymer formed on the substrate. [Figure 3] This is an atomic force microscope image of a block copolymer film annealed for 2 hours. [Figure 4] This is an atomic force microscope image of a block copolymer film annealed for 5 hours.

[0026] The drawings are not drawn to scale and have various viewpoints and perspectives. The drawings show several implementations and embodiments. In addition, some components and / or operations may be separated into different blocks or combined into a single block for the purpose of illustrating some embodiments of the disclosed technology. Furthermore, the technology is applicable to various modifications and alternative forms, specific embodiments are shown in the drawings as examples and are described in detail below. However, the technology is not intended to be limited to the specific implementations described. In contrast, the technology is intended to encompass all modifications, equivalents, and alternatives that fall within the scope of the technology as defined by the appended claims. [Modes for carrying out the invention]

[0027] Unless the context clearly requires otherwise, throughout the specification and claims, terms such as “comprise” and “comprising” shall be interpreted in a comprehensive sense, i.e., “including, but not limited to,” as opposed to an exclusive or thorough sense. In addition, the terms “as specified,” “above,” “below,” and terms of similar intent, when used in this application, refer to the entire application and not to any particular part of this application. Where the context allows, terms in forms for carrying out an invention using singular or plural forms may also include plural or singular forms, respectively. The term “or” in relation to a list of two or more items encompasses all of the following interpretations of that term: any of the items in the list, all of the items in the list, and any combination of the items in the list. When used in this application, a reference to a layer “above” another layer means that the layers may be in direct contact or one or more intervening layers may be present.

[0028] As used in this application, a reference to a layer "on top of" another layer means that the layers are in direct contact. A reference to a specific atom includes any isotope of that atom unless otherwise specified.

[0029] The teachings of the technology provided herein may be applied to systems other than those described below. Further implementations of the technology can be provided by combining elements and operations of the various embodiments described below. Some alternative implementations of the technology may include fewer elements than those described below, as well as additional elements.

[0030] These and other modifications may be made to the Art in light of the detailed description below. This specification describes specific embodiments of the Art and the best possible ways of doing so, but no matter how detailed the description may seem, the Art can be carried out in many ways. As described above, any specific terms used to describe a particular feature or aspect of the Art should not be construed as meaning that the terms are redefined herein to be limited to any particular characteristic, feature, or aspect of the Art relating to the term. In general, the terms used in the following claims should not be construed as limiting the Art to the specific embodiments disclosed herein unless such terms are explicitly defined elsewhere in the section on modes for carrying out the invention. Thus, the actual scope of the Art includes not only the disclosed embodiments but also all equivalent ways of carrying out or implementing the Art based on the claims.

[0031] To reduce the number of claims, certain aspects of the technology are presented below in the form of specific claims, although the applicant intends to present various aspects of the technology in any number of claim forms.

[0032] In the following description, numerous specific details are provided for illustrative purposes to provide a full understanding of the implementations of the disclosed technology. However, it will be apparent to those skilled in the art that the embodiments of the disclosed technology can be implemented without some of these specific details.

[0033] This disclosure provides a rod-coil block copolymer comprising at least one rod block and at least one coil block. For brevity, a rod-coil block copolymer having a single rod block and a single coil block is described herein, but unless otherwise specified, it will be understood that such a block copolymer may have multiple rod blocks and / or multiple coil blocks.

[0034] Compared to coil blocks, rod blocks have relatively limited conformations that they can adopt. The inventors have found that such rod-coil block copolymers can form self-assembled structures on their surfaces by induced self-assembly (DSA).

[0035] In DSA, a solution of block copolymers is deposited onto a surface, allowing the block copolymers to self-assemble. Those skilled in the art will understand that the shape and relative dimensions of the self-assembled domains are influenced by the relative volume fraction (f), the Florey-Huggins interaction parameter (χ), and the degree of polymerization (N) of each block. The pattern formed by self-assembly can be induced by one or more surface features on the substrate.

[0036] Referring to Figure 1, surface feature regions 103 are formed on the surface of the substrate 101, for example, a silicon substrate. The surface feature regions are relatively far apart due to the resolution limitations of the process for forming the surface feature regions. The surface feature regions that induce the organization of the block copolymer may be physical feature regions (graphoepitaxy) such as ridges on the substrate. The surface feature regions that induce the organization of the block copolymer may also be feature regions formed by chemical treatment of the substrate surface (chemoepitaxy), for example, by changing the hydrophilicity of the substrate in the surface feature region. The formation of the surface feature regions may be as described in C. Pinto Gomez, “Directed Self-Assembly of Block Copolymers for the Fabrication of Functional Devices”, Polymers 2020, 12(10), 2432, the details of which are incorporated herein by reference.

[0037] In the embodiment shown in Figure 1, rod block A has a higher affinity for the surface features than coil block B. As a result, during the drying of the solution, the rods self-assemble on the surface features as shown in Figure 2. This, in turn, affects the arrangement of block copolymer chains that are not present on the substrate features, and as shown in Figure 2, the rod block A and coil block B of the polymer chains in the solution self-assemble with the rod block A and coil block B on the surface, respectively, causing replication of the block chain copolymer structure organization throughout the entire region of the deposited solution.

[0038] The resulting self-assembled structure includes rod domains and coil domains with dimensions smaller than the distance between surface features used to induce self-assembly of the block copolymer, e.g., narrower widths. Preferably, the distances between surface features and / or between surface features are at least twice or at least five times larger than the dimensions of the self-assembled structure. Optionally, the self-assembled structure has dimensions (e.g., width) of 20 nm or less.

[0039] Preferably, the substrate does not include a brush layer for preventing vertical phase separation.

[0040] Preferably, a topcoat to prevent vertical phase separation is not applied to the surface of the self-assembled layer.

[0041] The high degree of ordering possible in the induced self-assembly of rod-coil block copolymers can enable the formation of domains with low edge roughness (e.g., low linear edge roughness between domains in Figure 1) and / or low domain size variation, even when one or more surface features used in the induced self-assembly have relatively high edge roughness and / or size variation, as shown in Figure 1.

[0042] The self-assembled structure may be processed to selectively remove either coil domains or rod domains using methods known to those skilled in the art, such as wet etching or plasma etching, as described in H. Puliyalil et al, “Selective Plasma Etching of Polymeric Substrates for Advanced Applications”, Nanomaterials (Basel). 2016 Jun, 6(6):108, ACS Nano, 2020, 14, 4, 4289-4297, Nano Lett., 2014, 14, 10, 5698-5705, and Hiroyuki Miyazoe et al 2017 J.Phys.D:Appl.Phys.50 204001 (their contents are incorporated herein by reference), and the remaining domains may be used to pattern the underlying substrate. For example, the remaining domains may be used as a positive or negative photoresist to pattern the underlying substrate. Preferably, coil domains are removed.

[0043] In the embodiments shown in Figures 1 and 2, rod block A has a higher affinity for surface features than coil block B. In other embodiments, coil block B has a higher affinity for surface features than rod block A.

[0044] In the embodiment shown in Figure 1, two surface features are indicated to induce self-organization. In other embodiments, the surface may have no surface features, one surface feature, or two or more surface features.

[0045] In the embodiment shown in Figure 1, striped surface features are shown to induce self-assembly, but it will be understood that one or more surface features may have any shape depending on the desired pattern of the self-assembled block copolymer. For example, the surface features may be in the form of one or more islands on the surface of the substrate.

[0046] Preferably, the polymers described herein have a polystyrene-equivalent weight-average molecular weight (Mw) of the polymers described herein, optionally in the range of 5,000 to 1,000,000, more preferably in the range of 9,000 to 500,000.

[0047] Preferably, the polymers described herein have a glass transition temperature greater than 80°C, preferably less than 200°C, as measured by differential scanning calorimetry.

[0048] The inventors have discovered that the rod-block copolymer described herein undergoes phase separation upon deposition on a surface, forming a lamellar phase-separated structure having phase-separated feature regions of less than 100 nm, optionally less than 50 nm or less than 20 nm, and optionally at least 5 nm, as measured by an atomic force microscope.

[0049] Rod block The block copolymer includes at least one rod block A.

[0050] In some embodiments, the block copolymer comprises a single rod block. Exemplary block copolymers according to these embodiments are A-B and B-A-B block copolymers.

[0051] In some embodiments, the block copolymer comprises a plurality of rod blocks. An exemplary block copolymer according to these embodiments is A-B-A.

[0052] The rod block comprises a chain of groups selected from vinylene, acetylene, imine, proline, Ar 1 , and combinations thereof, where Ar 1 is an arylene group or a heteroarylene group. Combinations include, for example, arylene vinylene groups and arylene acetylene groups. The rod block is preferably at least partially conjugated along its backbone and may be conjugated along the entire length of its backbone. However, the rod block may be formed from non-conjugated units, such as proline.

[0053] Compared to the coil block, the rod block has relatively restricted adoptable conformations, and it will be understood that the degree of freedom of movement along the backbone of the rod is mainly restricted by the rotation of the Ar 1 groups relative to each other. Therefore, the rod block is relatively rigid compared to the coil block.

[0054] Rod block A has the formula -(Ar 1 ) n -, where Ar 1 is an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents, and n is greater than 1.

[0055] Preferably, n is at least 3, and optionally 3 to 20. In preferred embodiments, the rod block is monodisperse, i.e., n is the same for all molecules of the block copolymer. In other embodiments, the rod block is polydisperse, in which case n is the number mean. Preferably, if the rod block is polydisperse, the degree of polydispersity of the rod block is less than 2, more preferably less than 1.5, and even more preferably 1.1 or less.

[0056] Preferred aromatic Ar 1 The base is formula -(Ar 1 ) n -May be in a rod block, or may be used in combination with one or more vinylene, acetylene, and imine units, selected from formulas (IA) to (IF), more preferably (IA) or (IB), [ka] [ka] [ka] [ka] [ka] [ka]

[0057] In the formula, R 2 , R 3 , R 4 , R 5 and R 6 In each occurrence, is H or a substituent, and X is O, S, NR 7 , C(R 8 )2 or Si(R 8 )2, and of which, R 7 is H or a substituent, R 8 Each occurrence is independently a substituent.

[0058] R 2 , R 3 , R 4 , R 5 and R 6 These are H, F, and C, respectively, independently. 1-20 Selected from alkyl, one or more non-adjacent non-terminal C atoms are O, S, NR 7 , Si(R 8 )2, OSi(R 8 )2, CO, COO or CONR 7 It may be replaced by one or more H atoms, and one or more H atoms may be replaced by optionally substituted aryl or heteroaryl groups or F, optionally substituted aryl groups, and optionally substituted heteroaryl groups.

[0059] As used herein, the term "non-terminal C atom" of an alkyl group means a C atom of an alkyl group other than the C atom of the methyl group at the end of an n-alkyl chain or the C atom of each methyl group at the end of a branched alkyl chain.

[0060] R 2 , R 3 , R 4 , R 5 and R 6 Any of the aryl or heteroaryl groups is preferably C 6-12 The group is an aryl group, more preferably a phenyl group, which may be unsubstituted or substituted with one or more substituents. The substituents are F, Cl, NO2, CN, and C. 1-12 The alkyl group may be selected, and one or more non-adjacent non-terminal carbon atoms may be O, S, or NR. 6 , Si(R 8 )2, OSi(R 8 )2, CO, COO or CONR 6 It may be replaced by , and one or more H atoms may be replaced by F.

[0061] For formulas (IA), (IB), and (ID), preferably at least one base R 2 , more preferably one or two base R2 It's not H, but the remaining R 2 The base is H.

[0062] Preferably, each R 3 H is H, and / or each R 4 H is H.

[0063] Each R 5 It is preferably H.

[0064] R 7 Preferably H or C 1-20 It is a hydrocarbyl group. C as described anywhere in this specification. 1-20 The hydrocarbyl group is unsubstituted or has one or more C 1-12 C substituted with alkyl group 1-20 Alkyl and phenyl compounds may be selected.

[0065] R 8 In each occurrence, may be the same or different, preferably C 1-20 Selected from alkyl groups, one or more non-adjacent non-terminal carbon atoms are O, S, NR 7 CO, COO or CONR 7 It may be replaced by one or more H atoms, and one or more H atoms may be replaced by optionally substituted aryl or heteroaryl groups or F, optionally substituted aryl groups, and optionally substituted heteroaryl groups.

[0066] R 8 The aryl or heteroaryl group is preferably C 6-12 An aryl group, more preferably a phenyl group, which may be unsubstituted or substituted with one or more substituents. Substituents include F, Cl, NO2, CN, and C. 1-12 It can be selected from alkyl groups, and one or more non-adjacent non-terminal C atoms are O, S, NR 7 CO, COO or CONR 7 It may be replaced by , and one or more H atoms may be replaced by F.

[0067] Preferred heteroaromatic group Ar 1 These are thiophene and furan, which may be unsubstituted or substituted with one or more substituents. Heteroaromatic group Ar 1 The substituents are optionally the above non-H group R 2 Selected from.

[0068] Coil block The coil block's frame has a greater degree of freedom of movement than a rod block. As a result, the coil block is relatively more flexible than a rod block.

[0069] The coil block framework preferably does not contain conjugated double or triple bonds, and more preferably does not contain double or triple bonds. The coil block may contain, for example, C=O or C=N units, and only C atoms of C=O or C=N units are present in the coil block framework. According to some embodiments, the coil block has sp in its framework. 3 Hybrid atoms, for example, sp 3 It contains only hybrid C, O, S, and / or N atoms.

[0070] A preferred coil block B is given by equations (II) to (VII): [ka] [ka] [ka] [ka] [ka] [ka] It includes,

[0071] In the formula, R1 is H or a substituent at each occurrence, and m is greater than 2. Preferably, m ranges from 10 to 5,000, optionally 20 to 3,000.

[0072] Each R 1 is preferably independently H, F, Cl, an aromatic group or a heteroaromatic group Ar 2 , preferably phenyl or pyridyl, COOR 7 , CONR 7 2, and C 1-20 alkyl, and one or more non-terminal C atoms of the alkyl may be replaced by O, S, NR 7 , CO, COO or CONR 7 and R 7 is as described above, and one or more H atoms of the C 1-20 alkyl may be replaced by F.

[0073] Each Ar 2 may be unsubstituted or substituted with one or more substituents. The substituents of Ar 2 , when present, may be selected from F, CN, NO2, and C 1-20 alkyl, and one or more non-terminal C atoms of the alkyl may be replaced by O, S, NR 6 , CO, COO or CONR 6 , and one or more H atoms of the alkyl may be replaced by F.

[0074] Preferred substituents R 1 are optionally substituted benzene (i.e., those in which the repeating unit of formula (II) is styrene or its substituted analog) and -COO-C 1-19 alkyl (i.e., those in which the repeating unit of formula (II) is acrylate, such as methacrylate). According to these embodiments, preferably, only one R 1 is a substituent and all other R 1 groups are H.

[0075] Terminal group Ends of a rod block or coil block that are not connected to the other end of the rod block or coil block via a connecting unit may be replaced with H or a substituent.

[0076] If the block copolymer has rod block A at the ends of the polymer backbone, for example in the case of AB or ABA block copolymers, the ends of the rod block may be substituted with terminal groups containing or consisting of optionally substituted condensed aromatic ring systems or heteroaromatic ring systems.

[0077] Optionally, the terminal group is a fused aromatic ring system or a heteroaromatic ring system comprising at least four fused rings, optionally at least six fused rings, or optionally at least eight or at least ten fused rings. The fused ring system is preferably a fused aromatic ring system. In a preferred embodiment, the fused ring system consists of fused benzene rings.

[0078] If substituents in the fused ring system are present, the above non-H group R 2 It can be selected from the following.

[0079] The following are exemplary terminal groups of the rod block: [ka] Terminal groups of planar condensed aromatic ring systems or heteroaromatic ring systems may promote pi-pi stacking of rod block A.

[0080] Connection Unit In some embodiments, the rod block or each rod block is directly coupled to at least one coil block.

[0081] In some embodiments, the block copolymer includes at least one connecting unit that connects the coil block to the rod block.

[0082] In some preferred embodiments, the rod block and coil block are connected via imine connection units. In these embodiments, the ends of the rod block A are connected to an aldehyde (-C(=O)H) reactant and an amine (-NHR) reactant. 9 ) One of the reactive groups is substituted, and the end of coil block B is substituted with the other of the aldehyde group and the amine group, R 9 is H or a substituent, preferably H or C 1-12 The group is alkyl, more preferably H. In the case of ABA block copolymer, both ends of coil block B are substituted with the same reactive group. In the case of BAB block copolymer, both ends of rod block A are substituted with the same reactive group.

[0083] Polymer synthesis The formation of the rod-coil block copolymer described herein may include providing a rod block, providing a coil block, and covalently connecting at least one rod block to at least one coil block using any connection known to those skilled in the art.

[0084] If the rod block contains condensed aromatic terminal groups or heteroaromatic terminal groups, the terminal groups may be formed before or after connecting the rod block and the coil block. The rod blocks described herein may be formed by any method known to those skilled in the art.

[0085] In some embodiments, the rod block is grown by adding units of the rod block in stages to form a monodisperse rod block.

[0086] In some embodiments, the rod block is formed by polymerization. Exemplary methods known to those skilled in the art for forming conjugated polymers include Suzuki polymerization and Yamamoto polymerization, as described in WO 00 / 53656 or US 5777070, the contents of which are incorporated herein by reference. The polydispersity of the polymerized rod block can be controlled by any method known to those skilled in the art, for example, the methods disclosed in Macromolecules 2011, 44, 9, 3388-3397 or J. Am. Chem. Soc. 2007, 129, 23, 7236-7237, the contents of which are incorporated herein by reference.

[0087] The coil blocks described herein may be formed by any method known to those skilled in the art, for example, by free radical polymerization of optionally substituted ethylene.

[0088] In some preferred embodiments, the polymer comprises a plurality of parallel rod blocks and / or a plurality of parallel coil blocks. According to these embodiments, the rod blocks and coil blocks are connected via a monocyclic ring connecting group or a fused ring connecting group, optionally via a connecting group of formula (VIII),

Chemical formula

[0089] Preferably, Cy is benzene or,

Chemical formula

[0090] The block copolymer containing the connecting group of formula (VIII) may have the following formula, where block A 1 is the first rod block, block A 2Block B is the second rod block, and Block B is the coil block. [ka] Examples of rod-coil block copolymers include the following, where R 2 and R 8 As described above, each is preferably C 4-12 It is an alkyl group.

[0091] [ka] [ka] [ka] [ka] [ka]

[0092] Formation of a membrane Self-assembled polymer films can be formed by depositing a solution containing one or more solvents and a polymer onto a surface having one or more optionally induced surface features, and then evaporating one or more of the solvents.

[0093] One or more solvents may be selected depending on the solubility of the block copolymer, which may depend on the solubility of the individual blocks.

[0094] The solvent can be optionally Cl or C. 1-6 Alkyl, and two alkyl groups may be linked to form a ring C 1-6 One or more benzenes substituted with one or more substituents selected from alkoxys, e.g., toluene, xylene, trimethylbenzene, anisole, indan, tetralin, dichlorobenzene, cyclic or acyclic ethers, e.g., tetrahydrofuran, dioxane, or di(C)1-6 Alkyl ether, Chlorinated C 1-6 Alkanes, such as chloroform or dichloromethane, and mixtures thereof, are selected.

[0095] After the solution is deposited, heat is optionally applied to remove one or more solvents. After film formation, the polymer is preferably heated to a temperature above its glass transition temperature. Optionally, the heating is carried out at a temperature of at least 120°C, and optionally at at least 180°C.

[0096] The film containing the block copolymer preferably has a thickness of 500 nm or less, and optionally 100 nm or less.

[0097] In some embodiments, the surface is preferably a silicon surface.

[0098] The inventors have found that self-assembly can be achieved without any treatment of the surface on which the block copolymer is deposited. Therefore, the deposition surface preferably does not include regions with different surface properties, and preferably, the solution containing the block copolymer is deposited directly onto the silicon surface. [Examples]

[0099] The rod-coil block copolymer was synthesized by linking rod block oligomer A1 to coil blocks B1, B2, or B3.

[0100] Synthesis of oligomer A1 [ka]

[0101] To a stirred solution of 1,4-dibromo-2,5-dihexylbenzene (100 g, 0.25 mol) in THF (1 L), n-BuLi (2.5 M, 108 mL, 0.27 mol) was added at -78°C. After stirring at -78°C for 3 hours, triisopropyl borate (60.48 g, 73.9 mL, 0.32 mol) was added, and the mixture may be warmed to room temperature, and then stirred for a further 16 hours. After this, 6 M HCl (150 mL) was added, and the mixture was stirred at 25°C for 1 hour. The reaction mixture was concentrated under vacuum, and the resulting solid was pulverized with acetonitrile (500 mL). Further purification by recrystallization with a mixture of hot toluene (1 L) and acetonitrile (500 mL) yielded intermediate 1-2 (80 g, yield 88%).

[0102] 1 H-NMR (400MHz, MeOD): δ[ppm]0.92(t, J=5.60Hz, 6H), 1.33~1.36(m, 12H), 1.57~1.5 8(m, 4H), 2.56(t, J=8.00Hz, 2H), 2.71(t, J=8.00Hz, 2H), 7.15(s, 1H), 7.37(s, 1H). LCMS: Purity 98.0%.

[0103] [ka]

[0104] Potassium carbonate (4.68 g, 33.8 mmol) was added to a stirred solution of (4-bromo-2,5-dihexylphenyl)boronic acid (intermediate 1-2, 5 g, 13.5 mmol) in acetonitrile (50 mL). The reaction mixture was purged with N2 gas for 15 minutes, then iodine (6.85 g, 27 mmol) was added, and the reaction mixture was heated at 80°C for 16 hours. The reaction mixture was concentrated under vacuum, diluted with ethyl acetate (100 mL), and washed with water (100 mL). The organic layer was separated, passed through a fluorosyl plug, concentrated, and purified by column chromatography (SiO2 230-400 mesh) using 100% hexane as the eluent to obtain intermediate 1-3 (4 g, yield 65%).

[0105] 1H-NMR (400MHz, MeOD): δ[ppm]0.93(t, J=5.60Hz, 6H), 1.34~1.35(m, 12H), 1.54~1.55(m, 4H), 2.65~2.65(m, 4H), 7.41(s, 1H), 7.70(s, 1H). HPLC: 99.2% purity.

[0106] [ka]

[0107] A mixture of intermediates 1-2 (7 g, 18.9 mmol) and naphthalene-1,8-diamine (3.29 g, 20.8 mmol) in toluene (350 mL) was heated at 140 °C for 4 hours. The reaction products were then concentrated, and the crude product was purified twice by column chromatography to obtain intermediate 1-4 (4.8 g, 68% yield).

[0108] 1 H-NMR (400MHz, CDCl3): δ[ppm]0.86(t, J=3.60Hz, 3H), 0.93(t, J=3.60Hz, 3H), 1.27~1.37(m, 12H), 1.61~1.61(m, 4H), 2.68~2.70(m, 4H) , 5.79(s, 2H), 6.37(d, J=7.20Hz, 2H), 7.09(d, J=8.40Hz, 2H), 7.14(s, 1H), 7.17(d, J=8.00Hz, 1H), 7.28(d, J=2.00Hz, 1H), 7.42(s, 1H). HPLC: 99.7% purity.

[0109] [ka]

[0110] Potassium carbonate (8.41 g, 60.9 mmol) was added to a stirred solution of intermediate 1-2 (15 g, 40.6 mmol) and iodobenzene (8.28 g, 40.6 mmol) in a mixture of toluene (80 mL), ethanol (60 mL), and water (20 mL). The reaction mixture was purged with N2 for 15 minutes, and tetrakis(triphenylphosphine)palladium(0) (1.39 g, 1.21 mmol, 3 mol%) was added. The reaction mixture was heated at 100 °C for 16 hours. The reaction mixture was concentrated under vacuum, and the crude residue was purified by column chromatography (230-400 silica mesh) using 30% ethyl acetate in hexane as the eluent, and by recrystallization (toluene:acetonitrile) to obtain intermediate 1-5 (10.5 g, yield 61%) as a white solid.

[0111] 1 H-NMR (400MHz, CDCl3): δ[ppm]0.84(t, J=7.20Hz, 3H), 0.91(t, J=7.20Hz, 3H), 1.15~1.16(m, 6H), 1.33~1.47(m, 8H), 1.61~1.62(m, 2H), 2.51(t, J=8.00Hz, 2H), 2.72(t, J=8.00Hz, 2H), 7.06(s, 1H), 7.28~7.29(m, 2H), 7.35~7.46(m, 4H).

[0112] [ka]

[0113] To a stirred solution of intermediate 1-5 (10 g, 24.9 mmol) in 1,4-dioxane (100 mL), KOAc (6.1 g, 62.2 mmol) and B2Pin2 (7.56 g, 29.8 mmol) were added. The reaction mixture was purged with N2 for 15 minutes, PdCl2 (dppf) (610 mg, 745 μmol, 3 mol%) was added, and the reaction mixture was refluxed at 100°C for 16 hours. Subsequently, it was diluted with water, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, the crude solid was pulverized with hexane, and filtered to obtain intermediate 1-6 (10.5 g, yield 94%).

[0114] 1 H-NMR (400MHz, CDCl3): δ[ppm]0.83(t, J=7.20Hz, 3H), 0.90(t, J=6.80Hz, 3H), 1.17~1.18(m, 6H), 1.30~1.58(m, 22 H), 2.56(t, J=7.20Hz, 2H), 2.87(t, J=8.00Hz, 2H), 7.04(s, 1H), 7.31~7.39(m, 3H), 7.41~7.41(m, 2H), 7.69(s, 1H).

[0115] [ka]

[0116] To a solution of intermediates 1-6 (328 mg, 0.73 mmol) and 3-13 (600 mg, 0.50 mmol, synthesis described below) in THF (10 mL), Na2CO3 (103 mg, 1.0 mmol) in water (1 mL) was added, and the reaction mixture was purged with N2 for 5 minutes. Tetrakis(triphenylphosphine)palladium(0) (16.9 mg, 3 mol%) was added, and the reaction mixture was heated at 90°C for 5 hours until the starting materials were completely consumed. The reaction mixture was diluted with water, extracted with EtOAC, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was subjected to reverse-phase column chromatography (GRACE RP, C) using acetonitrile:THF (50%) as the eluent. 18 The solution was purified by column chromatography, followed by grinding with a mixture of hexane and ethyl acetate to obtain intermediates 1-7 (0.35 g, 49% yield). LC-MS: Purity 94.9%.

[0117] [ka]

[0118] A solution of intermediate 1-7 (0.85 g, 579 μmol) in THF (30 mL) was mixed with 5 N HCl (20 mL), and the reaction mixture was refluxed at 75 °C for 4 hours. After cooling to room temperature, the resulting solid was filtered and washed with acetonitrile to obtain intermediate 1-8 (0.7 g, yield 85%) as a white solid. LC-MS: Purity 90.8%.

[0119] [ka]

[0120] Intermediate 1-2 (15 g, 40.5 mmol), 4-iodobenzaldehyde (9.4 g, 40.5 mmol), and potassium carbonate (11.2 g, 81 mmol) were purged with N2 for 15 minutes in a mixture of toluene (120 mL), ethanol (90 mL), and water (30 mL). Tetrakis(triphenylphosphine)palladium(0) (1.39 g, 3 mol%) was added, and the reaction mixture was heated at 95°C for 16 hours. The mixture was concentrated, and the crude product was purified by column chromatography (SiO2, 230-400 mesh) using 3% ethyl acetate in hexane as the eluent to obtain intermediate 2-2 (12.5 g, yield 72%).

[0121] 1 H-NMR (400MHz, CDCl3): δ[ppm]0.86(t, J=6.80Hz, 3H), 0.91~0.92(m, 3H), 1.15~1.21(m, 6H), 1.32~1.46(m, 8H), 1.60~1.6 6(m, 2H), 2.50(t, J=8.00Hz, 2H), 2.73(t, J=8.00Hz, 2H), 7.04(s, 1H), 7.46~7.46(m, 3H), 7.94~7.94(m, 2H), 10.10(s, 1H).

[0122] [ka]

[0123] Sodium borohydride (520 mg, 139 mmol) was added in five portions to a solution of intermediate 2-2 (6 g, 13.9 mmol) in a mixture of THF (50 ml) and methanol (10 ml), and the mixture was cooled to 0°C. The reaction mixture was stirred at room temperature for 3 hours, quenched with 1.5 N HCl, and extracted by DCM. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain intermediate 2-3 (4 g, 66% yield).

[0124] 1 2 .51(t, J=8.00Hz, 2H), 2.72(t, J=8.00Hz, 2H), 4.78(s, 2H), 7.04(s, 1H), 7.29(d, J=8.00Hz, 2H), 7.43(d, J=8.40Hz, 2H), 7.46(s, 1H). LCMS purity: 95.4%.

[0125] [ka]

[0126] To a solution of intermediate 2-3 (6.2 g, 14.3 mmol) in 1,4-dioxane (60 ml), potassium acetate (3.50 g, 35.7 mmol) and B2Pin2 (4.34 g, 17.2 mmol) were added. The reaction mixture was purged with nitrogen for 15 minutes, then PdCl2 (dppf) (350 mg, 429 μmol, 3 mol%) was added, and the reaction mixture was refluxed at 100°C for 16 hours. Subsequently, it was diluted with ethyl acetate, passed through a Celite plug, and concentrated under vacuum. The crude product was purified by column chromatography (SiO2 230-400 mesh) using 30% ethyl acetate in hexane as the eluent to obtain intermediate 2-4 (5 g, yield 74%) as a white solid.

[0127] 1H-NMR (400MHz, CDCl3): δ[ppm]0.84(t, J=7.20Hz, 3H), 0.90(t, J=6.80Hz, 3H), 1.17~1.27(m, 6H), 1.29~1.35(m, 8H), 1.38(s, 12 H), 1.40~1.48(m, 4H), 1.55~1.56(m, 2H), 4.78(s, 2H), 7.02(s, 1H), 7.32(d, J=8.00Hz, 2H), 7.42(d, J=8.00Hz, 2H), 7.69(s, 1H).

[0128] [ka]

[0129] Potassium carbonate (211 mg, 1.53 mmol) in water (1.2 ml) was added to the solutions of intermediates 2-4 (439 mg, 0.92 mmol) and 3-22 (0.6 g, 0.61 mmol) in THF (12 ml). The reaction mixture was purged with N2 for 15 minutes. Tetrakis(triphenylphosphine)palladium(0) (21 mg, 3 mol%) was added, and the reaction mixture was heated at 90°C for 3 hours. A further amount of potassium carbonate (0.1 equivalent) was added, and after continuing the N2 purging for another 5 minutes, tetrakis(triphenylphosphine)palladium(0) (21 mg, 3 mol%) was added. After stirring at 90°C for 45 hours, the reaction mixture was cooled, diluted with water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and analyzed by reverse-phase column chromatography (GRACE RP, C) using 50% THF in acetonitrile as the eluent. 18 The crude product was purified by column chromatography, and then recrystallized in a mixture of ethyl acetate in hexane to obtain intermediate 2-5 (0.65 g, yield 86%) as a white solid.

[0130] 1H-NMR (400MHz, CDCl3): δ[ppm]0.83~0.88(m, 24H), 1.22~1.22(m, 50H), 1.46~1.52(m, 14H), 1.65~1.70(m, 2H), 2.33~2.47(m, 12H), 2.60~2 .65(m, 2H), 2.76~2.80(m, 2H), 4.81(s, 2H), 5.94(s, 1H), 6.41(d, J=7.20Hz, 2H), 7.16~7.20(m, 11H), 7.39(s, 1H), 7.45(q, J=8.40Hz, 4H). HPLC: Purity 88.4%.

[0131] [ka]

[0132] To a solution of intermediate 2.5 (0.9 g, 0.72 mmol) in THF (20 mL), 5N HCl (10 mL) was slowly added. The reaction mixture was refluxed at 75°C for 16 hours, cooled and filtered, and the resulting solid was washed with acetonitrile to obtain intermediate 2.6 (0.73 g, yield 90%) as a white solid. LCMS: Purity 84.3% (Note: Mass measured as acetate adduct ion).

[0133] [ka]

[0134] To the N2-purged solutions of intermediates 1-2 (10 g, 27.1 mmol) and 1-4 (9.11 g, 18.5 mmol) in a mixture of toluene (180 mL) and ethanol (60 mL), a solution of Na2CO3 (5.74 g, 54.2 mmol) in water (15 mL) was added. After purging again with N2 for 15 minutes, tetrakis(triphenylphosphine)palladium(0) (3.1 g, 10 mol%) was added, and the reaction mixture was refluxed and stirred at 90°C for 16 hours. Subsequently, the reaction mixture was diluted with water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Reverse-phase column chromatography (GRACE RP, C) was performed using acetonitrile:THF as the eluent. 18The crude product was purified using column chromatography to obtain intermediates 3-11 (F1: 2.5 g), 3-12 (F2: 1.6 g), and 3-12 (F3: 1.1 g).

[0135] [ka]

[0136] Potassium carbonate (730 mg, 0.53 mmol) was added to solutions of intermediates 1-3 (143 mg, 0.32 mmol) and 2-6 (0.3 g, 0.27 mmol) in a mixture of toluene (5 mL), ethanol (2 mL), and water (2 mL). The reaction mixture was purged with N2 for 10 minutes, and tetrakis(triphenylphosphine)palladium (0) (9.18 mg, 7.95 μmol, 3 mol%) was added. The mixture was refluxed at 90°C for 4 days. The reaction mixture was cooled, filtered through a fluorosyl plug, diluted with water, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and analyzed by reverse-phase column chromatography (GRACE RP, C) using 58% THF:acetonitrile as the eluent. 18 The crude product was purified by column chromatography to obtain intermediate 4-1 (310 mg, 83% yield) as an off-white solid. LC-MS: Purity 95.2% (Note: Mass measured as acetate adduct ion).

[0137] [ka]

[0138] A solution of sodium carbonate (33.8 mg, 0.32 mmol) in water (0.1 mL) was added to solutions of intermediates 4-1 (225 mg, 0.16 mmol) and 1-8 (214 mg, 0.16 mmol) in a mixture of THF (5 mL) and ethanol (1 mL). The reaction mixture was purged with N2 for 15 minutes, tetrakis(triphenylphosphine)palladium (0) (18.4 mg, 0.016 mmol, 10 mol%) was added, and the mixture was refluxed at 90°C for 24 hours. The cooled reaction mixture was diluted with water and stirred for 10 minutes. The resulting solid was filtered, pulverized in a mixture of DCM and hexane (1:1), and then pulverized with acetonitrile to obtain intermediate 4-2 (0.2 g, yield 48%). LCMS: Purity 80.0%.

[0139] [ka]

[0140] Manganese dioxide (165 mg, 1.90 mmol) was added to a solution of intermediate 4-2 (0.5 g, 0.19 mmol) in chloroform (30 mL). The reaction mixture was heated at 65°C for 16 hours, then filtered while hot, and the filtrate was concentrated under reduced pressure. The crude product was recrystallized from acetonitrile to obtain oligomer A1 (330 mg, yield 66%) as a white solid.

[0141] 1 H-NMR (400MHz, CDCl3): δ[ppm]0.85~0.86(m, 60H), 1.03~1.12(m, 120H), 7.02~7.21(m, 20H), 7.3 8~7.40(m, 1H), 7.42~7.54(m, 4H), 7.61(d, J=8.00Hz, 2H), 7.99(d, J=8.40Hz, 2H), 10.12(s, 1H). LCMS: Purity 93.1%.

[0142] TIFF2026514745000046.tif72158

[0143] Polymer Examples 1 and 2 were prepared from rod oligomer A1 and polymer coils B1 and B2, respectively, according to the following reaction scheme. [ka]

[0144] Polymer Example 1 A 2 mL glass vial with a septum screw cap or an ACE pressure-resistant tube (4 mL) filled with oligomer A1 (20 mg, 1.0 eqv.), polymer coil B1 (156 mg, 1.0 eqv.), m-cresol (5 mL), and toluene (1 mL) was sealed under N2, and the reaction mixture was stirred at 90-95°C for 24 hours. After cooling to room temperature, the reaction mixture was poured into n-heptane, the precipitate was filtered, washed with methanol, and dried under vacuum to obtain Polymer Example 1 (yield 91%) as a colorless solid powder.

[0145] The melting point of the material is 140-152°C, and the material is around 110°C. g This indicates that crystallization was not observed in the DSC experiment.

[0146] Polymer Example 2 A 2 mL glass vial with a septum screw cap or an ACE pressure-resistant tube (4 mL) filled with oligomer A1 (2 mg, 1.0 eqv.), polymer coil B2 (228 mg, 1.0 eqv.), m-cresol (5 μL), and toluene (1 mL) was sealed under N2, and the reaction mixture was stirred at 90-95°C for 24 hours. After cooling to room temperature, the reaction mixture was poured into n-heptane, the precipitate was filtered, washed with methanol, and dried under vacuum to obtain Polymer Example 2 (yield 73%) as a colorless powder.

[0147] Polymer Example 3 [ka]

[0148] A 2 mL glass vial with a septum screw cap or an ACE pressure-resistant tube (4 mL) filled with oligomer A1 (20 mg, 1.0 eqv.), polymer coil B3 (175 mg, 1.0 eqv.), m-cresol (5 mL), and toluene (1 mL) was sealed under N2, and the reaction mixture was stirred at 90-95°C for 48 hours. After cooling to room temperature, the reaction mixture was poured into n-heptane, the precipitate was filtered, washed with methanol, and dried under vacuum to obtain Polymer Example 3 (yield 91%) as a colorless powder.

[0149] The melting point of the material is 140-152°C, and the material is around 110°C. g This indicates that crystallization was not observed in the DSC experiment.

[0150] self-organization A solution of rod-coil polymer (less than 2 wt.% in toluene) was cast onto a silicon wafer by spin coating to produce films less than 100 nm thick. The films were thermally annealed under vacuum conditions at a temperature well above the glass transition temperature of the block copolymer (>180°C) for at least 2 hours. The polymer properties and annealing conditions are shown in Table 1.

[0151] [Table 1]

[0152] After cooling, the phase separation structure was observed using AFM imaging.

[0153] Referring to Figures 3 and 4, AFM images confirmed the presence of lamellar structures with characteristic dimensions of 6–10 nm within the film.

Claims

1. A method for forming a self-assembled film on a surface, comprising depositing a solution containing a block copolymer and a solvent onto the surface, and evaporating the solvent, wherein the block copolymer is a rod-coil copolymer containing a rod block A and a coil block B.

2. The method according to claim 1, wherein the rod block A has a conjugated skeleton.

3. The aforementioned rod block A is made of vinylene, acetylene, imine, Ar １ , and units selected from combinations thereof, each of which may be unsubstituted or substituted with one or more substituents, Ar １ The method according to claim 1 or 2, wherein the group is an arylene group or a heteroarylene group.

4. The aforementioned rod block A is given by formula (I): 【Chemistry 1】 It has, In the formula, Ar １ The method according to claim 3, wherein n is a monocyclic group, a fused aromatic group, or a heteroaromatic group, and n is greater than 1.

5. Ar １ The method according to claim 3 or 4, wherein is an unsubstituted or substituted phenylene.

6. The method according to any one of the prior claims, wherein the coil block has a skeleton that does not contain conjugated double or triple bonds.

7. The method according to claim 6, wherein the coil block skeleton does not contain double or triple bonds.

8. The coil block B is given by equations (II) to (VII): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 Selected from, In the formula, R １ The method according to claim 1 or 2, wherein in each occurrence, is independently H or a substituent, and m is greater than 1.

9. The method according to any one of the prior claims, wherein the block copolymer includes a connecting unit for connecting the rod block A to the coil block B.

10. The aforementioned connecting unit is given by the formula -N = CR ９ It is the imine unit of -, and in the formula, R ９ The method according to claim 9, wherein is H or a substituent.

11. The method according to claim 9, wherein the linking unit is a monocyclic or polycyclic group that has been optionally substituted.

12. The method according to any one of the prior claims, wherein the block copolymer is selected from A-B block copolymer, A-B-A block copolymer, and B-A-B block copolymer.

13. The method according to any one of the prior claims, wherein the block copolymer comprises a fused aromatic terminal group or a heteroaromatic terminal group comprising at least four fused aromatic rings or heteroaromatic rings.

14. The method according to any one of the prior claims, wherein the surface comprises at least one feature portion for inducing the self-assembly of the block copolymer.

15. The method according to claim 14, wherein the at least one feature portion for inducing self-assembly defines one or more regions of the substrate having a surface energy different from that of the rest of the substrate.

16. The method according to any one of the prior claims, wherein the deposited block copolymer is heated to a temperature exceeding the glass transition temperature of the block copolymer.

17. A method for patterning a substrate, comprising: providing an inductively self-assembled rod-coil copolymer, comprising a rod block A and a coil block B, on the surface of the substrate; selectively removing one of the rod block A and the coil block B; and patterning the substrate.

18. The method according to claim 17, wherein the substrate is a silicon substrate.

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