JP-7855124-B2 - Film deposition method and film deposition apparatus

JP7855124B2JP 7855124 B2JP7855124 B2JP 7855124B2JP-7855124-B2

Inventors

藤田成樹
光成正
菊地貴倫

Assignees

東京エレクトロン株式会社

Dates

Publication Date: 20260507
Application Date: 20250623
Priority Date: 20200508

Claims (18)

The process involves supplying liquid to the recesses of a substrate whose surface includes adjacent recesses and protrusions, The process involves supplying a processing gas that chemically alters the liquid to the surface of the substrate, moving the liquid from the recess to the top surface of the protrusion through a reaction between the processing gas and the liquid, and selectively forming a film on the top surface of the protrusion on the surface of the substrate. A method for forming a film, wherein the liquid is a liquid halide, a liquid metal, or a liquid polymer or ionic liquid supplied to the recess by a spin coating method.
The aforementioned liquid is a liquid halide, The method for forming a film according to claim 1, wherein supplying the liquid to the recess is to form the liquid by a reaction between the source gas of the halide and a reaction gas that reacts with the source gas.
Supplying the liquid into the recess means When the raw material gas and the reaction gas are supplied simultaneously, the process includes plasma formation of both the raw material gas and the reaction gas. The film formation method according to claim 2, wherein when the raw material gas and the reaction gas are supplied alternately, the reaction gas is plasma-generated.
The film-forming method according to any one of claims 1 to 3, wherein the processing gas used to chemically alter the liquid contains elements incorporated into the liquid.
The film-forming method according to claim 4, wherein the processing gas used to chemically alter the liquid includes an oxygen-containing gas.
The film-forming method according to claim 4, wherein the processing gas used to chemically alter the liquid includes a nitrogen-containing gas.
The film-forming method according to claim 4, wherein the processing gas used to chemically alter the liquid includes a hydride gas.
The method for forming a film according to claim 7, wherein the hydride comprises Si, Ge, B, C, or P.
The film-forming method according to any one of claims 1 to 3, wherein the processing gas used to chemically alter the liquid degasses the elements constituting the liquid.
The film-forming method according to claim 9, wherein the processing gas used to chemically alter the liquid includes a reducing gas.
The film-forming method according to claim 10, wherein the reducing gas is hydrogen gas or deuterium gas.
The method for forming a film according to any one of claims 1 to 11, wherein selectively forming the film on the top surface of the protrusion includes plasma-forming the processing gas that chemically alters the liquid.
A film-forming method according to any one of claims 1 to 12, comprising repeatedly supplying the liquid to the recess and selectively forming the film on the top surface of the protrusion.
A film-forming method according to any one of claims 1 to 13, further comprising modifying the film formed on the top surface of the protrusion.
The film-forming method according to any one of claims 1 to 14, wherein when the liquid is supplied to the recess, the temperature of the substrate is lower than the decomposition point of the liquid.
Processing container and Inside the processing container, there is a holding part that holds the substrate horizontally with the surface including the recess and protrusion facing upward, A gas supply unit supplies a raw material gas, a reaction gas that reacts with the raw material gas, and a processing gas that chemically alters the liquid formed by the reaction between the raw material gas and the reaction gas to the surface of the substrate held by the holding unit. It includes a control unit that controls the gas supply unit, The control unit, The liquid formed by the reaction between the raw material gas and the reaction gas is supplied to the recess of the substrate, The process gas is supplied to the surface of the substrate, and the reaction between the process gas and the liquid causes the liquid to move from the recess to the top surface of the protrusion, thereby selectively forming a film on the top surface of the protrusion on the surface of the substrate. We will implement the following: A film deposition apparatus in which the liquid is a liquid halide or a liquid metal.
Processing container and Inside the processing container, there is a holding part that holds the substrate horizontally with the surface including the recess and protrusion facing upward, A gas supply unit supplies a processing gas to the surface of the substrate held by the holding unit, which chemically alters the liquid previously supplied to the recess by a spin coating method, It includes a control unit that controls the gas supply unit, The control unit, The substrate, which has had the liquid supplied to the recesses in advance by a spin coating method, is held in the holding part, The process gas is supplied to the surface of the substrate, and the reaction between the process gas and the liquid causes the liquid to move from the recess to the top surface of the protrusion, thereby selectively forming a film on the top surface of the protrusion on the surface of the substrate. We will implement the following: The aforementioned liquid is a liquid polymer or an ionic liquid, in a film-forming apparatus.
The film deposition apparatus according to claim 16 or 17, comprising a plasma generation unit that generates plasma inside the processing vessel.

Description

This disclosure relates to a film deposition method and a film deposition apparatus. Patent Document 1 discloses a method for selectively forming a film on a specific region of a substrate without using photolithography. This method involves selectively forming Si adsorption sites on the flat surface of the substrate, rather than on the flat surface itself or on the walls of trenches recessed from it. Japanese Patent Publication No. 2018-117038 Figure 1 is a flowchart showing a film deposition method according to one embodiment.Figure 2 is a cross-sectional view showing an example of a substrate, where (A) is a cross-sectional view showing the period after step S1 and before step S2, (B) is a cross-sectional view showing the middle of step S2, and (C) is a cross-sectional view showing the period after step S2.Figure 3 is a cross-sectional view showing a film deposition apparatus according to one embodiment.Figure 4 is a flowchart showing a modified example of the film deposition method shown in Figure 1.Figure 5 shows SEM images of the substrate according to Example 1, where (A) is an SEM image after step S1 and before step S2, (B) is an SEM image taken during step S2, and (C) is an SEM image taken after step S2.Figure 6 shows SEM images of the substrate according to Example 2, where (A) is an SEM image taken after step S1 and before S2, and (B) is an SEM image taken after step S2.Figure 7 shows the relationship between the processing time in step S4 (Table 2) according to Example 3 and the thickness of the liquid in the recess.Figure 8(A) is an SEM image of the substrate after processing according to Example 4, Figure 8(B) is an SEM image of the substrate after processing according to Example 5, Figure 8(C) is an SEM image of the substrate after processing according to Example 6, and Figure 8(D) is an SEM image of the substrate after processing according to Example 7.Figure 9(A) is an SEM image of the substrate after processing according to Example 8, Figure 9(B) is an SEM image of the substrate after processing according to Example 9, and Figure 9(C) is an SEM image of the substrate after processing according to Example 10.Figure 10(A) is an SEM image of the substrate after processing according to Example 11, and Figure 10(B) is an SEM image of the substrate after processing according to Example 12.Figure 11(A) is an SEM image of the substrate after processing according to Example 13, and Figure 11(B) is an SEM image of the substrate after processing according to Example 14.Figure 12 is an SEM image of the substrate after processing according to Example 17.Figure 13 is an SEM image of the substrate after processing according to Example 18. 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. Referring to Figure 1, an example of a film deposition method will be described. The film deposition method comprises steps S1 and S2. In step S1, as shown in Figure 2(A), liquid L is supplied to the recess Wb of the protrusion Wc that constitutes the substrate surface Wa. The liquid L may be supplied directly to the recess Wb, or it may be supplied to the recess Wb from the top surface Wd of the protrusion. Furthermore, the liquid L may overflow from the recess Wb and cover the top surface Wd of the protrusion. The substrate surface Wa includes the bottom surface of the recess, the side surface of the recess, and the top surface Wd of the protrusion. The top surface Wd of the protrusion is a flat surface, and the recess Wb is recessed from the top surface Wd of the protrusion. The substrate W includes, for example, a base substrate W1 including a silicon wafer, and a textured film W2 formed on the base substrate W1. The textured film W2 forms recesses Wb and protrusions Wc. The recesses Wb are trenches or via holes, etc. In this embodiment, the recesses Wb penetrate the textured film W2, but they do not necessarily have to. The protrusions Wc may be pillars, etc. In this embodiment, the textured film W2 is an insulating film, but it may also be a conductive film or a semiconductor film. However, the recesses Wb and protrusions Wc may be formed on the surface of a silicon wafer. Liquid L is preferably one that possesses strong intermolecular forces. The stronger the intermolecular forces, the stronger the cohesive force. If the cohesive force of liquid L is large, evaporation of liquid L can be prevented. The intermolecular forces of liquid L are, for example, 30 kJ/mol or higher. Liquid L is, for example, a halide. A liquid halide is formed, for example, by the reaction of a source gas for the halide and a reaction gas that reacts with the source gas. The formation of liquid L may be promoted by plasmaizing both the source gas and the reaction gas, or the reaction gas. The gas is, for example, TiCl₄ gas, and the reaction gas is, for ex