Method for preparing and applying a class of silicon-containing fast patterning block copolymer

Abstract

The present application relates to the technical field of polymer materials, and particularly relates to a silicon-containing rapid patterning block copolymer with highly controllable assembly size and assembly morphology and small PDI, a preparation method of the silicon-containing rapid patterning block copolymer and application of the silicon-containing rapid patterning block copolymer as a composite patterning material. The present application designs and synthesizes a kind of silicon-containing DSA rapid patterning block copolymer with ultrahigh resolution, high etching contrast and capable of being rapidly self-assembled at low temperature. The silicon-containing rapid patterning block copolymer can form stable ultrahigh nanostructure by only 1 min annealing at 80 DEG C, and due to the presence of the silicon-containing component, the silicon-containing rapid patterning block copolymer also has high etching selectivity.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a silicon-containing rapid patterning block copolymer with highly controllable assembly size and morphology and low PDI, as well as a method for preparing the silicon-containing rapid patterning block copolymer and its application as a composite patterning material. Background Technology

[0002] Integrated circuits (ICs) are one of the most critical technologies of the information age. From daily life to industrial production, all devices involving electronic computing rely on chips. It is precisely because of the ever-increasing power of chips that personal computers have been able to integrate increasingly powerful functions, and mobile phones have entered the 3G and 4G era. In the manufacturing of integrated circuits, photolithography is a crucial and indispensable technology. The continuous improvement of chip functionality is inseparable from the development of photolithography materials and processes.

[0003] Photolithography is the process of transferring a pre-defined pattern from a mask onto a substrate using a photochemical reaction. In photolithography, photoresist is the most critical material. Incident light passes through the mask, projecting the pattern onto the photoresist coated on the substrate, stimulating a photochemical reaction. After baking and development, the photoresist pattern is formed. This pattern then acts as a barrier layer, selectively blocking subsequent etching or ion implantation.

[0004] Starting with the 22 / 20nm nodes, technology nodes and half-pitch (HP) no longer correspond one-to-one. Due to the introduction of FinFETs, although the reduction in HP is relatively slow, the number of transistors can still grow rapidly because of the three-dimensional structure of the transistors. Therefore, the 7nm and 5nm technology chips currently marketed by chip manufacturers do not necessarily mean that they were fabricated using photolithography to create line patterns at 7nm or even 5nm dimensions. Currently, 0.33NA EUV lithography can achieve mass production of 13nm HP chips (High Volume Manufacturing, HVM), but lithography technology for HP below 10nm is still under research.

[0005] Besides extreme ultraviolet (EUV) lithography, the International Technology Roadmap for Semiconductor (ITRS) has mentioned that next-generation lithography technologies include electron-beam lithography (EBL), nanoimprint lithography (NIL), and directed self-assembly (DSA). While EBL achieves high resolution, it suffers from high production costs and low throughput. Nanoimprint lithography, although less expensive, is plagued by template defects, contact contamination, and other process issues, resulting in less than satisfactory pattern quality. Therefore, among these alternative technologies, directed self-assembly and EUV are more favored by industry and academia.

[0006] The main steps of guided self-assembly involve filling a template prepared using mature photolithography technology with DSA material exhibiting microphase separation properties. After thermal annealing or solvent annealing, the DSA material undergoes microphase separation. The resulting structure, guided by the template, exhibits a specific orientation. Subsequently, selective etching removes one phase, followed by further etching, transferring the microphase-separated pattern to the underlying substrate. This results in a denser, smaller pattern within the template, achieving a density multiplication of the pre-designed pattern and improving the resolution achievable by the process. Furthermore, besides achieving density multiplication of line / space patterns, DSA technology can also multiply the density of other structures such as contact holes.

[0007] Block copolymer systems used in guided self-assembly technology require phase separation to form ordered structures with ultra-high resolution, while also possessing high etch resistance to meet the requirements of subsequent pattern transfer. Although various block copolymer systems have been developed that can form nanopatterns with ultra-high resolution (3-10 nm), and some organic-inorganic block copolymer systems possess high etch resistance, most block copolymer systems require prolonged thermal annealing (>10 hours) or high-temperature annealing (>160°C) to reach microphase separation equilibrium. Modern semiconductor manufacturing processes require thermal annealing to be completed within minutes; excessively long annealing times or excessively high annealing temperatures will hinder the progress of the entire process. Summary of the Invention

[0008] This invention addresses the problem that while existing partial block copolymers used in photoresists can form nanopatterns with ultra-high resolution (3-10 nm) and some organic-inorganic block copolymer systems have high etching contrast, most block copolymer systems require long-term or high-temperature thermal annealing to achieve microphase separation equilibrium. This invention provides a silicon-containing rapid patterning block copolymer with ultra-high resolution, high etching contrast, and rapid self-assembly at low temperatures, as well as a method for preparing this silicon-containing rapid patterning block copolymer and its application as a composite patterning material.

[0009] To achieve the above objectives, the present invention adopts the following technical solution.

[0010] In a first aspect, a silicon-containing rapid patterning block copolymer comprises block A and block B;

[0011] The block A contains a single structural unit MA1 and / or MA2;

[0012] The block B contains a single structural unit MB1, or the block B contains single structural units MB1 as well as MB2 and / or MB3;

[0013] The structure of MA1: The structure of MA2:

[0014] The structure of MB1: The structure of MB2:

[0015] The structure of MB3:

[0016] Further, R1 in MA1 and MA2 is selected from: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C1-C20 siloxane, substituted or unsubstituted C1-C20 germanyl, substituted or unsubstituted C1-C20 germanoxane, substituted or unsubstituted C1-C20 tinyl, substituted or unsubstituted C1-C20 tinoxane;

[0017] Wherein, the substitution mentioned in R1 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl.

[0018] Furthermore, the number of R1s in MA1 and MA2 is 1, 2, 3, 4, or 5.

[0019] Furthermore, R2 in MB1 is selected from: unsubstituted or halogenated C1-C10 straight-chain alkyl, unsubstituted or halogenated C1-C10 branched alkyl, and unsubstituted or halogenated C6-C20 cyclic alkyl.

[0020] Furthermore, R3 in MB1 is selected from: H, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl;

[0021] Wherein, the substitution mentioned in R3 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl.

[0022] Further, R4 in MB2 is selected from: H, substituted or unsubstituted silyl groups containing 1-5 Si, substituted or unsubstituted germanyl groups containing 1-5 Ge, substituted or unsubstituted tinyl groups containing 1-5 Sn, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted alkyloxy groups, substituted or unsubstituted ester groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, substituted or unsubstituted heteroaryl groups containing 1-3 N, O, S selected from C6-C10, hydroxyl groups, and halogens;

[0023] Wherein, the substitution mentioned in R4 refers to substitution by one or more of the following substituents: C1-C6 alkyl, silyl containing 1-5 Si, C1-C6 alkoxy-substituted silyl containing 1-5 Si, silyloxy containing 1-5 Si, silyloxy containing 1-5 Si, C1-C6 alkoxy, and hydroxyl.

[0024] Furthermore, the block B contains structural units that can be post-modified:

[0025] The post-modification is performed using amine compounds selected from the following structures:

[0026] The R5 is selected from: substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 alkoxy, substituted or unsubstituted C3-C18 cycloalkoxy, substituted or unsubstituted 3-18 membered heterocyclic group containing 1-9 heteroatoms selected from N, O, P and S, substituted or unsubstituted straight-chain or branched C1-C18 alkyl containing 1-9 heteroatoms selected from N, O, P, Si and S, and substituted or unsubstituted C3-C20 alkyl containing 1-3 metal atoms;

[0027] Wherein, the substitution mentioned in R5 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl.

[0028] The metal atoms are selected from: Fe, Ti, Hf, V, Zr, Ge, Sn.

[0029] Furthermore, the structure of the silicon-containing rapid patterning block copolymer described above is an AB biblock structure composed of block A and block B.

[0030] Furthermore, the silicon-containing rapid patterning block copolymer described above has at least one of the following characteristics:

[0031] 1) The polydispersity index (PDI) of the silicon-containing rapid patterning block copolymer is ≤1.20;

[0032] 2) The number average molecular weight of the silicon-containing rapid patterning block copolymer is 1,000-200,000;

[0033] 3) The annealing temperature required for phase separation and self-assembly of the silicon-containing rapid patterned block copolymer is ≤200℃;

[0034] 4) The annealing time required for phase separation and self-assembly of the silicon-containing rapid patterned block copolymer is ≤12h;

[0035] 5) The assembly spacing of the product obtained by the self-assembly of the silicon-containing rapid patterned block copolymer is ≤50nm.

[0036] In a second aspect of the present invention, the method for preparing the silicon-containing rapid patterning block copolymer described above includes the following steps: mixing block A and block B together to carry out a polymerization reaction to obtain the silicon-containing rapid patterning block copolymer.

[0037] In a third aspect, the above-described silicon-containing rapid patterning block copolymer is used in the preparation of photoresists.

[0038] A fourth aspect of the present invention is a composite patterning material comprising a solvent and the silicon-containing rapid patterning block copolymer described above.

[0039] In a fifth aspect of the present invention, the application of the composite patterning material described above includes the following steps:

[0040] 1) The composite patterned material is coated onto a substrate to form a film;

[0041] 2) Bake the formed material film;

[0042] 3) The baked material film is subjected to plasma etching to obtain the pattern.

[0043] Compared with the prior art, the main advantages of the present invention are:

[0044] (1) The assembly size and morphology of the silicon-containing rapid patterned block copolymer are highly controllable, and the specific assembly results vary depending on the different modified molecules introduced.

[0045] (2) The silicon-containing rapid patterning block copolymer can obtain a microphase size of 1 nm after post-modification and thermal annealing;

[0046] (3) The silicon-containing rapid patterning block copolymer has the property of forming regular nanostructures by rapid thermal annealing at low temperature;

[0047] (4) The preparation method of the silicon-containing rapid patterning block copolymer is simple, safe and low cost. The silicon-containing rapid patterning block copolymer with multiple unit structures and small PDI can be obtained by post-modification.

[0048] (5) The two blocks of the silicon-containing rapid patterning block copolymer have large differences in etching resistance, and the overall etching contrast of the silicon-containing rapid patterning block copolymer is high.

[0049] This invention designs and synthesizes a class of silicon-containing DSA rapid patterning block copolymers that simultaneously possess ultra-high resolution, high etching contrast, and rapid self-assembly at low temperatures. The silicon-containing rapid patterning block copolymers can not only form stable ultra-high nanostructures by annealing at 80°C for only 1 minute, but also exhibit high etching selectivity due to the presence of silicon components. Attached Figure Description

[0050] Figure 1 The image shows the molecular weight distribution of the PHFBMA macromolecular chain transfer agent corresponding to the silicon-containing rapid patterning block copolymer S1 prepared in Example 2 and the overall molecular weight distribution.

[0051] Figure 2 SAXS diagram of the self-assembled product of silicon-containing rapid patterned block copolymers S1-S5 after thermal annealing at 160°C for 1 hour.

[0052] Figure 3 SAXS diagram of the self-assembled products of silicon-containing rapid patterned block copolymer S5 after thermal annealing at different temperatures and times;

[0053] Figure 4 This is a schematic diagram of hot assembly annealing;

[0054] Figure 5 SEM image of silicon-containing rapid patterning block copolymer S1;

[0055] Figure 6 SAXS diagram of the self-assembled product of silicon-containing rapid patterned block copolymers T1-T4 after thermal annealing at 160°C for 1 hour;

[0056] Figure 7 SAXS diagrams of the self-assembled products of silicon-containing rapid patterned block copolymer T1 after thermal annealing at different temperatures and times;

[0057] Figure 8 SEM image of silicon-containing rapid patterning block copolymer T1;

[0058] Figure 9 The 19F NMR spectra of Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterned block copolymer and the silicon-containing rapid patterned block copolymer obtained after post-modification are shown.

[0059] Figure 10 SEM image of Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer;

[0060] Figure 11 SEM image of Poly(NBMAA-co-StNPOSS)-b-PHFBMA, a silicon-containing rapid patterning block copolymer. Detailed Implementation

[0061] To better understand the technical content of the present invention, the technical solution of the present invention will be further introduced and explained below in conjunction with specific embodiments.

[0062] Example 1

[0063] Synthesis of styrene derivative monomers containing POSS side chains

[0064]

[0065] Heptaisobutylaminopropyl POSS (NH2-POSS, 9.59 g, 10 mmol) was dissolved in dichloromethane (DCM, 50 mL), followed by the addition of 1-hydroxybenzotriazole (HOBT, 1.86 g, 10 mmol), 4-vinylbenzoic acid (1.48 g, 10 mmol), N,N-diisopropylethylamine (3.10 g, 20 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.86 g, 10 mmol). The reaction mixture was allowed to react at room temperature for 10 h. Afterward, dichloromethane (50 mL) was added for appropriate dilution, and the mixture was washed three times with distilled water (3 × 100 mL). Following washing, an appropriate amount of anhydrous magnesium sulfate was added to the organic phase to remove water, and the mixture was allowed to stand for 2–3 h. The mixture was filtered, and the solvent was removed by rotary evaporation to obtain 6.40 g of a white solid product (StNPOSS), with a yield of 64%.

[0066] Example 2

[0067] PStNPOSS-b-PHFBMA Silicon-Containing Rapidly Patterned Block Copolymer and Its Preparation Method

[0068]

[0069] In a dry 100 mL polymerization tube, 1H,1H-perfluorobutyl methacrylate (HFBMA, 9.17 g, 34.20 mmol), cyanoisopropyl dithiobenzoate (CPDB, 378.8 mg, 1.71 mmol), azobisisobutyronitrile (AIBN, 14 mg, 0.086 mmol), and hexafluoroisopropanol (HFIP, 25 mL) were added. The reaction system was subjected to three freeze-thaw cycles to remove oxygen. The polymerization tube was then sealed in a 70 °C oil bath and reacted for 8 h. After the reaction, the polymerization tube was rapidly quenched in liquid nitrogen, and then diluted with an appropriate amount of HFIP. The diluted solution was added dropwise to a large amount of n-hexane, the precipitate was filtered, and this process was repeated three times. The resulting product was dried under vacuum at room temperature for 24 h to obtain 4.40 g of a pink powder. The obtained product is PHFBMA, a macromolecular chain transfer agent.

[0070] In a dry 10 mL polymerization tube, PHFBMA (240 mg, 0.05 mmol), StNPOSS (250 mg, 0.25 mmol), AIBN (0.82 mg, 0.005 mmol), and cyclohexanone (2 mL) were added. The reaction system was subjected to three freeze-thaw cycles to remove oxygen. The polymerization tube was then sealed in a 65°C oil bath and reacted for 16 h. After the reaction, the polymerization tube was rapidly quenched in liquid nitrogen, and then diluted with an appropriate amount of THF. The diluted solution was added dropwise to a large amount of n-hexane, the precipitate was filtered, and this process was repeated three times. The resulting product was vacuum dried at room temperature for 24 h to obtain 200 mg of a pink solid powder product (silicone-containing rapid patterning block copolymer S1). The obtained product (silicone-containing rapid patterning block copolymer S1) is the PStNPOSS-b-PHFBMA silicon-containing rapid patterning block copolymer. The number-average molecular weight of silicon-containing rapid patterning block copolymer S1, measured by GPC, was 28314, and the weight-average molecular weight was 30862. The molecular weight distribution of the corresponding PHFBMA macromolecular chain transfer agent and the overall molecular weight of silicon-containing rapid patterning block copolymer S1 is as follows: Figure 1 As shown.

[0071] Following the preparation method of silicon-containing rapid patterning block copolymer S1, by changing the type of macromolecular chain transfer agent PHFBMA and the feed ratio of PHFBMA to StNPOSS, silicon-containing rapid patterning block copolymers with different segment lengths and segment ratios can be obtained, namely PStNPOSS-b-PHFBMA. In silicon-containing rapid patterning block copolymers S1-S5, different feed ratios of the two monomers (PHFBMA and StNPOSS) were used. The number-average molecular weight and molecular weight distribution of silicon-containing rapid patterning block copolymers S1-S5 are shown in Table 1.

[0072] Table 1. Number-average molecular weight and molecular weight distribution of silicon-containing rapid patterning block copolymers S1-S5

[0073]

[0074]

[0075] Silicon-containing rapid patterning block copolymers S1-S5 were subjected to thermal annealing treatment respectively. Figure 2 SAXS diagrams of the self-assembled products of silicon-containing rapidly patterned block copolymers S1-S5 after thermal annealing at 160°C for 1 hour are shown. Among them, S4 achieved a full-pitch self-assembly of 11.6 nm, and its assembled structure is a layered phase.

[0076] Thermal annealing tests were conducted on silicon-containing rapid patterning block copolymer S5 at different temperatures and times. Figure 3SAXS diagrams of the self-assembled products of silicon-containing rapid patterned block copolymer S5 after thermal annealing at different temperatures and times. Stable nanostructures can be formed after 1 min of thermal annealing at 80℃.

[0077] Example 3

[0078] Self-assembly performance test of silicon-containing rapid patterning block copolymer S1.

[0079] Figure 4 This is a schematic diagram of thermal assembly annealing. (Example) Figure 4 As shown, the obtained silicon-containing rapid patterning block copolymer S1 was dissolved in toluene to prepare a 0.5% (w / w) solution, which was then spin-coated onto a clean silicon wafer using a spin coater (4000 rpm / min, 1 min). The wafer was then dried in a vacuum oven for 2 h to remove the solvent. The silicon wafer was baked at 120°C on a hot plate, rapidly annealed, and then quenched with a cold plate. The resulting sample was further measured using SEM (scanning electron microscopy). The SEM measurement results are shown below. Figure 5 As shown, the scale bar is 100 nm.

[0080] Example 4

[0081] Poly(St-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer and its preparation method.

[0082]

[0083] In a dry 10 mL polymerization tube, PHFBMA (240 mg, 0.05 mmol), styrene (104 mg, 1 mmol), StNPOSS (250 mg, 0.25 mmol), AIBN (0.82 mg, 0.005 mmol), and ultra-dry tetrahydrofuran (2 mL) were added. The reaction system was subjected to three freeze-thaw cycles to remove oxygen. The polymerization tube was then sealed in a 65°C oil bath and reacted for 16 h. After the reaction, the polymerization tube was rapidly quenched in liquid nitrogen, and then diluted with an appropriate amount of THF. The diluted solution was added dropwise to a large amount of n-hexane, the precipitate was filtered, and this process was repeated three times. The resulting product was vacuum dried at room temperature for 24 h to obtain 314 mg of a pink solid powder product (silicone-containing rapid patterning block copolymer T1). The obtained product (silicone-containing rapid patterning block copolymer T1) is Poly(St-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer.

[0084] Referring to the preparation method of silicon-containing rapid patterning block copolymer T1, by changing the type of macromolecular chain transfer agent PHFBMA used and the feed ratio of PHFBMA, styrene and StNPOSS, Poly(St-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymers with different segment lengths, different segment ratios and different monoblock silicon contents can be obtained.

[0085] In the silicon-containing rapid patterning block copolymers T1-T4, PHFBMA, styrene, and StNPOSS were used in different feed ratios. The number-average molecular weight and molecular weight distribution of the silicon-containing rapid patterning block copolymers T1-T4 are shown in Table 2.

[0086] Table 2. Number-average molecular weight and molecular weight distribution of silicon-containing rapid patterning block copolymers T1-T4

[0087]

[0088] Silicon-containing rapid patterning block copolymers T1-T4 were subjected to thermal annealing treatment respectively. Figure 6 SAXS diagrams of the self-assembled products of silicon-containing rapidly patterned block copolymers T1-T4 after thermal annealing at 160°C for 1 hour are shown. Among them, T1 achieved a full-pitch self-assembly of 12.8 nm, and its assembled structure is a layered phase.

[0089] Thermal annealing tests were conducted on silicon-containing rapid patterning block copolymer T1 at different temperatures and times. Figure 7 SAXS diagrams of the self-assembled products of silicon-containing rapid patterned block copolymer T1 after thermal annealing at different temperatures and times. Stable nanostructures can be formed after 1 min of thermal annealing at 80°C.

[0090] Example 5

[0091] Self-assembly performance test of silicon-containing rapid patterning block copolymer T1

[0092] like Figure 4 As shown, the obtained silicon-containing rapid patterning block copolymer T1 was dissolved in chloroform to prepare a 0.5% (w / w) solution, which was then spin-coated onto a clean silicon wafer using a spin coater (4000 rpm / min, 1 min). The wafer was then dried in a vacuum oven for 2 h to remove the solvent. The silicon wafer was baked at 120°C on a hot plate, rapidly annealed, and then quenched with a cold plate. The resulting samples were further measured using SEM (scanning electron microscopy). The SEM measurement results are shown below. Figure 8 As shown, the scale bar is 100 nm.

[0093] Example 6

[0094] Preparation and Post-Modification Methods of Poly(PFPMA-co-StNPOSS)-b-PHFBMA Silicon-Containing Rapidly Patterned Block Copolymer

[0095] The preparation steps of the Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer are as follows:

[0096]

[0097] In a dry 25 mL polymerization tube, PHFBMA (480 mg, 0.1 mmol), PFPMA (418 mg, 1.66 mmol), StNPOSS (600 mg, 0.6 mmol), AIBN (1.6 mg, 0.01 mmol), and ultra-dry tetrahydrofuran (4 mL) were added. The reaction system was subjected to three freeze-thaw cycles to remove oxygen. The polymerization tube was then sealed in a 65°C oil bath and reacted for 16 h. After the reaction, the polymerization tube was rapidly quenched in liquid nitrogen, and then diluted with an appropriate amount of THF. The diluted solution was added dropwise to a large amount of n-hexane, the precipitate was filtered, and this process was repeated three times. The resulting product was vacuum dried at room temperature for 24 h to obtain 834 mg of a pink solid powder. The obtained product is Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterned block copolymer.

[0098] By adjusting the type of macromolecular chain transfer agent PHFBMA used, and the feed ratio of PHFBMA, PFPMA, and PStNPOSS, poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymers with different segment lengths, different segment ratios, and different monoblock silicon contents can be obtained.

[0099] The post-modification steps for the Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer are as follows:

[0100]

[0101] Taking the post-modification of Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterned block copolymer with benzylamine as an example, Poly(PFPMA-co-StNPOSS)-b-PHFBMA (226 mg, 0.02 mmol) was added to a dry 10 mL polymerization tube. The tube was evacuated three times, and then ultra-dry THF (2 mL) was added under a nitrogen atmosphere. After the solid material was completely dissolved, benzylamine (43 mg, 0.4 mmol) and triethylamine (Et3N, 41 mg, 0.4 mmol) were added sequentially under stirring at room temperature. The polymerization tube was sealed in an oil bath at room temperature and reacted for 10 h. After the reaction was completed, the polymerization tube was quickly placed in liquid nitrogen for quenching. The thawed solution was added dropwise to a large amount of n-hexane, and the precipitate was filtered. This process was repeated three times. The obtained product was vacuum dried at room temperature for 24 h to obtain 154 mg of a pale yellow solid powder. The resulting product is Poly(NBMAA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer.

[0102] By changing the type of small molecule amine and the corresponding alkaline catalyst (triethylamine, DIEA), silicon-containing fast patterned block copolymers containing StNPOSS components modified with different functional groups can be obtained.

[0103] Small molecule amines used for post-modification can be selected from amine compounds with the following structures: R5 is selected from: substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 alkoxy, substituted or unsubstituted C3-C18 cycloalkoxy, substituted or unsubstituted 3-18 membered heterocyclic groups containing 1-9 heteroatoms selected from N, O, P and S, substituted or unsubstituted straight-chain or branched C1-C18 alkyl containing 1-9 heteroatoms selected from N, O, P, Si and S, and substituted or unsubstituted C3-C20 alkyl containing 1-3 metal atoms.

[0104] In R5, the substitution refers to substitution with one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, and unsubstituted or hydroxyl-substituted aryl. The metal atom is selected from: Fe, Ti, Hf, V, Zr, Ge, and Sn.

[0105] Figure 9The images show the 19F NMR spectra of the poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterned block copolymer and the silicon-containing rapid patterned block copolymer obtained after post-modification. The spectra show that the PFPMA component in the original poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterned block copolymer was completely replaced after post-modification. The resulting silicon-containing rapid patterned block copolymer is poly(NBMAA-co-StNPOSS)-b-PHFBMA.

[0106] Example 7

[0107] Self-assembly performance test of Poly(PFPMA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer

[0108] like Figure 4 As shown, the obtained silicon-containing rapid patterning block copolymer was dissolved in tetrahydrofuran to prepare a 0.5% (w / w) solution, which was then spin-coated onto a clean silicon wafer using a spin coater (3000 rpm / min, 1 min). The wafer was then dried in a vacuum oven for 2 h to remove the solvent. The silicon wafer was baked at 120°C on a hot plate, rapidly annealed, and then quenched with a cold plate. The resulting samples were further measured using SEM (scanning electron microscopy). The SEM measurement results are shown below. Figure 10 As shown, the scale bar is 100 nm.

[0109] Example 8

[0110] Self-assembly performance test of Poly(NBMAA-co-StNPOSS)-b-PHFBMA silicon-containing rapid patterning block copolymer

[0111] like Figure 4 As shown, the obtained silicon-containing rapid patterning block copolymer was dissolved in tetrahydrofuran to prepare a 0.5% (w / w) solution, which was then spin-coated onto a clean silicon wafer using a spin coater (3000 rpm / min, 1 min). The wafer was then dried in a vacuum oven for 2 h to remove the solvent. The silicon wafer was baked at 120°C on a hot plate, rapidly annealed, and then quenched with a cold plate. The resulting samples were further measured using SEM (scanning electron microscopy). The SEM measurement results are shown below. Figure 11 As shown, the scale bar is 100 nm.

[0112] The above description is merely an example to further illustrate the technical content of the present invention, so as to facilitate the reader's understanding. However, it does not mean that the implementation of the present invention is limited to this. Any technical extension or re-creation made in accordance with the present invention is protected by the present invention.

Claims

1. A silicon-containing rapid patterning block copolymer, characterized in that: The silicon-containing rapid patterning block copolymer comprises block A and block B; The block A contains a single structural unit MA1 and / or MA2; The block B contains a single structural unit MB1, or the block B contains single structural units MB1 as well as MB2 and / or MB3; The structure of MA1: The structure of MA2: The structure of MB1: The structure of MB2: The structure of MB3: R1 in MA1 and MA2 is selected from: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C1-C20 siloxane, substituted or unsubstituted C1-C20 germanyl, substituted or unsubstituted C1-C20 germanoxane, substituted or unsubstituted C1-C20 tinyl, substituted or unsubstituted C1-C20 tinoxane; wherein, the substitution in R1 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl; R2 in MB1 is selected from: unsubstituted or halogenated C1-C10 straight-chain alkyl, unsubstituted or halogenated C1-C10 branched alkyl, and unsubstituted or halogenated C6-C20 cyclic alkyl. R3 in MB1 is selected from: H, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C10 aryl; wherein, the substitution in R3 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl; R4 in MB2 is selected from: H, substituted or unsubstituted silyl groups containing 1-5 Si, substituted or unsubstituted germanyl groups containing 1-5 Ge, substituted or unsubstituted tinyl groups containing 1-5 Sn, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted alkyloxy groups, substituted or unsubstituted ester groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C10 aryl groups, substituted or unsubstituted heteroaryl groups containing 1-3 N, O, S, hydroxyl groups, and halogens; wherein, the substitution in R4 refers to substitution by one or more of the following substituents: C1-C6 alkyl groups, silyl groups containing 1-5 Si, C1-C6 alkoxy-substituted silyl groups containing 1-5 Si, silyloxy groups containing 1-5 Si, silyloxy groups containing 1-5 Si, C1-C6 alkoxy groups, and hydroxyl groups.

2. The silicon-containing rapid patterning block copolymer according to claim 1, characterized in that, Block B contains structural units that can be post-modified: The post-modification is performed using amine compounds selected from the following structures: The R5 is selected from: substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C1-C18 alkoxy, substituted or unsubstituted C3-C18 cycloalkoxy, substituted or unsubstituted 3-18 membered heterocyclic group containing 1-9 heteroatoms selected from N, O, P and S, substituted or unsubstituted straight-chain or branched C1-C18 alkyl containing 1-9 heteroatoms selected from N, O, P, Si and S, and substituted or unsubstituted C3-C20 alkyl containing 1-3 metal atoms; Wherein, the substitution mentioned in R5 refers to substitution by one or more of the following substituents: halogen, hydroxyl, trimethylsilyl, trimethylsilyloxy, triethoxysilyl, trimethylgermanyl, trimethylgermanyloxy, triethoxygermanyl, trimethyltinyl, trimethyltinyloxy, triethoxytinyl, unsubstituted or hydroxyl-substituted alkyl, unsubstituted or hydroxyl-substituted aryl. The metal atoms are selected from: Fe, Ti, Hf, V, Zr, Ge, Sn.

3. The silicon-containing rapid patterning block copolymer according to any one of claims 1-2, characterized in that, The structure of the silicon-containing rapid patterning block copolymer is an AB biblock structure composed of block A and block B.

4. The silicon-containing rapid patterning block copolymer according to any one of claims 1-2, characterized in that, The silicon-containing rapid patterning block copolymer has at least one of the following characteristics: 1) The polydispersity index (PDI) of the silicon-containing rapid patterning block copolymer is ≤1.20; 2) The number average molecular weight of the silicon-containing rapid patterning block copolymer is 1,000-200,000; 3) The annealing temperature required for phase separation and self-assembly of the silicon-containing rapid patterned block copolymer is ≤200℃; 4) The annealing time required for phase separation and self-assembly of the silicon-containing rapid patterned block copolymer is ≤12h; 5) The assembly spacing of the product obtained by the self-assembly of the silicon-containing rapid patterned block copolymer is ≤50nm.

5. A method for preparing a silicon-containing rapid patterning block copolymer as described in claim 1, characterized in that, The process includes the following steps: mixing block A and block B together and performing a polymerization reaction to obtain the silicon-containing rapid patterning block copolymer.

6. A composite patterning material, characterized in that, The composite patterning material contains a solvent and the silicon-containing rapid patterning block copolymer as described in any one of claims 1-4.

7. The application of the composite patterning material according to claim 6, characterized in that, Includes the following steps: 1) The composite patterned material is coated onto a substrate to form a film; 2) Bake the formed material film; 3) The baked material film is subjected to plasma etching to obtain the pattern.

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