Search

JP-7855631-B2 - Patterning composition, precursor and patterning of organotin oxide hydroxides

JP7855631B2JP 7855631 B2JP7855631 B2JP 7855631B2JP-7855631-B2

Inventors

  • スティーブン・ティ・マイヤーズ
  • ジェレミー・ティ・アンダーソン
  • ブライアン・ジェイ・カーディノー
  • ジョセフ・ビー・エドソン
  • カイ・ジアン
  • ダグラス・エイ・ケシュラー
  • アラン・ジェイ・テレッキー

Assignees

  • インプリア・コーポレイション

Dates

Publication Date
20260508
Application Date
20240501
Priority Date
20151013

Claims (20)

  1. The process includes a step of depositing a tin precursor composition having a radiosensitive Sn-C bond and a hydrolyzable ligand on the surface of a substrate to form an organic tin oxide-containing film. When the aforementioned film is completely hydrolyzed, the following formula is obtained: R z SnO (2-(z/2)-(x/2)) (OH) x (In the formula, 0 < (z + x) < 4 and z > 0, and R is an alkyl, cycloalkyl, or substituted alkyl moiety having 1 to 31 carbon atoms.) The composition comprises a composition formed from the hydrolysis of the tin precursor composition, represented by the following: A method for forming a radiosensitive, pattern-forming organic tin oxide-containing film, wherein the tin precursor composition contains 0.005 M to 1.4 M of tin.
  2. The method according to claim 1, wherein the film comprises Sn-OH bonds, Sn-O-Sn bonds, and the radiosensitive Sn-C bonds.
  3. The method according to claim 1 or 2, wherein the organic tin oxide film is cleavable by at least one of UV light, EUV light, and electron beam irradiation.
  4. The method according to any one of claims 1 to 3, wherein the hydrolyzable ligand comprises a halide, alkoxide, alkylamide, alkynide, azide, dialkylamide, siloxo, silylamide, disilylamide, aryloxo, amidato, amidinato, imide, or a fluorinated analog thereof or a mixture thereof.
  5. The method according to any one of claims 1 to 3, wherein the tin precursor composition comprises t-butyltris(dimethylamide)tin, i-propyltris(dimethylamide)tin, t-butyltris(diethylamide)tin, i-propyltin trichloride, or a combination thereof.
  6. The method according to any one of claims 1 to 5, wherein the deposition step is carried out by a gas-based deposition process including chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD).
  7. The method according to any one of claims 1 to 5, wherein the deposition step is performed by a spin coating method, a spray coating method, a dip coating method, a knife-edge coating method, a printing method, or a combination thereof.
  8. A patterning method comprising the steps of forming a radiosensitive organotin oxide-containing film using the method according to any one of claims 1 to 7, and patterning the film to at least one of UV light, EUV light, and electron beam irradiation to form exposed and unexposed portions in which the Sn-C bond cleavage occurs in the exposed portions.
  9. The method according to claim 8, wherein the exposed portion is at least partially condensed compared to the unexposed portion.
  10. The method according to claim 8, wherein the unexposed portion is soluble in an organic solvent.
  11. The method according to claim 8, wherein the exposed portion is insoluble in organic solvents.
  12. The method according to claim 8, further comprising removing at least a portion of the exposed portion during the developing process.
  13. The method according to claim 12, wherein the exposed portion is removed using an aqueous base in the developing step.
  14. The organotin composition is produced by hydrolysis of a precursor composition comprising two or more organotin compounds having different hydrocarbyl ligands and ligands independently having hydrolyzable bonds with Sn. The organotin composition is given by the following formula: a1 R1 z1 SnO ( 2-z1/2-x1/2) (OH) x1 + a2 R2 z2 SnO ( 2-z2/2-x2/2) (OH) x2 + a3 R3 z3 SnO ( 2-z3/2-x3/2) (OH) x3 (where 0 < (z1, z2, z3) ≤ 2, 0 < (x1, x2, x3) < 3, a1 > 0, a2 > 0, a3 ≥ 0, and R1 , R2 , and R3 are independently hydrocarbyl ligands having 1 to 31 carbon atoms.) Represented by, A radiosensitive film comprising an organotin composition having a blend of two or more different hydrocarbyl ligands, where R1 , R2 , and R3 are different hydrocarbyl ligands.
  15. The film according to claim 14, wherein the hydrocarbyl ligand includes a linear, branched, cyclic, aryl, alkenyl, benzyl, alkynyl, heteroatomic functional group-substituted hydrocarbyl group, or a combination thereof.
  16. The film according to claim 15, wherein the heteroatom functional group comprises a cyano, thio, silyl, ether, keto, ester, halogenated group, or a combination thereof.
  17. The film according to claim 14, wherein the hydrocarbyl ligand comprises methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, sec-butyl, tert-amyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, 1-adamantyl, 2-adamantyl, or a combination thereof.
  18. The film according to claim 14, wherein the hydrocarbyl ligand comprises tert-butyl, isopropyl, and/or methyl.
  19. The film according to any one of claims 14 to 18, wherein the precursor composition comprises an organotin compound represented by the formula R1 y1 SnX1 4-y1 and an organotin compound represented by the formula R2 y2 SnX2 4 - y2 (wherein R1 and R2 are bonded to Sn by a metal-carbon bond, 1 < (y1, y2) ≤ 2, and X1 and X2 are ligands independently having hydrolyzable bonds with Sn).
  20. The film according to claim 19, wherein the precursor composition contains at least 5 mole percent of each organotin compound.

Description

Cross-reference of related applications This application is a concurrently pending U.S. Provisional Patent Application No. 62/240,812, filed on 13 October 2015 with Meyers et al., entitled “Organotin Oxide Hydroxide Patterning Compositions With Precursor Vapor Deposition”, and a concurrently pending application to Cardineau et al., filed on 19 February 2016, entitled “Precursor Compositions for Organotin Oxide Hydroxide Photographist This invention claims priority to the concurrently pending U.S. Provisional Patent Application No. 62/297,540, entitled “Flims”, both of which are incorporated herein by reference. This invention relates to a precursor composition that can be coated and hydrolyzed in situ to form a coating containing organotin oxide hydroxide. The invention further relates to a radiosensitive organotin oxide hydroxide coating that can be effectively patterned using UV, EUV, or electron beam irradiation to form a high-resolution pattern with low linewidth roughness. To form semiconductor-based devices and other electronic devices or other complex microstructures, materials are generally patterned to integrate their structure. Therefore, these structures are typically formed through an iterative process of deposition and etching, where patterns are formed from various materials. In this way, many devices can be formed in a small area. Some technological advancements involve reducing the mounting area for devices, which can be desirable for improving performance. Organic compositions can also be used as radiation-patterned resists, allowing the chemical structure of the organic composition to be altered to match the pattern created by radiation. For example, the process of patterning semiconductor wafers requires lithographically transferring a desired image from a thin film of radiation-sensitive organic material. Resist patterning generally involves several steps, such as exposing the resist to a selected energy source (e.g., through a mask) to record a latent image, and then developing the resist to remove selected areas. In the case of positive resists, the exposed areas can be transformed to allow for selective removal, whereas in the case of negative resists, unexposed areas can be removed more easily. Generally, patterns are developed using radiation, reactive gases, or liquid solutions to selectively remove highly sensitive areas of the resist, while other parts of the resist function as an etching-resistant protective layer. Liquid developers can be particularly effective in developing latent images. The substrate can be selectively etched through windows or gaps in the remaining areas of the protective resist layer. Alternatively, material can be deposited in the exposed areas of the substrate beneath through the developed windows or gaps in the remaining areas of the protective resist layer. Finally, the protective resist layer is also removed. This process can be repeated to form further layers of material to be patterned. Materials can be deposited using chemical vapor deposition, physical vapor deposition, or other desired methods. Further processing steps, such as the deposition of conductive materials or dopant injection, are also possible. In the fields of microfabrication and nanofabrication, features in integrated circuits have become extremely small for the purpose of achieving high integration density and improving circuit functionality. This is a schematic perspective view of a radiation patterned structure with latent images.This is a side view of the structure shown in Figure 1.Figure 1 is a schematic perspective view of the structure after developing the latent image, removing the unirradiated coating material, and forming a patterned structure.Figure 3 is a side view of the patterned structure.Figure 1 is a schematic perspective view of the structure after developing the latent image, removing the irradiated coating material, and forming a patterned structure.Figure 5 is a side view of the patterned structure.This is a scanning electron microscope (SEM) image of a fixed pattern formed on a substrate with a line spacing of 16.7 nm, using an EUV dose of 56 mJ/ cm² .This is a plot of the film thickness after exposure and development as a function of EUV dose, formed from 50 circular pads with a diameter of 500 microns, which were exposed at stepwise doses using radiation resist on a substrate coated by in situ hydrolysis as described herein.This is a plot of two FTIR spectra comparing a film formed using solution-based hydrolysis and a film formed by in-situ hydrolysis during coating.This is a set of plots using EUV contrast curves, including a function of dose, for coatings formed using three different amounts of Sn( NMe2 ) 4 in a radiosensitive coating before in-situ hydrolysis.This is a set of micrographs of five patterned coatings formed using the described compositions and irradiation doses.This is a plot of linewidth roughness (LWR) as a function of dose-size value for