Method for rapidly forming nano pattern by using block copolymer and application thereof

Abstract

The invention discloses a method for rapidly forming a nano pattern by using a block copolymer and application thereof. The method for rapidly forming the nano-pattern by using the block copolymer comprises the following steps: dissolving the polystyrene-polymethyl methacrylate block copolymer in a mixed solvent consisting of a low-boiling-point organic solvent and a high-boiling-point organic solvent, wherein the boiling point of the low-boiling-point organic solvent is lower than 150 DEG C, and the boiling point of the high-boiling-point organic solvent is lower than 150 DEG C; the boiling point of the high-boiling-point organic solvent is higher than 150 DEG C, the high-boiling-point organic solvent is spin-coated on the surface of a substrate to form a thin film, annealing and plasma etching are carried out, and the periodic nano-pattern is obtained. According to the method for rapidly forming the nano pattern by using the segmented copolymer, the annealing time is shortened to be within 5 min, the production efficiency is remarkably improved, the formed nano pattern is high in structural orderliness and low in defect rate, and the method is suitable for the fields of semiconductor guided self-assembly photoetching, nanoimprint template manufacturing, high-density storage device preparation and the like.

Description

Technical Field

[0001] This invention relates to the field of nanofabrication technology, and more specifically to a method for rapidly forming nanopatterns using block copolymers and its applications. Background Technology

[0002] Nanofabrication is a technology for designing, controlling, and manufacturing materials and structures at the nanoscale (typically 1nm to 100nm), and it is the cornerstone of modern high-tech industries. As semiconductor devices evolve towards smaller sizes (3nm and below) and higher integration, the demand for nanopatterns with feature sizes of 10nm to 50nm, long-range order (>10μm), and a defect rate of <5% is increasingly urgent. However, traditional photolithography faces insurmountable technical and cost barriers at this scale, specifically: 193nm immersion lithography is limited by the optical diffraction limit, making it difficult to stably achieve resolutions below 10nm even with multiple exposures, and each exposure step requires precise alignment, leading to exponential increases in process complexity and cost; while extreme ultraviolet (EUV) lithography can cover the 7nm node, the cost of a single unit exceeds $150 million, and it is limited by the power of the EUV light source (currently a maximum of 250W), processing only 120 wafers per hour, far below the throughput requirement of "hundreds of wafers per hour" for semiconductor mass production lines, making it difficult to support large-scale commercial applications.

[0003] Directed self-assembly lithography (DSA) is a photolithography technique that utilizes block copolymers (BCPs) to spontaneously form ordered nanostructures on silicon wafers. Its "bottom-up" molecular patterning capability has made it a core alternative to overcome the aforementioned bottlenecks. The core principle of DSA is to utilize block copolymers containing two chemically incompatible segments to form periodic ordered nanostructures (e.g., columnar, layered, spherical) through microphase separation and self-assembly. The size of the nanostructures formed by DSA can be precisely controlled by the molecular weight of the block copolymer segments (error <5%), and it is easily mass-produced through large-area coating (>300mm wafers). Furthermore, the cost of DSA is only 1 / 10 to 1 / 20 of EUV lithography, and it has been listed as a key technology "beyond Moore's Law" by the International Technology Roadmap for Semiconductors (IRDS).

[0004] Currently, the core obstacle to the industrial application of DSA lies in the self-assembly kinetic efficiency. Due to the presence of high molecular chain entanglement (the higher the molecular weight of the chain segment, the greater the degree of entanglement), BCPs such as polystyrene-polymethyl methacrylate block copolymer (PS-b-PMMA) require long-term annealing (24h to 48h) to allow the molecular chains to fully relax and form a long-range ordered structure. This is in serious conflict with the "hour-level" process cycle required by semiconductor mass production lines. To address the above issues, existing improvement solutions include the following: 1) Laser annealing: This method utilizes localized high temperatures (>300℃) to accelerate chain segment movement. Although it can shorten the annealing time to the minute level, the temperature gradient formed by the instantaneous high temperature can lead to phase region fusion (merging of adjacent ordered structures), resulting in a defect rate as high as 15% to 20%, which cannot meet the structural integrity requirements of high-end devices; 2) Solvent vapor annealing: This method utilizes the solvent swelling effect to reduce the chain segment interaction energy, thereby accelerating microphase separation. However, commonly used solvents (e.g., chloroform, toluene) are highly toxic, and solvent residues can cause fluctuations in substrate surface energy (contact angle deviation >20°), which can lead to structural orientation disorder (e.g., tilting of columnar phases); 3) Small molecule regulation: This method enhances chain segment fluidity by introducing homopolymers (e.g., PS homopolymers) to form a "wet brush" effect. However, the compatibility between homopolymers and BCP is difficult to control precisely, which can easily lead to uneven domain size in phase separation and increase the cost of raw material purity control (impurity content must be <0.1%). Furthermore, as the molecular weight of BCP increases (to match the requirements of larger period patterns, such as above 50 nm), the chain segment entanglement degree will exhibit a non-linear growth, which will lead to a further increase in the time cost of traditional annealing methods (when the molecular weight of BCP is 500,000 g / mol, the annealing time even exceeds 72 hours), which seriously restricts the application of DSA in the field of medium and high period nanopatterns.

[0005] Therefore, it is of great significance to develop a method for forming nanopatterns that can compress annealing time to the minute or even second level while maintaining high resolution and low defect rate. Summary of the Invention

[0006] The purpose of this invention is to provide a method for rapidly forming nanopatterns using block copolymers and its applications.

[0007] The technical solution adopted in this invention is: A method for rapidly forming nanopatterns using block copolymers includes the following steps: dissolving a polystyrene-polymethyl methacrylate block copolymer in a mixed solvent composed of a low-boiling-point organic solvent and a high-boiling-point organic solvent, wherein the low-boiling-point organic solvent has a boiling point below 150°C and the high-boiling-point organic solvent has a boiling point above 150°C, then spin-coating it onto a substrate surface to form a thin film, followed by annealing and plasma etching to obtain periodic nanopatterns.

[0008] Preferably, the number-average molecular weight of the polystyrene-polymethyl methacrylate block copolymer (PS-b-PMMA) is 40,000 g / mol to 450,000 g / mol.

[0009] Preferably, the low-boiling-point organic solvent is one of toluene, tetrahydrofuran, and propylene glycol methyl ether acetate.

[0010] Preferably, the high-boiling-point organic solvent is at least one selected from anisole, diethylene glycol dimethyl ether, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), dibutyl phthalate (DBP), glycerol (Gly), bis(2-ethylhexyl) sebacate (DOS), and bis(2-ethylhexyl) adipate (DOA).

[0011] Preferably, the volume percentage of high-boiling-point organic solvent in the mixed solvent is 0.1% to 30%.

[0012] Preferably, the mass fraction of the solution formed by dissolving the polystyrene-polymethyl methacrylate block copolymer in the mixed solvent is 0.5% to 10%.

[0013] Preferably, the spin coating speed is 1000 rpm to 10000 rpm, and the spin coating time is 30 s to 60 s.

[0014] Preferably, the substrate is one of a silicon substrate, a glass substrate, a quartz substrate, a polyimide substrate, or a metal oxide substrate.

[0015] Preferably, the substrate surface is covered with a modification layer, which is composed of a hydroxyl-containing polymer.

[0016] Preferably, the hydroxyl-containing polymer is PS-r-PMMA-OH.

[0017] Preferably, the thickness of the film is 20 nm to 150 nm.

[0018] Preferably, the annealing is performed at a temperature of 150℃ to 320℃ for a time of 30s to 300s. When the number-average molecular weight of PS-b-PMMA is 40000g / mol to 150000g / mol, the annealing time is 30s to 60s; when the number-average molecular weight of PS-b-PMMA is 150000g / mol to 450000g / mol, the annealing time is 60s to 300s.

[0019] Preferably, the annealing includes the following operations: first, controlling the heating rate to rise from room temperature to 150℃ to 320℃ at a rate of 10℃ / s to 50℃ / s, holding at that temperature for 30s to 300s, and then rapidly quenching.

[0020] Preferably, the annealing method is hot plate annealing.

[0021] Preferably, the power of the plasma etching is 20W to 100W, and the etching time is 10s to 60s.

[0022] Preferably, the etching gas used in the plasma etching is at least one of O2, Ar, and CF4.

[0023] Preferably, the period of the periodic nanopattern is 20nm to 80nm, and the defect rate is ≤5%.

[0024] Preferably, the nanostructures on the periodic nanopattern are layered phases or hexagonal columnar phases, with the period of the layered phase being 20 nm to 80 nm and the period of the columnar phase being 25 nm to 50 nm.

[0025] Note: The period of a periodic nanopattern: the average distance between corresponding points of adjacent repeating units in a periodic nanopattern (usually determined by the natural period L0 of the polymer blocks, which can be controlled by adjusting the polymer molecular weight or block ratio).

[0026] Defect rate of periodic nanopatterns: The proportion of defective patterns (mainly classified into the following types: dislocations, bridging and holes) that deviate from the ideal pattern in periodic nanopatterns. The calculation formula is as follows: Defect rate (%) = N / A × 100%, where N is the number of defective pattern units and A is the total number of pattern units.

[0027] The application of a method for rapidly forming nanopatterns using block copolymers as described above in semiconductor-guided self-assembly lithography, nanoimprint template fabrication, or high-density memory device fabrication.

[0028] The beneficial effects of this invention are: the method of rapidly forming nanopatterns using block copolymers shortens the annealing time to within 5 minutes (as short as 30 seconds), significantly improving production efficiency. Moreover, the formed nanopatterns have high structural order and low defect rate, making them suitable for fields such as semiconductor-guided self-assembly lithography, nanoimprint template manufacturing, and high-density memory device fabrication.

[0029] Specifically: 1) The method of rapidly forming nanopatterns using block copolymers in this invention can shorten the annealing time to 1 / 100 of the traditional method, significantly improving production efficiency; 2) The high-boiling-point solvent used in the method of rapidly forming nanopatterns using block copolymers in this invention will slowly evaporate during the annealing process, thus avoiding structural collapse and reducing the defect rate of the formed nanopatterns. 3) The method of rapidly forming nanopatterns using block copolymers of the present invention is applicable to a variety of block copolymer systems and complex substrates, and is suitable for large-scale industrial applications. Attached Figure Description

[0030] Figure 1 This is a SEM image of the periodic nanopatterns prepared in Example 1.

[0031] Figure 2 This is a SEM image of the periodic nanopatterns prepared in Example 2.

[0032] Figure 3 This is a SEM image of the periodic nanopatterns prepared in Example 3.

[0033] Figure 4 This is a SEM image of the periodic nanopatterns prepared in Example 4.

[0034] Figure 5 This is a SEM image of the periodic nanopatterns prepared in Example 5.

[0035] Figure 6 This is a SEM image of the periodic nanopatterns prepared in Example 6.

[0036] Figure 7 This is a SEM image of the periodic nanopatterns prepared in Example 7.

[0037] Figure 8 This is a SEM image of the periodic nanopatterns prepared in Example 8.

[0038] Figure 9 This is a SEM image of the periodic nanopatterns prepared in Example 9.

[0039] Figure 10 This is a SEM image of the periodic nanopatterns prepared in Example 10.

[0040] Figure 11 This is a SEM image of the periodic nanopatterns prepared in Example 11.

[0041] Figure 12 This is a SEM image of the periodic nanopatterns prepared in Example 12.

[0042] Figure 13 This is a SEM image of the periodic nanopatterns prepared in Example 13.

[0043] Figure 14 This is a SEM image of the periodic nanopatterns prepared in Example 14.

[0044] Figure 15This is a SEM image of the periodic nanopatterns prepared in Example 15.

[0045] Figure 16 This is a SEM image of the periodic nanopatterns prepared in Example 16.

[0046] Figure 17 This is a SEM image of the periodic nanopatterns prepared in Example 17.

[0047] Figure 18 The image shows a SEM image of the nanopatterns prepared in Comparative Example 1.

[0048] Figure 19 The image shows a SEM image of the nanopatterns prepared in Comparative Example 2.

[0049] Figure 20 The image shows a SEM image of the nanopatterns prepared in Comparative Example 3.

[0050] Figure 21 This is a SEM image of the nanopatterns prepared in Comparative Example 4.

[0051] Figure 22 This is a SEM image of the nanopatterns prepared in Comparative Example 5.

[0052] Figure 23 This is a SEM image of the nanopatterns prepared in Comparative Example 6. Detailed Implementation

[0053] The present invention will be further explained and described below with reference to specific embodiments.

[0054] The silicon wafers in the examples and comparative examples underwent pretreatment as follows: The silicon wafers were ultrasonically cleaned sequentially with toluene, acetone, and isopropanol for 15 minutes each time. They were then immersed in a piranha solution (a mixture of concentrated sulfuric acid and 30% hydrogen peroxide at a volume ratio of 7:3) at 120°C for 30 minutes. Afterward, the wafers were repeatedly rinsed with ultrapure water until neutral, dried with high-purity nitrogen, and then treated in an oxygen plasma cleaner (100W) for 3 minutes. Finally, the wafers were placed on a spin coater, and a suitable amount of 0.7% (by mass) monohydroxy random copolymer (PS-r-PMMA-OH; manufacturer: Polymer Source) was dropped onto the center of the wafer surface. The silicon wafer was coated with a toluene solution from Inc., and the spin coater was rotated at 500 rpm for 5 seconds. Then, it was accelerated to 3500 rpm for 60 seconds. The wafer was then placed in a vacuum oven and annealed at 160°C for 36 hours. The wafer was then removed and ultrasonically cleaned with toluene for 10 minutes. The surface was then dried with high-purity nitrogen (a neutral PS-r-PMMA-OH layer was formed on the surface of the wafer).

[0055] Example 1: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (number average molecular weight 104000 g / mol, PDI=1.08; manufacturer: Polymer Source Inc.) was dissolved in a mixed solvent of toluene and glycerol (Gly) in a volume ratio of 70:30 to prepare a 1% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness 20nm~50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 250℃ at a controlled heating rate of 30℃ / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 100W to obtain periodic nanopatterns.

[0056] The scanning electron microscope (SEM) image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 1 As shown.

[0057] Depend on Figure 1 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 48 nm and a defect rate of less than 3%.

[0058] Example 2: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was stirred and dissolved in a mixed solvent of toluene and diethylene glycol dimethyl ether in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 50W to obtain periodic nanopatterns.

[0059] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 2 As shown.

[0060] Depend on Figure 2 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 48 nm and a defect rate of less than 3%.

[0061] Example 3: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was stirred and dissolved in a mixed solvent of toluene and N-methylpyrrolidone (NMP) in a volume ratio of 90:10 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300°C at a controlled heating rate of 30°C / s, held at that temperature for 30s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 80W to obtain periodic nanopatterns.

[0062] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 3 As shown.

[0063] Depend on Figure 3 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 48 nm and a defect rate of less than 5%.

[0064] Example 4: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was stirred and dissolved in a mixed solvent composed of tetrahydrofuran and γ-butyrolactone (GBL) in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 30W to obtain periodic nanopatterns.

[0065] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 4 As shown.

[0066] Depend on Figure 4 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 48 nm and a defect rate of less than 2%.

[0067] Example 5: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (number average molecular weight 133000 g / mol, PDI=1.05; manufacturer: Polymer Source Inc.) was dissolved in a mixed solvent of propylene glycol methyl ether acetate and dibutyl phthalate (DBP) in a volume ratio of 90:10 to prepare a 1% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness 20nm~50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300℃ at a controlled heating rate of 30℃ / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 100W to obtain periodic nanopatterns.

[0068] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 5 As shown.

[0069] Depend on Figure 5 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 3%.

[0070] Example 6: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent of toluene and anisole in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 7000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 320°C at a controlled heating rate of 30°C / s, held at that temperature for 30s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 100W to obtain periodic nanopatterns.

[0071] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 6 As shown.

[0072] Depend on Figure 6 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 5%.

[0073] Example 7: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent composed of toluene and bis(2-ethylhexyl) sebacate (DOS) in a volume ratio of 85:15 to prepare a PS-b-PMMA solution with a mass fraction of 1.5%. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 6000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 250°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 35s at a power of 100W to obtain periodic nanopatterns.

[0074] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 7 As shown.

[0075] Depend on Figure 7 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 2%.

[0076] Example 8: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent consisting of tetrahydrofuran and bis(2-ethylhexyl) adipate (DOA) in a volume ratio of 70:30 to prepare a PS-b-PMMA solution with a mass fraction of 1.5%. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 3500rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 220°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 90W to obtain periodic nanopatterns.

[0077] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 8 As shown.

[0078] Depend on Figure 8 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 5%.

[0079] Example 9: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent of tetrahydrofuran and glycerol (Gly) in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 250°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 45s at a power of 50W to obtain periodic nanopatterns.

[0080] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 9 As shown.

[0081] Depend on Figure 9 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 4%.

[0082] Example 10: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent of toluene and N-methylpyrrolidone (NMP) in a volume ratio of 90:10 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 7000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 80W to obtain periodic nanopatterns.

[0083] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 10 As shown.

[0084] Depend on Figure 10 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 5%.

[0085] Example 11: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in a mixed solvent of toluene and glycerol (Gly) in a volume ratio of 75:25 to prepare a PS-b-PMMA solution with a mass fraction of 1.5%. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 6000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 290°C at a controlled heating rate of 30°C / s, held at that temperature for 50s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 60W to obtain periodic nanopatterns.

[0086] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 11 As shown.

[0087] Depend on Figure 11 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 3%.

[0088] Example 12: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was dissolved by stirring in a mixed solvent composed of toluene and bis(2-ethylhexyl) sebacate (DOS) in a volume ratio of 70:30 to prepare a 1% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 6000rpm and the spin-coating time was 60 seconds. The wafer was then placed on a hot plate and heated from room temperature to 300°C at a controlled heating rate of 30°C / s, held at that temperature for 45 seconds, and then rapidly quenched. Finally, plasma etching was performed with O2 for 30 seconds at a power of 20W to obtain periodic nanopatterns.

[0089] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 12 As shown.

[0090] Depend on Figure 12 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 56 nm and a defect rate of less than 3%.

[0091] Example 13: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (number-average molecular weight 263000 g / mol, PDI=1.03; manufacturer: Polymer Source Inc.) was dissolved in a mixed solvent of tetrahydrofuran and bis(2-ethylhexyl) adipate (DOA) in a volume ratio of 90:10 to prepare a 5% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness 20nm~50nm). The spin-coating speed was 3000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300℃ at a controlled heating rate of 30℃ / s, held at that temperature for 300s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 30s at a power of 100W to obtain periodic nanopatterns.

[0092] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 13 As shown.

[0093] Depend on Figure 13 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 90 nm and a defect rate of less than 5%.

[0094] Example 14: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 13) was stirred and dissolved in a mixed solvent composed of propylene glycol methyl ether acetate and diethylene glycol dimethyl ether in a volume ratio of 97:3 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 4000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280°C at a controlled heating rate of 30°C / s, held at that temperature for 240s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 60s at a power of 40W to obtain periodic nanopatterns.

[0095] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 14 As shown.

[0096] Depend on Figure 14 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 90 nm and a defect rate of less than 5%.

[0097] Example 15: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was stirred and dissolved in a mixed solvent composed of propylene glycol methyl ether acetate and anisole in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 290°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 100W to obtain periodic nanopatterns.

[0098] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 15 As shown.

[0099] Depend on Figure 15 It can be seen that this embodiment successfully prepared a highly ordered fingerprint-like periodic nanopattern with a period of 90 nm and a defect rate of less than 5%.

[0100] Example 16: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (number-average molecular weight 309000 g / mol, PDI=1.08; manufacturer: Polymer Source Inc.) was dissolved in a mixed solvent of toluene and N-methylpyrrolidone (NMP) in a volume ratio of 95:5 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness 20nm~50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280℃ at a controlled heating rate of 30℃ / s, held at that temperature for 180s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 30s at a power of 60W to obtain periodic nanopatterns.

[0101] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 16 As shown.

[0102] Depend on Figure 16 It can be seen that this embodiment successfully prepared highly ordered columnar periodic nanopatterns with a period of 40 nm and a defect rate of less than 3%.

[0103] Example 17: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 16) was stirred and dissolved in a mixed solvent of toluene and glycerol (Gly) in a volume ratio of 80:20 to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 290°C at a controlled heating rate of 30°C / s, held at that temperature for 300s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 30s at a power of 70W to obtain periodic nanopatterns.

[0104] The SEM image of the periodic nanopatterns prepared in this embodiment is shown below. Figure 17 As shown.

[0105] Depend on Figure 17 It can be seen that this embodiment successfully prepared highly ordered columnar periodic nanopatterns with a period of 40 nm and a defect rate of less than 3%.

[0106] Comparative Example 1: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was dissolved in toluene to prepare a 2% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (20nm to 50nm thick). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 250°C at a controlled heating rate of 30°C / s. The temperature was held for 60s and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a power of 100W to obtain nanopatterns.

[0107] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 18 As shown.

[0108] Depend on Figure 18 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0109] Comparative Example 2: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 1) was stirred and dissolved in tetrahydrofuran to prepare a PS-b-PMMA solution with a mass fraction of 2%. An appropriate amount of PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 15s at a plasma etching power of 80W to obtain nanopatterns.

[0110] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 19 As shown.

[0111] Depend on Figure 19 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0112] Comparative Example 3: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was dissolved in toluene to prepare a PS-b-PMMA solution with a mass fraction of 1.5%. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 320°C at a controlled heating rate of 30°C / s. The temperature was held for 30s and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 100W to obtain nanopatterns.

[0113] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 20 As shown.

[0114] Depend on Figure 20 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0115] Comparative Example 4: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 5) was stirred and dissolved in propylene glycol methyl ether acetate to prepare a PS-b-PMMA solution with a mass fraction of 1.5%. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 300°C at a controlled heating rate of 30°C / s, held at that temperature for 60s, and then rapidly quenched. Finally, plasma etching was performed with O2 for 25s at a power of 100W to obtain nanopatterns.

[0116] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 21 As shown.

[0117] Depend on Figure 21 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0118] Comparative Example 5: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 13) was stirred and dissolved in toluene to prepare a 5% PS-b-PMMA solution. An appropriate amount of the PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 3000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280°C at a controlled heating rate of 30°C / s. The temperature was held for 180s and then rapidly quenched. Finally, plasma etching was performed with O2 for 30s at a power of 100W to obtain nanopatterns.

[0119] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 22 As shown.

[0120] Depend on Figure 22 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0121] Comparative Example 6: A method for rapidly forming nanopatterns using block copolymers, comprising the following steps: PS-b-PMMA (same as in Example 16) was stirred and dissolved in toluene to prepare a PS-b-PMMA solution with a mass fraction of 2%. An appropriate amount of PS-b-PMMA solution was then spin-coated onto the surface of a silicon wafer to form a thin film (thickness of 20nm to 50nm). The spin-coating speed was 5000rpm and the spin-coating time was 60s. The wafer was then placed on a hot plate and heated from room temperature to 280°C at a controlled heating rate of 30°C / s. The temperature was held for 180s and then rapidly quenched. Finally, plasma etching was performed with O2 for 30s at a power of 100W to obtain nanopatterns.

[0122] SEM images of the nanopatterns prepared in this comparative example are shown below. Figure 23 As shown.

[0123] Depend on Figure 23 It can be seen that this comparative example failed to prepare periodic nanopatterns.

[0124] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for rapidly forming nanopatterns using block copolymers, characterized in that, Includes the following steps: Polystyrene-polymethyl methacrylate block copolymer is dissolved in a mixed solvent consisting of a low-boiling-point organic solvent (boiling point below 150°C) and a high-boiling-point organic solvent (boiling point above 150°C). The solution is then spin-coated onto a substrate to form a thin film, followed by annealing and plasma etching to obtain periodic nanopatterns.

2. The method for rapidly forming nanopatterns using block copolymers according to claim 1, characterized in that: The number-average molecular weight of the polystyrene-polymethyl methacrylate block copolymer is 40,000 g / mol to 450,000 g / mol.

3. The method for rapidly forming nanopatterns using block copolymers according to claim 1, characterized in that: The low-boiling-point organic solvent is one of toluene, tetrahydrofuran, and propylene glycol methyl ether acetate.

4. The method for rapidly forming nanopatterns using block copolymers according to claim 1, characterized in that: The high-boiling-point organic solvent is at least one of anisole, diethylene glycol dimethyl ether, N-methylpyrrolidone, γ-butyrolactone, dibutyl phthalate, glycerol, bis(2-ethylhexyl) sebacate, and bis(2-ethylhexyl) adipate.

5. The method for rapidly forming nanopatterns using block copolymers according to any one of claims 1 to 4, characterized in that: The volume percentage of high-boiling-point organic solvent in the mixed solvent is 0.1% to 30%.

6. The method for rapidly forming nanopatterns using block copolymers according to any one of claims 1 to 4, characterized in that: The spin coating speed is 1000rpm to 10000rpm, and the spin coating time is 30s to 60s.

7. The method for rapidly forming nanopatterns using block copolymers according to any one of claims 1 to 4, characterized in that: The thickness of the film is 20nm to 150nm.

8. The method for rapidly forming nanopatterns using block copolymers according to any one of claims 1 to 4, characterized in that: The annealing is carried out at a temperature of 150℃ to 320℃ for a time of 30s to 300s.

9. The method for rapidly forming nanopatterns using block copolymers according to any one of claims 1 to 4, characterized in that: The plasma etching power is 20W to 100W, and the etching time is 10s to 60s.

10. The application of a method for rapidly forming nanopatterns using block copolymers as described in any one of claims 1 to 9 in semiconductor guided self-assembly lithography, nanoimprint template manufacturing, or high-density memory device fabrication.

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