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CN-121978863-A - Lithographic method and element and device obtainable by the method

CN121978863ACN 121978863 ACN121978863 ACN 121978863ACN-121978863-A

Abstract

The present invention relates to a lithographic process comprising using a novel organometallic compound, a polymer obtained by subjecting one or more compounds to polymerization conditions, a composition comprising an organometallic compound and/or a polymer, and developing the formed exposed resist film with one or more developers, thereby forming a patterned resist film. The present disclosure also provides an optical element, an optically active device or an optical or semiconductor device obtainable by the method defined in the present disclosure.

Inventors

  • Jagadish Salancik
  • Juha Lantala
  • Thomas. Al-Qaeda
  • Yeli Paula Sari
  • ZENG LITING
  • XU FENG

Assignees

  • 湃邦(浙江)新材料有限公司

Dates

Publication Date
20260505
Application Date
20241231
Priority Date
20241025

Claims (20)

  1. 1. A lithographic method, comprising: i) Applying an organometallic compound represented by the formula (I) or (II), or Polymers obtained by subjecting one or more compounds of formula (I) and/or formula (II) to polymerization conditions, optionally in the presence of oxygen, or Comprising an organometallic compound represented by the formula (I) or (II) and/or a polymer, For use with a resist on a substrate, Wherein, the M represents a metal, in particular a transition metal, a non-metal or a group 1 to 15 metalloid; R 1 represents hydrogen or an optionally substituted hydrocarbyl residue; R 2 represents hydrogen, a hydrocarbyl residue that is a saturated or unsaturated, linear, branched or cyclic hydrocarbon, optionally substituted with one or more reactive or non-reactive groups, preferably containing heteroatoms; R 3 represents an alkenyl radical having 2 to 10 carbon atoms, which alkenyl radical may optionally be substituted by one or more alkyl radicals having 1 to 10 carbon atoms, or an acrylate, methacrylate, urethane, thiocarbamate or acetate, or R 3 represents a residue corresponding to the structure in brackets to the left of formula (II), wherein R 1 represents hydrogen or an optionally substituted hydrocarbyl residue, R 2 represents hydrogen, a hydrocarbyl residue or a saturated or unsaturated, linear, branched or cyclic hydrocarbon, optionally substituted with one or more reactive or non-reactive groups, preferably containing heteroatoms, at least one of said substituents R1 and R2 being different in the sense of R3 from the corresponding substituent of the structure placed in brackets to the left of formula (II); A represents a heteroatom selected from oxygen and sulfur, and U and v are respectively selected from integers with the value range of 1 to 10; Thereby forming a resist film on the substrate; ii) exposing the formed resist film to light or electron beam radiation to form an exposed resist film on the substrate, and Iii) Developing the formed exposed resist film with one or more developing agents selected independently from the group of compounds represented by formula (VIII), formula (IX), formula (X), formula (XI) and formula (XII), Wherein R 10 、R 11 、R 12 、R 13 、R 14 and R 15 are each independently selected from the group consisting of linear and branched hydrocarbon groups having 1 to 10 carbon atoms, and R 16 and R 17 are each independently selected from the group consisting of hydrogen having 1 to 10 carbon atoms, linear and branched hydrocarbon groups, linear and branched alkoxy groups having 1 to 10 carbon atoms, and halogen.
  2. 2. The lithographic method as claimed in claim 1, wherein at least one of the one or more developers has a hansen solubility parameter (δh) between 3 and 12.
  3. 3. The lithographic method of any of claims 1-2, wherein at least one of the one or more developers is independently selected from the group of compounds represented by formula (VIII), wherein R 10 and R 11 are independently selected from methyl, ethyl, propyl, isopropyl, butyl, pentyl, neopentyl and neopropyl, respectively.
  4. 4. The lithographic method of any of claims 1-2, wherein at least one of the one or more developers is each independently selected from the group of compounds represented by formula (IX), wherein R 12 is methyl, ethyl, propyl, or butyl.
  5. 5. The lithographic method of any of claims 1-2, wherein at least one of the one or more developers is independently selected from the group of compounds represented by formula (X), wherein R 13 and R 14 are independently selected from methyl, ethyl, isobutyl, hexyl, heptyl, nonyl and decyl, respectively.
  6. 6. The lithographic method of any one of claims 1-2, wherein at least one of the one or more developers is each independently selected from the group of compounds represented by formula (XI), wherein R 15 is ethyl, propyl, isopropyl, pentyl, neopentyl, neopropyl, butyl, pentyl or hexyl, preferably propyl or butyl, more preferably isopropyl, sec-butyl or tert-butyl, even more preferably sec-butyl or tert-butyl.
  7. 7. The lithographic process of any of claims 1-2, wherein at least one of the one or more developers is each independently selected from the group of compounds represented by formula (XII), wherein R 16 and R 17 are each independently selected from hydrogen, methyl, methoxy and chloro, preferably R 16 is hydrogen and R 17 is methyl, methoxy or chloro, more preferably R1 6 is hydrogen and R 17 is methoxy.
  8. 8. The lithographic method of any of claims 1-2, wherein the one or more developers are selected from the group consisting of sec-butyl acetate, tert-butyl acetate, isopropyl acetate, and anisole.
  9. 9. The lithographic method of any of claims 1-2, wherein the one or more developers are two developers selected from N-bromoacetamide and propylene glycol methyl ether acetate, N-bromoacetamide and 2-heptanone, propylene glycol methyl ether acetate and 2-heptanone, toluene and propylene glycol methyl ether.
  10. 10. The lithographic method of any of claims 1-9, wherein exposing the formed resist film to light or electron beam radiation is exposing the formed resist film to light having a wavelength selected from 13.5nm, 193nm, 248nm, and 365nm, or a combination thereof.
  11. 11. The lithographic method of any of claims 1-10, wherein in ii) the formed resist film is exposed to electron beam radiation (EBEAM).
  12. 12. The lithographic method of any of claims 1-11, wherein the one or more developers are toluene and propylene glycol methyl ether, and the propylene glycol methyl ether is present in an amount of at least 1% by weight based on the total weight of toluene and propylene glycol methyl ether.
  13. 13. The lithographic method of any of claims 1-12, wherein developing the formed exposed resist film with the one or more developers takes from 10 to 240 seconds.
  14. 14. The lithographic method of any of claims 1-13, wherein the substrate is a semiconductor substrate.
  15. 15. A lithographic method for producing a semiconductor device according to any of claims 1-14, wherein the method comprises: applying the compound, the polymer or the composition as defined in any one of claims 1 to 14 to a semiconductor substrate to form a thin film, and baking the compound, the polymer or the composition to form an underlying film on the substrate; applying a resist on the formed underlayer film to form a resist film; Exposing the formed resist film to light or electron beam radiation to form an exposed resist film; developing the formed exposed resist film with the one or more developers to form a patterned resist film on the substrate; etching the underlying film according to the pattern of the patterned resist film, and The semiconductor substrate is processed according to the pattern of the resist film and the resist underlayer film.
  16. 16. A lithographic method for producing an optical or semiconductor device according to any of claims 1-14, the method comprising: applying an organic underlayer film composition on a surface of a semiconductor substrate, and baking the organic underlayer film composition to form an organic underlayer film; applying the compound, the polymer or the composition as defined in any one of claims 1 to 14 on the organic underlayer film formed, and baking the compound, polymer or composition to form a resist film; Exposing the resist film formed to light or electron beam radiation; Developing the formed exposed resist film with the one or more developers, thereby forming a patterned resist film; etching a resist underlayer film according to the pattern of the patterned resist film; Etching the organic underlayer film according to the pattern of the patterned resist underlayer film, and The semiconductor substrate is processed according to the pattern of the imaged organic underlayer film.
  17. 17. A lithographic method for producing an optical or semiconductor device according to any of claims 1-14, the method comprising: applying a spin carbon (SOC), such as a high temperature (350 ℃ to 400 ℃) SOC, or an a-carbon layer obtained by CVD on the surface of the substrate; Applying a layer of high silicon containing compound or silicon nitride or metal oxide on said SOC or said alpha-carbon layer; Applying a functional coating comprising the compound, the polymer or the composition as defined in any one of claims 1-14 on the high silicon content composition layer or the silicon oxide nitride or metal oxide layer on the SOC or the alpha-carbon layer to form a resist underlayer functional layer; applying a resist on the resist underlayer functional layer to form a resist film; exposing the formed resist film to light or electron beam radiation to form an exposed resist film; Developing the formed exposed resist film with the one or more developers, thereby forming a patterned resist film; etching the resist underlayer functional layer according to the pattern of the patterned resist film, and The substrate is processed according to the pattern of the resist film and the resist underlayer functional layer.
  18. 18. A lithographic method for producing an optical element or an optically active device according to any of claims 1 to 14, the method comprising: Applying the compound, the polymer or the composition as defined in any one of claims 1 to 14 to form a resist underlayer film on the surface of a substrate, and baking the compound, polymer or composition to form a resist underlayer film; exposing the resist underlayer film formed to light or electron beam radiation; developing the formed exposed resist underlayer film with the one or more developers, thereby forming a patterned resist film; etching a resist underlayer film according to the pattern of the patterned resist film, and The substrate is processed according to the pattern of the resist film and the resist underlayer film.
  19. 19. The lithographic method of any of claims 1-18, wherein the substrate is made of TiO 2 , si, or GaAs.
  20. 20. A lithographic method for patterning a semiconductor substrate as claimed in claim 19, the method comprising: Forming an organic underlayer film on a surface of a semiconductor substrate; forming an inorganic oxide containing an intermediate layer film on the formed organic underlayer film; Applying the compound, the polymer, or the composition for forming a resist film as defined in any one of claims 1 to 14 on the formed inorganic oxide containing an interlayer film, and baking the compound, the polymer, or the composition to form a resist film; Exposing the resist film formed to light or electron beam radiation; Developing the formed exposed resist film with the one or more developers, thereby forming a patterned resist film; Etching the resist film according to the pattern of the patterned resist film; Etching the inorganic oxide containing the interlayer film according to the pattern of the patterned resist film; Etching the organic underlayer film according to the pattern of the patterned resist film, and The semiconductor substrate is processed according to the pattern of the imaged organic underlayer film.

Description

Lithographic method and element and device obtainable by the method Technical Field The present invention relates to radiation-sensitive organometallic complexes that can be used in lithographic processes and methods of making components and devices using the same. In particular, the present invention relates to functional solution processable organic/multi-metal electronic or photoresist complexes, metal organic and organic multi-metal complex compositions and polymers thereof useful for coating semiconductor and optical substrates and forming metal oxide films, particularly those methods involving the use of one or more developers. Background Advanced lithographic methods using electron beams or extreme ultraviolet light (extreme ultraviolet light, EUV) as radiation sources are of great interest due to their imaging capabilities at resolutions below 10 nm. However, existing EUV resist materials still face many challenges, and a trade-off is typically made between sensitivity (S), line edge roughness (L), and resolution (R). Currently, chemically amplified resists (CHEMICALLY AMPLIFIED RESISTS, CAR) are used to increase sensitivity. CARs consist essentially of a major polymer or molecular component as a matrix, a photoacid generator molecule, and a base quencher molecule. After irradiation, photoacid generator molecules (PAGs) interact with light to generate acids, which then begin to alter the dissolution rate of the matrix during the subsequent post-exposure baking (PEB) step. In this step, the reaction of specific groups of the matrix is catalyzed by photo-generated acid molecules, changing hydrophilicity, or inducing cross-linking or backbone cleavage, thereby changing solubility in a developer, such as an aqueous-based developer. A considerable disadvantage of current CARs is that acid diffusion can cause a large random effect, resulting in bridging between patterns, the hydrodynamic radius of the polymer in CAR making it difficult to achieve feature sizes below 10 nm. In conventional CAR photoresists, the root mean square of the polymer chain end-to-end distance ranges from 6 to 10 nanometers, and in fact, the presence of additives may lead to increased defects. Non-CAR compositions utilizing metal clusters or metal complexes avoid some of the drawbacks of CARs, but still have insufficient shelf life stability due to the presence of environmentally or moisture sensitive functions/functionalities that limit the use of the materials in industrial scale production. It is an object of the present invention to solve at least some of these problems by providing new resist materials and lithographic methods. It is a particular object of the present invention to provide a lithographic patterning method that includes selecting an appropriate developer to increase or adjust throughput. Disclosure of Invention The summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. It is an object of the present invention to provide lithographic methods that can be used in optical lithography applications. The present invention relates to a lithographic method using a metal-organic complex having a first metal chelating moiety and a second polymerizable organic moiety. The invention also provides the use of the novel complexes and oligomers thereof and polymers thereof for forming layers and films, such as metal oxide layers and films, particularly in lithographic applications. It is a further object of the present invention to provide an optical element, an optically active device or an optical or semiconductor device obtainable by the method defined in the present disclosure. In one aspect, there is provided a lithographic method comprising: i) Applying an organometallic compound represented by the formula (I) or (II), or Polymers obtained by subjecting one or more compounds of formula (I) and/or formula (II) to polymerization conditions, optionally in the presence of oxygen, or Comprising an organometallic compound represented by the formula (I) or (II) and/or a polymer, For use with a resist on a substrate, Wherein, the M represents a metal, in particular a transition metal, a non-metal or a group 1 to 15 metalloid; R 1 represents hydrogen or an optionally substituted hydrocarbyl residue; R 2 represents hydrogen, a hydrocarbyl residue that is a saturated or unsaturated, linear, branched or cyclic hydrocarbon, optionally substituted with one or more reactive or non-reactive groups, preferably containing heteroatoms; R 3 represents an alkenyl radical having 2 to 10 carbon atoms, which alkenyl radical may optionally be substituted by one or more alkyl radicals having 1 to 10 carbon atoms, or an acrylate, methacrylate, urethane, thiocarbamate or acetate, or