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JP-7856373-B2 - Thin film deposition method and thin film deposition apparatus

JP7856373B2JP 7856373 B2JP7856373 B2JP 7856373B2JP-7856373-B2

Inventors

  • 山田 一希
  • 村上 博紀
  • 酒井 宗一朗
  • 山地 智仁

Assignees

  • 東京エレクトロン株式会社

Dates

Publication Date
20260511
Application Date
20220927

Claims (9)

  1. Prepare a substrate having a resist film with an opening formed on its upper surface, By supplying a metal-containing gas to the substrate, the metal is impregnated into at least the upper part of the resist film. By supplying a precursor gas containing silanol to the substrate, a protective film containing silicon and oxygen is selectively formed on the upper surface of the resist film compared to the side and bottom surfaces of the opening. It has, The aforementioned metal is a metal or metalloid having Lewis acid properties, or a compound thereof, and is used in a film formation method.
  2. The resist film comprises an uppermost layer and one or more lower layers provided below the uppermost layer. The film-forming method according to claim 1, wherein the uppermost layer is more easily permeated with the metal than all of the lower layers.
  3. The film formation method according to claim 2, wherein the uppermost layer has a higher surface density of metal-incorporating functional groups compared to all the lower layers.
  4. A film formation method according to claim 1, comprising the steps of: impregnating the resist film with the metal at least into the upper part of the resist film; forming a flattening film on the resist film to flatten any steps in the resist film; exposing the upper part of the resist film by scraping off the flattening film; forming the protective film on the upper part of the resist film; and removing the flattening film that seals the openings in the resist film.
  5. The method for forming a film according to claim 4, wherein the planarization film is an organic film.
  6. A film formation method according to claim 1, comprising the steps of: impregnating the resist film with the metal at least into the upper part of the resist film; forming a conformal film along the step in the resist film on the upper surface of the resist film and the side surface of the opening; selectively etching the upper part of the conformal film to expose the upper part of the resist film; forming the protective film on the upper part of the resist film; and removing the conformal film remaining on the side surface of the opening, in this order.
  7. The film formation method according to claim 6, wherein the conformal film is an inorganic film.
  8. The method for forming a film according to claim 1 , wherein the metal comprises one or more elements selected from Al, Ti, Zr, Zn, Hf, B, and In.
  9. Processing container and The processing container includes a substrate holding section that holds the substrate inside, A gas supply unit that supplies gas to the inside of the processing container, A gas discharge unit that discharges gas from inside the processing container, A transport unit for loading and unloading the substrate into and out of the processing container, A control unit that controls the gas supply unit, the gas discharge unit, and the transport unit, and carries out the film formation method according to any one of claims 1 to 8 , A film deposition apparatus equipped with the following features.

Description

This disclosure relates to a film deposition method and a film deposition apparatus. Patent Document 1 discloses a technique for impregnating a resist film with a metal. Patent Document 2 discloses a technique for forming a thin film of silicon dioxide on a substrate by alternately supplying a metal precursor such as trimethylaluminum (TMA) and a silanol such as tris(tert-pentoxy)silanol (TPSOL) to the substrate. Japanese Patent Publication No. 2020-38929Japanese Patent Publication No. 2010-10686 Figure 1 is a flowchart showing a film deposition method according to one embodiment.Figure 2(A) shows an example of S101, Figure 2(B) shows an example of S102, and Figure 2(C) shows an example of S103.Figure 3(A) shows a modified version of Figure 2(A), Figure 3(B) shows a modified version of Figure 2(B), and Figure 3(C) shows a modified version of Figure 2(C).Figure 4 shows an example of the infrared spectral spectrum of a resist film supplied with TMA gas only, and an example of the infrared spectral spectrum of a resist film supplied with TMA gas and TPSOL gas in that order.Figure 5 is a flowchart showing the post-processing steps of a film deposition method according to one embodiment.Figure 6(A) shows an example of S201, Figure 6(B) shows an example of S202, and Figure 6(C) shows an example of S203.Figure 7 is a flowchart showing the film formation method according to the first modified example.Figure 8(A) shows an example of S301, Figure 8(B) shows an example of S302, Figure 8(C) shows an example of S303, Figure 8(D) shows an example of S304, Figure 8(E) shows an example of S305, and Figure 8(F) shows an example of S306.Figure 9 is a flowchart showing the film formation method according to the second modified example.Figure 10(A) shows an example of S401, Figure 10(B) shows an example of S402, Figure 10(C) shows an example of S403, Figure 10(D) shows an example of S404, Figure 10(E) shows an example of S405, and Figure 10(F) shows an example of S406.Figure 11 is a cross-sectional view showing a film deposition apparatus according to one embodiment. The embodiments of this disclosure will be described below with reference to the drawings. Note that identical or corresponding components in each drawing are denoted by the same reference numerals, and their descriptions may be omitted. A film deposition method according to one embodiment will be described with reference to Figures 1 to 3. The film deposition method includes, for example, steps S101 to S103 shown in Figure 1. Step S101 includes preparing the substrate 100 shown in Figure 2(A). Preparing the substrate 100 includes, for example, loading the substrate 100 into the processing container. The substrate 100 comprises, for example, a base substrate 110, an etching target film 120, a hard mask film 130, and a resist film 140, in this order. The base substrate 110 is, for example, a silicon wafer, a compound semiconductor wafer, or a glass substrate. The etchable film 120 is a film that transfers the aperture pattern of the resist film 140. The etchable film 120 is, for example, a spin-on carbon film. A spin-on carbon film is an amorphous film mainly composed of carbon (C). The hard mask film 130 is used when the resist film 140 has a thin film thickness. An example of a thin resist film 140 is a resist film for EUV (Extreme Ultraviolet) exposure. The hard mask film 130 is, for example, a spin-on-glass film. A spin-on-glass film is an amorphous film mainly composed of silicon (Si) and oxygen (O). The resist film 140 has openings formed on its upper surface. The resist film 140 is formed from a photoresist composition. The photoresist composition is, for example, a chemically amplified type. The resist film 140 has functional groups that incorporate metal in step S102, which will be described later. The functional groups can be general types, but for example, phenyl groups or acrylic groups. Step S102, as shown in Figure 2(B), includes supplying a metal-containing gas to the substrate 100 to impregnate the metal into at least the upper part of the resist film 140, that is, to allow the metal to penetrate at least the upper part of the resist film 140. In Figure 2(B), 140A is the portion of the resist film 140 that has been impregnated with metal. The metal penetrates from the surface to the interior of the resist film 140, for example, by a nucleophilic substitution reaction. The metal includes metals or metalloids having Lewis acid properties, or compounds thereof. Specifically, the metal includes, for example, one or more elements selected from Al, Ti, Zr, Zn, Hf, B, and In. As metal-containing gases, for example, organometallic compound gases are used. The smaller the molecular weight of the organometallic compound gas, the easier it is for the metal to penetrate. Examples of organoaluminum compound gases include trimethylaluminium (TMA) gas or triethylaluminium (TEA) gas. Examples of organotitanium compound gases include tetrakis(dimethylamino)titanium