Micro-nano structure based on block copolymer and processing method thereof
By coating a block copolymer solution on a substrate template and using a single physical adsorption layer to guide self-assembly, the problem that block copolymers are difficult to self-assemble into vertical layered structures is solved, thereby simplifying the processing steps and expanding the scope of application.
Patent Information
- Application Number
- CN202510924860.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2025-10-17
AI Technical Summary
Existing block copolymer self-assembly technology makes it difficult to form vertical layered structures. Traditional methods are cumbersome, have poor material compatibility and high costs, and have a narrow range of chemically modified substrates or external electric field regulation.
By coating a block copolymer solution on a substrate template, a single-layer physical adsorption layer is used to guide the self-assembly of the upper block copolymer to form a phase structure perpendicular to the substrate, including steps such as coating, driving phase separation, thinning and annealing, which simplifies the processing process.
It realizes the universal regulation of the structural morphology of block copolymers, simplifies the processing steps, expands the scope of application, and does not require the special design of neutral layer materials.
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Figure CN120795729A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of block copolymer directed self-assembly, and particularly relates to a micro-nano structure based on block copolymer and a processing method thereof. BACKGROUND
[0002] In block copolymer directed self-assembly, achieving vertical orientation is a key technology for breaking the optical diffraction limit and constructing high-density nanostructures. Traditional block copolymer self-assembly technology relies on a neutral layer to achieve vertical phase separation, but the preparation process of the neutral layer is complex, the material compatibility is poor, and the cost is high. The physical and chemical properties of the two blocks of high-chi block copolymer often have large differences, which leads to the arrangement of the phase structure more parallel to the substrate, and it is difficult to form the required vertical layered structure.
[0003] The prior art adjusts the orientation by chemical modification of the substrate or introduction of an external electric field, which has problems such as complicated steps and narrow application range. Therefore, there is an urgent need for a universal method for adjusting the morphology of block copolymer directed self-assembly. SUMMARY
[0004] The present application is carried out to solve the above problems, and aims to provide a micro-nano structure based on block copolymer and a processing method thereof.
[0005] The present application provides a micro-nano structure based on block copolymer and a processing method thereof, which has the following characteristics: S1, providing a substrate template, and performing block affinity treatment on the substrate template with a clean surface; S2, coating a mixed solution of block copolymer or homopolymer on the substrate template, and physically adsorbing the mixed solution on the surface of the substrate by a driven phase separation process to form a first layer of film; S3, removing the unadsorbed part of the upper layer of the first layer of film by a film thinning process to form a single-layer physical adsorption layer; and S4, coating the mixed solution of block copolymer or homopolymer on the single-layer physical adsorption layer again, and self-assembling the upper layer of block copolymer under the guidance of the single-layer physical adsorption layer by a driven phase separation process to form a phase structure perpendicular to the substrate template, thereby forming a straight line stripe array and a vertical through hole.
[0006] In the micro-nano structure based on block copolymer and the processing method thereof provided by the present application, the mixed solution of block copolymer or homopolymer can further have the following characteristics: the block copolymer solution in the mixed solution of block copolymer or homopolymer includes block copolymer and an organic solvent.
[0007] In the micro-nano structure based on block copolymer and the processing method thereof provided by the present application, the mixed solution of block copolymer or homopolymer can further have the following characteristics: the concentration of the block copolymer in the organic solvent is 0.1-5wt%, the organic solvent includes at least one of tetrahydrofuran, chloroform, toluene, and N,N-dimethylformamide, and the organic solvent does not react with the substrate template chemically.
[0008] In the micro-nano structure processing method based on block copolymer provided by the application, the method for coating the mixed solution of block copolymer or homopolymer can further include spin coating, drop coating and inkjet printing. In the spin coating, the spin coating speed is 1000-5000 rpm, and the spin coating time is 30-60 s. In the drop coating, different block copolymers are dropped on different regions of the substrate template to form a pattern.
[0009] In the micro-nano structure processing method based on block copolymer provided by the application, the driving phase separation process can be any one of template guiding process, annealing process, crystallization driving process and dynamic response driving of photoelectricity and magnetism. The template guiding process can be any one of chemical epitaxy, template epitaxy and boundary-oriented epitaxy. The annealing process includes thermal annealing and solvent annealing. The thermal annealing temperature is 50-250°C, and the annealing time is 0.15-24 h. The solvent annealing temperature is 35-120°C, and the annealing time is 0.15-24 h. An electric field is applied during the annealing process, and the electric field strength is 0.1-10 V / μm.
[0010] In the micro-nano structure processing method based on block copolymer provided by the application, the thin film thinning process can be any one of chemical solution immersion, wet etching, dry etching, mechanical grinding and chemical mechanical planarization or transfer technology.
[0011] In the micro-nano structure processing method based on block copolymer provided by the application, the mixed solution of block copolymer or homopolymer can further include block A and block B. Block A is any one of fluorine-containing block, metal-containing block and main chain or side chain containing silicon. Block B has different physical and chemical properties from block A. The metal includes iron, platinum, ruthenium, gold, lead and tin.
[0012] In the micro-nano structure processing method based on block copolymer provided by the application, the substrate template can be a periodic nano pattern. The depth of the substrate template is 5-50 nm, and the width is 1-20 times the phase separation period of the block copolymer. The substrate template is used to guide the block copolymer to form a vertical hole and line linear array. The periodic nano pattern is a parallel line or a hexagonal array with a line width of 10-100 nm.
[0013] In the micro-nano structure processing method based on block copolymer provided by the application, the material of the substrate template can include silicon or a compound of silicon, mica or an elastic resin.
[0014] Preferably, the material of the substrate template is selected from silicon, silicon dioxide, silicon nitride, quartz, glass, mica sheet and polydimethylsiloxane.
[0015] The present application provides a micro-nano structure based on block copolymer, which has the feature of being obtained by the micro-nano structure processing method based on block copolymer of any one of the above.
[0016] Effects and advantages of the present application
[0017] According to the micro-nano structure based on block copolymer and the processing method thereof, the present application provides a universal method for regulating the morphology of block copolymer directed self-assembly, uses the physical adsorption layer of single-layer block copolymer to guide the phase structure of the upper layer perpendicular to the substrate, and regulates the structure and morphology of the block copolymer without specially designing and synthesizing a suitable neutral layer material for regulating the orientation of the block copolymer, thereby simplifying the processing steps and expanding the application range. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 is a schematic diagram of the micro-nano structure processing method of the vertically oriented lamellar phase block copolymer in embodiment one of the present application.
[0019] Figure 2 is an SEM image of the lamellar phase block copolymer self-assembled under the guidance of the physical adsorption layer of the single-layer block copolymer in embodiment one of the present application;
[0020] Figure 3 is an SEM image of the columnar phase BCP guided by the physical adsorption layer without template in embodiment two of the present application;
[0021] Figure 4 is a schematic diagram of the micro-nano structure processing method of the vertically oriented columnar phase block copolymer in embodiment three of the present application. DETAILED DESCRIPTION
[0022] In order to make the technical means, creative features, purposes and effects of the present application easy to understand, the following embodiments combined with the drawings will specifically describe the micro-nano structure based on block copolymer and the processing method thereof.
[0023] Embodiment one
[0024] Figure 1 is a schematic diagram of the micro-nano structure processing method of the vertically oriented lamellar phase block copolymer in embodiment one of the present application.
[0025] Figure 1 (a) is a schematic diagram of the columnar phase block copolymer oriented parallel to the substrate in the embodiment of the present application. Figure 1 (b) is a schematic diagram of the single-period BCP physical adsorption layer in the embodiment of the present application. Figure 1 (c) is a schematic diagram of the vertically oriented lamellar BCP self-assembled on the single-layer physical adsorption layer in the embodiment of the present application.
[0026] As Figure 1 shown in the embodiment, a layered phase block copolymer vertical orientation micro-nano structure is disclosed, and the processing method comprises the following steps:
[0027] S1, providing a substrate template 10, and performing block affinity treatment on the substrate template with a clean surface.
[0028] The substrate template 10 is a periodic nano pattern, the depth of the substrate template 10 is 5-50 nm, and the width is 1-20 times the phase separation period of the block copolymer, which is used to guide the block copolymer to form a vertical hole and a linear array of lines.
[0029] The periodic nano pattern is a parallel line or a hexagonal array with a line width of 10-100 nm.
[0030] The material of the substrate template 10 includes silicon, silicon dioxide, silicon nitride, quartz, glass, mica sheet, and polydimethylsiloxane.
[0031] S2, coating a block copolymer solution on the substrate template 10, and physically adsorbing the block copolymer solution on the substrate surface through a thermal annealing driven phase separation process to form a first layer of film.
[0032] In the mixed solution of the block copolymer and the homopolymer, the block copolymer solution includes the block copolymer and an organic solvent.
[0033] The concentration of the block copolymer in the organic solvent is 0.1-5 wt%.
[0034] The organic solvent includes at least one of tetrahydrofuran, chloroform, toluene, and N,N-dimethylformamide, and the organic solvent does not chemically react with the substrate template.
[0035] In the mixed solution of the block copolymer and the homopolymer, the block copolymer includes block A and block B, the block A is any one of a fluorine-containing block, a metal-containing block, and a main chain or side chain containing silicon, and the physical and chemical properties of the block B are different from those of the block A.
[0036] The method for coating the mixed solution of the block copolymer and the homopolymer includes spin coating, drop coating, and inkjet printing.
[0037] In the spin coating method, the spin coating speed is 1000-5000 rpm, and the spin coating time is 30-60 s.
[0038] The drop coating method forms a pattern by drop coating different block copolymer seeds to different areas of the substrate template.
[0039] The driven phase separation process is any one of a template guiding process, an annealing process, a crystallization driving process, and a dynamic response driving of photoelectricity and magnetism.
[0040] The template guiding process is any one of chemical epitaxy, template epitaxy and boundary guiding epitaxy.
[0041] The annealing process includes thermal annealing and solvent annealing, the thermal annealing temperature is 50-250℃, the annealing time is 0.15-24h, the solvent annealing temperature is 35-120℃, the time is 0.15-24h, an electric field is applied during the annealing process, the electric field strength is 0.1-10V / μm.
[0042] S3, the upper layer of the first layer of thin film is removed by a thin film thinning process through chemical solution immersion method, so that only a single period BCP physical adsorption layer is left, forming a single layer physical adsorption layer 20 as shown in Figure 1 (b).
[0043] The thin film thinning process is any one of chemical solution immersion method, wet etching, dry etching, mechanical grinding and chemical mechanical planarization or transfer technology.
[0044] S4, the target layer phase block copolymer is coated on the single layer physical adsorption layer again, and annealing treatment is carried out in a solvent atmosphere, so that the block copolymer is guided self-assembled in the solvent atmosphere, so as to realize the vertical orientation regulation of the layer phase block copolymer, as shown in Figure 1 (c).
[0045] Figure 2 It is the SEM image of the layer phase block copolymer self-assembled under the guiding action of the block copolymer single layer physical adsorption layer in the embodiment of the application.
[0046] As shown in Figure 2 , the lines can be clearly observed to present long-range ordered periodic arrangement.
[0047] Example two
[0048] Figure 3 It is the SEM image of the columnar phase BCP guided without template physical adsorption layer in the embodiment two of the application.
[0049] In this embodiment, a columnar phase self-assembly structure micro-nano structure guided without template physical adsorption layer is disclosed, and the processing method comprises the following steps:
[0050] S1, preparing a physical adsorption layer under the condition of no template;
[0051] S2, spin coating the columnar phase block copolymer on the physical adsorption layer and carrying out thermal annealing, presenting a horizontal columnar line structure as shown in Figure 3 .
[0052] Example three
[0053] Figure 4 is a schematic diagram of the processing method of the vertical columnar phase block copolymer micro-nano structure in embodiment three of the present application.
[0054] Figure 4 (a) is a schematic diagram of spin-coating photoresist on a substrate template in embodiment three of the present application. Figure 4 (b) is a schematic diagram of developing photoresist patterns in embodiment three of the present application. Figure 4 (c) is a schematic diagram of achieving pattern transfer by dry etching in embodiment three of the present application. Figure 4 (d) is a schematic diagram of the DSA morphology of columnar phase BCP in a physical template in embodiment three of the present application. Figure 4 (e) is a schematic diagram of a single physical adsorption layer in a physical template in embodiment three of the present application. Figure 4 (f) is a schematic diagram of guiding BCP columnar vertical orientation in a single physical adsorption layer in a physical template in embodiment three of the present application.
[0055] As shown in Figure 4 , the present embodiment discloses a columnar phase block copolymer vertical orientation micro-nano structure, and the processing method comprises the following steps:
[0056] S1, as shown in Figure 4 (a), a substrate template 10' is provided, and after spin-coating photoresist on the surface-cleaned substrate template, soft baking treatment, alignment, and exposure are performed, and a photoresist pattern as shown in Figure 4 (b) is obtained by development.
[0057] As shown in Figure 4 (c), pattern transfer is achieved by thin film thinning process of dry etching. Then the substrate template 10' is subjected to block affinity treatment.
[0058] S2, spin-coating a block copolymer on the substrate template 10' and obtaining a long-range ordered line pattern 30 guided by the template self-assembly after annealing treatment, as shown in Figure 4 (d).
[0059] S3, as shown in Figure 4 (e), thin film thinning treatment (such as solution immersion) is performed to leave only a single period BCP physical adsorption layer 40.
[0060] S4, spin-coating a target solution on the guiding template with the physical single-layer adsorption film, and guiding columnar phase block copolymer self-assembly to form a vertical phase structure by thermal annealing, as shown in (f).
[0061] Those skilled in the art should understand that the present application is not limited to the above-mentioned embodiments, and the above-mentioned embodiments and descriptions in the specification are only to illustrate the principles of the present application, and various changes and improvements can be made without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.
Claims
1. A method for processing micro-nano structures based on block copolymers, characterized in that: The steps include: S1, providing a base template, and performing block affinity treatment on the base template with a clean surface; S2, coating a mixed solution of block copolymers or homopolymers on the substrate template, and physically adsorbing the mixed solution on the substrate surface through a driven phase separation process to form a first thin film; S3, removing the unadsorbed upper portion of the first film by a film thinning process to form a single physical adsorption layer; S4, coating the mixed solution of the block copolymer or homopolymer again on the single-layer physical adsorption layer, and through the driven phase separation process, the upper block copolymer is self-assembled under the guidance of the single-layer physical adsorption layer to form a phase structure perpendicular to the base template, forming a straight stripe array and vertical through holes.
2. The method for processing micro-nano structures based on block copolymers according to claim 1, characterized in that: in, In the mixed solution of the block copolymer or homopolymer, the block copolymer solution comprises the block copolymer and an organic solvent.
3. The method for processing micro-nano structures based on block copolymers according to claim 2, characterized in that: in, The concentration of the block copolymer in the organic solvent is 0.1-5 wt %. The organic solvent comprises at least one of tetrahydrofuran, chloroform, toluene and N,N-dimethylformamide. The organic solvent does not chemically react with the base template.
4. The method for processing micro-nanostructures based on block copolymers according to claim 1, wherein: in, Methods for coating the mixed solution of the block copolymer or homopolymer include spin coating, drop coating, and inkjet printing. In the spin coating method, the spin coating speed is 1000-5000 rpm, and the spin coating time is 30-60 s. The drop coating method forms a pattern by drop coating different block copolymer seeds onto different areas of the substrate template.
5. The method for processing micro-nano structures based on block copolymers according to claim 1, characterized in that: in, The driving phase separation process is any one of a template-guided process, an annealing process, a crystallization-driven process, and a dynamic response drive such as an opto-electromagnetic process. The template-guided process is any one of chemical epitaxy, template epitaxy and boundary-guided epitaxy. The annealing process includes thermal annealing and solvent annealing. The temperature of the thermal annealing is 50-250°C and the annealing time is 0.15-24 hours. The temperature of the solvent thermal annealing is 35-120°C and the time is 0.15-24 hours. An electric field is applied during the annealing process with an electric field strength of 0.1-10V / μm.
6. The method for processing micro-nano structures based on block copolymers according to claim 1, characterized in that: in, The thin film thinning process is any one of a chemical solution immersion method, wet etching, dry etching, mechanical grinding, and chemical mechanical planarization or transfer technology.
7. The method for processing micro-nano structures based on block copolymers according to claim 1, characterized in that: in, In the mixed solution of the block copolymer or homopolymer, the block copolymer comprises block A and block B, the block A is any one of a fluorine-containing block, a metal-containing block, and a main chain or side chain containing silicon, and the physical and chemical properties of the block B are different from those of the block A. Such metals include iron, platinum, ruthenium, gold, lead and tin.
8. The method for processing micro-nano structures based on block copolymers according to claim 1, characterized in that: in, The base template is a periodic nano-pattern with a depth of 5 to 50 nm and a width of 1 to 20 times the phase separation period of the block copolymer, and is used to guide the columnar phase block copolymer to form vertical holes and linear arrays. The periodic nano pattern is a parallel line or hexagonal array with a line width of 10 to 100 nm.
9. The method for processing micro-nanostructures based on block copolymers according to claim 1, characterized in that: in, The material of the base template includes silicon or silicon compounds, mica or elastic resin.
10. A micro-nanostructure based on a block copolymer, characterized in that: The method is obtained by the block copolymer-based micro-nanostructure processing method according to any one of claims 1 to 9.