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KR-20260067329-A - CURABLE COMPOSITION AND METHODS FOR FORMING FILM AND MANUFACTURING ARTICLE

KR20260067329AKR 20260067329 AKR20260067329 AKR 20260067329AKR-20260067329-A

Abstract

The curable composition comprises a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d). The curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm. The amount of solvent (d) is in the range of more than 5 volume% to 95 volume% of the total curable composition. The boiling point of the solvent (d) is less than 250°C. The curable composition in the state excluding the solvent (d) has a viscosity of 8 mPa·s to 30 mPa·s at 23°C and 1 atm.

Inventors

  • 이토 유토
  • 이토 도시키
  • 가와타 이사오
  • 이마무라 히데키
  • 나카타 에이이치

Assignees

  • 캐논 가부시끼가이샤

Dates

Publication Date
20260512
Application Date
20251030
Priority Date
20241105

Claims (20)

  1. Polymerizable compound (a); Photopolymerization initiator (b), and A solvent (d) having a boiling point of less than 250°C in an amount greater than 5 volume% and up to 95 volume% of the total curable composition It is a curable composition comprising, Here, the curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23℃ and 1 atm, and A curable composition formed by excluding the solvent (d) from the above curable composition, wherein the viscosity of the composition is 8 mPa·s to 30 mPa·s at 23°C and 1 atm.
  2. Polymerizable compound (a); Photopolymerization initiator (b); A surfactant (c) having a viscosity of 500 mPa·s or less at 23℃ and 1 atm; and A solvent (d) having a boiling point of less than 250°C in an amount greater than 5 volume% and up to 95 volume% of the total curable composition It is a curable composition comprising, Herein, the curable composition is a curable composition having a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm.
  3. In paragraph 1 or 2, A curable composition formed by excluding the solvent (d) from the above curable composition, having a viscosity of 8 mPa·s to 20 mPa·s at 23°C and 1 atm.
  4. In paragraph 2, The above surfactant (c) is a curable composition having a viscosity of 400 mPa·s or less at 23°C and 1 atm.
  5. In paragraph 1 or 2, A curable composition wherein the solvent (d) comprises one or more solvents, and each of the one or more solvents has a boiling point in the range of 100°C to less than 250°C at 1 atm.
  6. In paragraph 1 or 2, A curable composition wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a boiling point of 250°C or higher at 1 atm.
  7. In paragraph 1 or 2, The above polymerizable compound (a) includes a monofunctional polymerizable compound and a polyfunctional polymerizable compound, and Herein, the polyfunctional polymerizable compound is a curable composition comprising 20 mass% or more of the polymerizable compound (a).
  8. In paragraph 1 or 2, A curable composition wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a molecular weight of 200 or more.
  9. In paragraph 1, The above polymerizable compound (a) is a curable composition comprising a polymer having polymerizable functional groups.
  10. In any one of paragraphs 1, 2, 4 and 9, The above-mentioned curable composition is a curable composition that exhibits a glass transition temperature of 70°C or higher after curing.
  11. In any one of paragraphs 1, 2, 4 and 9, A curable composition wherein the polymerizable compound (a) comprises one or more polymerizable compounds, and each of the one or more polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80°C and 1 atm.
  12. In any one of paragraphs 1, 2, 4 and 9, The above polymerizable compound (a) is a curable composition comprising a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.
  13. In any one of paragraphs 1, 2, 4 and 9, The above polymerizable compound (a) comprises one or more polymerizable compounds, and The above polymerizable compound (a) has an Onish parameter abbreviated as OP of 1.80 to 4.00, the Onish parameter is a mole fraction weighted average of the N/(Nc - N O ) values of each molecule of the above one or more polymerizable compounds, wherein N represents the total number of atoms in the molecule, Nc represents the number of carbon atoms in the molecule, and N O represents the number of oxygen atoms in the molecule, a curable composition.
  14. In any one of paragraphs 1, 2, 4 and 9, The composition obtained by removing the above solvent (d) is a curable composition containing 10 mass% or more of silicon atoms.
  15. In any one of paragraphs 1, 2, 4 and 9, The above-mentioned curable composition is a curable composition having a carbon dioxide solubility coefficient of 0.5 kg/ m³ ·atm to 10 kg/ m³ ·atm.
  16. In any one of paragraphs 1, 2, 4 and 9, The above curable composition is a curable composition used in an inkjet method.
  17. A film forming method for forming a film of a curable composition on a substrate using a mold, and A coating step of discretely applying a plurality of droplets of a curable composition according to any one of claims 1, 2, 4 and 9 onto the substrate; After applying the above droplets, a contact step of contacting the plurality of droplets on the substrate with a mold to form a liquid film between the substrate and the mold; A curing step of curing the liquid film into a cured film after contact between the above droplet and the mold; and A film forming method comprising a separation step of separating the cured film from the mold after the curing step.
  18. In Paragraph 17, A film forming method further comprising a waiting step between the coating step and the contact step, wherein a droplet of a curable composition is merged on a substrate to form a substantially continuous liquid film and a solvent in the liquid film is evaporated.
  19. In Paragraph 18, A film-forming method in which the above waiting step continues until the solvent in the liquid film volatilizes to 10 volume% or less relative to the entire liquid film.
  20. In Paragraph 18, A film forming method in which, in the above waiting step, the substrate is heated at a temperature of 30°C to 200°C for 10 seconds to 600 seconds.

Description

Curable composition, methods for forming a film, and methods for manufacturing an article The present disclosure relates to a curable composition and a method for forming a film and manufacturing an article. In semiconductor devices, microelectromechanical systems (MEMS), and similar technological fields, miniaturization is increasingly required, and imprinting technology (optical imprinting technology) is attracting attention as a microfabrication technology. In imprinting technology, a curable composition is supplied (applied) onto a substrate, and the composition is cured while a mold having a fine relief pattern on its contact surface is in contact with the composition. Consequently, the relief pattern of the mold is transferred to the cured film of the curable composition, thereby forming a pattern on the substrate. Imprinting technology enables the formation of fine patterns (structures) with a size of several nanometers on a substrate. An example of pattern formation using imprinting technology will be described. First, a liquid curable composition is discretely dropped (applied) to a pattern-forming area on a substrate. Droplets of the curable composition in the pattern-forming area diffuse onto the surface of the substrate. This phenomenon is called pre-diffusion. Subsequently, the curable composition on the substrate comes into contact with the contact surface of the mold (pressurized against it). Consequently, droplets of the curable composition diffuse across the gap between the substrate and the mold due to capillary action. This phenomenon is called diffusion. Additionally, the curable composition fills the recesses of the mold pattern due to capillary action. This phenomenon is called filling. The time required to complete these diffusion and filling is called the filling time. After filling is complete, the curable composition is cured by irradiating it with light. Subsequently, the cured composition on the substrate is separated from the mold. Thus, the cured pattern of the curable composition is formed by transferring the pattern of the mold onto the curable composition on the substrate through these steps. At this point, the cured pattern of the curable composition formed on the substrate has a residual film. The residual film is the cured film remaining between the concave portion (the convex portion of the mold pattern) of the cured film of the curable composition and the substrate. In addition, photolithography for manufacturing semiconductor devices requires the substrate to be planarized. For example, in extreme ultraviolet lithography (EUV), a photolithography technology that has attracted attention in recent years, the depth of focus at which the projected image is formed decreases as miniaturization progresses, so the relief pattern on the surface of the substrate supplied with the curable composition must be limited to tens of nanometers or less. Imprinting technology also requires planarization to the same extent as EUV to improve the filler content and linewidth accuracy of the curable composition. In the planarization technology (Japanese Patent Publication No. 2019-140394), a curable composition corresponding to the relief structure is discretely dropped onto a substrate provided with a relief structure, and subsequently, the composition is cured while in contact with a mold having a flat surface, thereby forming a flat surface. In a pattern formation method and planarization technique using imprinting, a curable composition on a substrate comes into contact with a mold without the droplets of the curable composition coming into contact with each other. This process inevitably causes bubbles to be trapped between the mold, the substrate, and the composition. Consequently, it takes a long time for the bubbles to diffuse and disappear across the mold and the substrate, which is one of the factors that reduces productivity (throughput). Therefore, a technique has been developed to merge the droplets of the curable composition on the substrate before bringing the curable composition into contact with the mold (see Japanese Patent Publication No. 2022-188736). FIGS. 1a to 1g are schematic representations illustrating a pattern forming method (film forming method) according to one embodiment of the present disclosure. Figures 2a to 2d are schematic representations illustrating the flow behavior of droplets of a curable composition during the waiting phase. Figure 3 is a schematic representation illustrating the separation of surfactants during the contact step. Figure 4 is a schematic representation illustrating the contact step. Figure 5 is a plot of the change in edge filling speed according to the change in the viscosity coefficient of the liquid film. Figure 6 is a plot of the result from the same calculation as in Figure 5, with the horizontal axis plotted as time/viscosity coefficient. Figure 7 is a plot of the change in edge filling rate according to the change in average li