A hydrogen bond-induced self-assembled lamellar homopolymer supramolecule with a characteristic size of 5 nm or less and a preparation method thereof
By inducing self-assembly of polyvinylimidazole and long alkyl chain carboxylic acids/alcohols through hydrogen bonding, layered homopolymer supramolecular structures with feature sizes below 5 nm were prepared, solving the problem of preparing extremely small-scale materials in integrated circuit manufacturing and realizing ultra-high resolution patterning and simplified processes.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUZHOU UNIV
- Filing Date
- 2026-05-07
- Publication Date
- 2026-06-23
Smart Images
Figure CN122255336A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of supramolecular self-assembly patterning, and more specifically to a layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a feature size of less than 5 nm, and a method for preparing the same. Background Technology
[0002] The self-assembly patterning technology of homopolymer materials is gradually becoming an important candidate material for next-generation integrated circuit manufacturing due to its inherent advantages such as simple synthesis, controllable feature size, and high batch stability. Compared with block copolymers (BCPs), which rely on the formation of microphase separation from chemically significantly different segments, homopolymer systems typically utilize specific non-covalent interactions (such as ionization, hydrogen bonding, crystallization, or π-π stacking) to drive the formation of ordered structures, thereby effectively avoiding the synthesis and purification steps of complex multi-block polymers. Based on these characteristics, homopolymer self-assembly shows unique technological potential in simplifying material preparation processes and improving process compatibility.
[0003] In the construction of ordered homopolymer structures, ionization (such as electrostatic interactions and ion pairing) has been widely used to induce the self-assembly of various phase structures. Typical approaches include introducing quaternary ammonium salts or sulfonate groups to form ionic layered phases. However, this approach has inherent limitations in practical applications: high charge density easily induces strong electrostatic adsorption and aggregation, leading to irreversible assembly; simultaneously, ionized homopolymers typically require counterions to maintain electroneutrality, which occupy interfacial space and increase interfacial width, making it difficult to achieve minimum feature sizes below 5 nm. In contrast, hydrogen bonding combines dynamic reversibility with fine-tuning of structures. The dissociation and recombination of hydrogen bonds can occur rapidly at room temperature or under mild hot casting conditions, which is beneficial for inducing the formation of self-assembled structures and promoting the self-repair of defects, thereby obtaining long-range ordered layered morphologies. Furthermore, hydrogen bonding does not require counterions, and the interdomain spacing can be precisely controlled by adjusting the structure of hydrogen bond donors / acceptors, providing a feasible approach to achieving higher pattern resolution. Based on the above advantages, a hydrogen bond-induced self-assembly homopolymer supramolecular structure is being developed, which is expected to break through the technical bottleneck of the ionization path in the preparation process of layered structure materials at extremely small scales, and provide a new solution for realizing ultra-high resolution patterned templates below 5 nm. Summary of the Invention
[0004] The purpose of this invention is to broaden the categories of patterned materials used in integrated circuit manufacturing and advanced photolithography processes, and to provide a layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a feature size of less than 5 nm, as well as a method for its preparation.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm is described, which consists of a polyvinylimidazolium backbone and long alkyl side chains containing hydrogen bond donors. Its structural formula is as follows:
[0006] Where the degree of polymerization n = 3-30, and the hydrogen bond donor HR is selected from one of the following structural formulas:
[0007] In long alkyl chain carboxylic acids, a = 10-22, and in long alkyl chain alcohols, b = 10-22.
[0008] The preparation method of the homopolymer supramolecular polymer specifically includes the following steps: (1) Polyvinylimidazolium (PVIm) n Free radical polymerization of vinylimidazole monomer, initiator, and solvent: The mixture is placed in a Schlenk flask, stirred under an inert atmosphere, and maintained at 60-70°C for 24-72 hours. The resulting mixture is precipitated in excess ethyl acetate to obtain a crude product. The precipitate is redissolved in ethanol and precipitated three times in ethyl acetate to remove residual unreacted monomers and impurities. The residue is dried under vacuum at 60°C to constant weight.
[0009] (2) In a round-bottom flask, the polyvinylimidazole and long alkyl chain carboxylic acid / alcohol (hydrogen bond donor) obtained in step (1) are dissolved in N,N-dimethylformamide. The mixed solution is stirred at 60-70°C for 12-24 hours. Subsequently, hydrogen bond formation is induced by hot casting and self-assembly is completed to obtain the homopolymer supramolecular PVIm. n -aCOOH or PVIm n -bOH.
[0010] Furthermore, the initiator used in step (1) is one of 2,2-azobisisobutyronitrile and benzoyl peroxide.
[0011] Furthermore, the solvent used in step (1) is one of N,N-dimethylformamide, ethanol, and methanol.
[0012] Furthermore, the molar ratio of polyvinylimidazole and long alkyl chain carboxylic acid / alcohol (hydrogen bond donor) used in step (2) is 1:1.
[0013] Furthermore, the hot casting described in step (2) involves transferring the mixture into a petri dish, placing it on a heating plate at 65°C, and heating it continuously for more than 24 hours until the solvent has completely evaporated before molding.
[0014] Furthermore, the homopolymer supramolecular structure yields layered nanopatterns with a characteristic size ≤ 5.0 nm.
[0015] Compared with the prior art, the present invention has the following advantages: (1) The homopolymer supramolecular prepared in this invention utilizes the hydrogen bonding between polyvinylimidazole and long-chain carboxylic acids / alcohols (hydrogen bond donors) to achieve a simple synthesis using a hot casting process. During the hot casting process, solvent evaporation promotes the formation of hydrogen bonds, inducing the orderly arrangement of polymer chain segments, thereby achieving efficient self-assembly of the supramolecular. This method completes the self-assembly process of the material simultaneously during the hot casting stage, eliminating the need for additional subsequent self-assembly steps and significantly lowering the barrier to entry for patterned materials.
[0016] (2) The homopolymer supramolecular prepared by the present invention can achieve precise control of the pattern feature size by adjusting the length of the long alkane side chain, thereby achieving precise controllability under ultra-high resolution.
[0017] (3) The minimum feature size of the homopolymer supramolecular prepared by the present invention can be as low as 2.64 nm, breaking through the limit of 3 nm, further breaking through the limit feature size of patterned materials, realizing ultra-high resolution patterned imaging, and providing a convenient and efficient new strategy for ultra-high resolution patterned materials used in the field of integrated circuit manufacturing. Attached Figure Description
[0018] Figure 1 The 1H NMR spectrum of the homopolymer supramolecular PVIm3-10COOH prepared in Example 1.
[0019] Figure 2 The small-angle X-ray scattering spectrum of the homopolymer supramolecular PVIm3-10COOH prepared in Example 1 is shown.
[0020] Figure 3 Transmission electron microscopy image of the homopolymer supramolecular PVIm3-10COOH prepared in Example 1.
[0021] Figure 4 The temperature-dependent small-angle X-ray scattering spectrum of the homopolymer supramolecular PVIm3-10COOH prepared in Example 1.
[0022] Figure 5 The homopolymer supramolecular PVIm prepared in Example 2 10 The 1H NMR spectrum of -16COOH.
[0023] Figure 6 The homopolymer supramolecular PVIm prepared in Example 2 10 Small-angle X-ray scattering spectrum of -16COOH.
[0024] Figure 7 The homopolymer supramolecular PVIm prepared in Example 2 10 Transmission electron microscopy image of -16COOH.
[0025] Figure 8 The homopolymer supramolecular PVIm prepared in Example 3 24 Small-angle X-ray scattering spectrum of -22OH.
[0026] Figure 9 The homopolymer supramolecular PVIm prepared in Example 3 24 Transmission electron microscopy image of -22OH. Detailed Implementation
[0027] The technical solutions of the present invention will be clearly, thoroughly, and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0028] Example 1: Preparation of homopolymer supramolecular PVIm3-10COOH (1) The monomer vinylimidazole (10.39 g, 110.4 mmol), the initiator 2,2-azobisisobutyronitrile (0.3629 g, 2.21 mmol), and the solvent 36 mL of ethanol were placed in a Schlenk flask and stirred under an inert atmosphere at 60 °C for 24 hours. The mixture after reaction was precipitated in excess ethyl acetate to obtain the crude product. The precipitate was redissolved in ethanol and precipitated three times in ethyl acetate to remove residual unreacted monomers and impurities. The residue was dried under vacuum at 60 °C to constant weight.
[0029] (2) In a round-bottom flask, dissolve the polyvinylimidazole (0.3764 g, 4 mmol) and n-decanoic acid (0.6890 g, 4 mmol) obtained in step (1) in 60 mL of N,N-dimethylformamide. Stir the mixture at 60 °C for 15 hours. Then transfer the mixture to a petri dish and place it on a heating plate at 65 °C for more than 24 hours. After the solvent has completely evaporated, the homopolymer supramolecular PVIm3-10COOH can be obtained.
[0030] (3) The homopolymer supramolecular PVIm3-10COOH was tested using small-angle X-ray scattering and transmission electron microscopy, revealing a layered self-assembled structure with a characteristic size of 2.64 nm. The dissociation and recombination of hydrogen bonds in PVIm3-10COOH under temperature changes are as follows: Figure 4 As shown, the layered structure disappears at 100℃ during the heating process, and reforms at 100℃ during the cooling process.
[0031] Example 2 Homopolymer supramolecular PVIm 10Preparation of -16COOH (1) The monomer vinylimidazole (5.19 g, 55.2 mmol), the initiator 2,2-azobisisobutyronitrile (0.0453 g, 0.28 mmol), and 20 mL of N,N-dimethylformamide solvent were placed in a Schlenk flask and stirred under an inert atmosphere at 70 °C for 48 hours. The mixture after reaction was precipitated in excess ethyl acetate to obtain a crude product. The precipitate was redissolved in ethanol and precipitated three times in ethyl acetate to remove residual unreacted monomers and impurities. The residue was dried under vacuum at 60 °C to constant weight.
[0032] (2) In a round-bottom flask, dissolve the polyvinylimidazole (0.3764 g, 4 mmol) and hexadecanoic acid (0.6890 g, 4 mmol) obtained in step (1) in 70 mL of N,N-dimethylformamide. Stir the mixture at 65 °C for 18 hours. Then transfer the mixture to a petri dish and heat it on a 65 °C hot plate for more than 24 hours. After the solvent has completely evaporated, the mixture is molded to obtain the homopolymer supramolecular PVIm. 10 -16COOH.
[0033] (3) Homopolymer supramolecular PVIm 10 -16COOH was tested using a small-angle X-ray scattering instrument and a transmission electron microscope, which revealed that its self-assembled structure is layered with a characteristic size of 3.16 nm.
[0034] Example 3 Homopolymer supramolecular PVIm 24 Preparation of -22OH (1) The monomer vinylimidazole (5.19 g, 55.2 mmol), the initiator benzoyl peroxide (0.0169 g, 0.07 mmol), and 20 mL of N,N-dimethylformamide solvent were placed in a Schlenk flask and stirred under an inert atmosphere for 72 hours at 70 °C. The mixture after reaction was precipitated in excess ethyl acetate to obtain a crude product. The precipitate was redissolved in ethanol and precipitated three times in ethyl acetate to remove residual unreacted monomers and impurities. The residue was dried under vacuum at 60 °C to constant weight.
[0035] (2) In a round-bottom flask, dissolve the polyvinylimidazole (0.3764 g, 4 mmol) and n-dodecyl alcohol (1.3064 g, 4 mmol) obtained in step (1) in 80 mL of N,N-dimethylformamide. Stir the mixture at 65 °C for 24 hours. Then transfer the mixture to a petri dish and heat it on a 65 °C hot plate for more than 24 hours. After the solvent has completely evaporated, the mixture is molded to obtain the homopolymer supramolecular PVIm. 24 -22OH.
[0036] (3) Homopolymer supramolecular PVIm 24 The self-assembled structure of -22OH was determined to be layered with a characteristic size of 3.85 nm by small-angle X-ray scattering and transmission electron microscopy.
[0037] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.
Claims
1. A layered homopolymer supramolecular structure that undergoes hydrogen bond-induced self-assembly and has a characteristic size of less than 5 nm, characterized in that: Its structural formula is: ； Where the degree of polymerization n = 3-30, and the hydrogen bond donor HR is selected from one of the following structural formulas: ； In long alkyl chain carboxylic acids, a = 10-22, and in long alkyl chain alcohols, b = 10-22.
2. The layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm as described in claim 1, characterized in that: Its preparation method specifically includes the following steps: (1) Polyvinylimidazolium (PVIm) n Free radical polymerization: The monomer vinylimidazole, initiator and solvent are put into a Schlenk flask, stirred under an inert atmosphere and kept at 60-70°C for 24-72 hours. The mixture after reaction is precipitated in excess ethyl acetate to obtain crude product. The precipitate is redissolved in ethanol and precipitated three times in ethyl acetate to remove residual unreacted monomers and impurities. The residue is dried under vacuum at 60°C to constant weight. (2) In a round-bottom flask, the polyvinylimidazole and long alkyl chain carboxylic acid or long alkyl chain alcohol obtained in step (1) are dissolved in N,N-dimethylformamide. The mixed solution is stirred at 60-70°C for 12-24 hours. Subsequently, hydrogen bonding is induced by hot casting and self-assembly is completed to obtain the homopolymer supramolecular PVIm. n -aCOOH or PVIm n -bOH.
3. The layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm as described in claim 2, characterized in that: The initiator used in step (1) is one of 2,2-azobisisobutyronitrile and benzoyl peroxide.
4. The layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm as described in claim 2, characterized in that: The solvent used in step (1) is one of N,N-dimethylformamide, ethanol, and methanol.
5. A layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm as described in claim 2, characterized in that: The molar ratio of polyvinylimidazolium and long alkyl chain carboxylic acid or long alkyl chain alcohol used in step (2) is 1:
1.
6. A layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm, as described in claim 2, characterized in that: The hot casting described in step (2) involves transferring the mixture into a petri dish, placing it on a heating plate at 65°C, and heating it continuously for more than 24 hours until the solvent has completely evaporated before molding.
7. The layered homopolymer supramolecular structure with hydrogen bond-induced self-assembly and a characteristic size of less than 5 nm as described in claim 1, characterized in that: The homopolymer supramolecular structure yields layered nanopatterns with a characteristic size ≤ 5.0 nm.