KR-102960913-B1 - SUBSTRATE PROCESSING METHOD, METHOD OF MANUFACTURING SEMICONDUCTOR DEVICE, SUBSTRATE PROCESSING APPARATUS, AND PROGRAM

KR102960913B1KR 102960913 B1KR102960913 B1KR 102960913B1KR-102960913-B1

Abstract

The present invention enhances selectivity in selective growth. It comprises: (a) a process of supplying a hydrocarbon-containing gas to a substrate having a first underlayer and a second underlayer exposed on its surface to modify the surface of the first underlayer to terminate with hydrocarbons; and (b) a process of supplying an oxygen and hydrogen-containing gas to the substrate after modifying the surface of the first underlayer to selectively form a film on the surface of the second underlayer.

Inventors

와세다, 다카유키
나카가와, 다카시
나카타니, 기미히코
데가이, 모토무
이자키, 다카오
하시모토, 요시토모

Assignees

가부시키가이샤 코쿠사이 엘렉트릭

Dates

Publication Date: 20260508
Application Date: 20240227
Priority Date: 20191227

Claims (20)

(a) (a1) A process of supplying a hydrocarbon-containing gas to a substrate having a first lower layer and a second lower layer on its surface to terminate the surface of the first lower layer with a hydrocarbon group, and (a2) a process of exhausting the space in which the substrate exists, and (b) (b1) a process of forming a first layer at room temperature (25°C) to 120°C by supplying a silicon-containing gas and a catalyst to the substrate having the surface of the first substrate terminated by a hydrocarbon group, and (b2) a process of forming a film on the surface of the second substrate by supplying an oxygen and hydrogen-containing gas and a catalyst to the substrate to oxidize the first layer and form a second layer, by performing these processes a predetermined number of times. having, A substrate processing method in which the temperature of the substrate in (b) is lower than or equal to the temperature of the substrate in (a).
A substrate processing method according to claim 1, wherein the temperature of the substrate in (b) is lower than the temperature of the substrate in (a).
A substrate treatment method according to claim 1, further comprising: (c) a process of performing post-treatment on the substrate having a film formed on the surface of the second lower portion, wherein the temperature of the substrate in (c) is greater than or equal to the temperature of the substrate in (b).
A substrate treatment method according to claim 1, further comprising: (c) a process of performing post-treatment on the substrate having a film formed on the surface of the second lower portion, wherein the temperature of the substrate in (c) is higher than the temperature of the substrate in (b).
A substrate treatment method according to claim 1, further comprising: (c) a process of supplying an oxidizing agent or a radical to the substrate having a film formed on the surface of the second lower part to remove hydrocarbon groups terminating the surface of the first lower part.
A substrate processing method according to claim 1, further comprising (c) a process of raising the temperature of the substrate on which a film is formed on the surface of the second lower portion to be greater than or equal to the temperature of the substrate in (b).
A substrate treatment method according to claim 1, further comprising: (c) raising the temperature of the substrate on which a film is formed on the surface of the second lower part to be higher than the temperature of the substrate in (b), thereby performing at least one of removing hydrocarbon groups terminating the surface of the first lower part and neutralizing the function as an inhibitor.
A substrate processing method according to claim 1, further comprising (c) a process of making the temperature of the substrate on which a film is formed on the surface of the second lower portion higher than the temperature of the substrate in (b).
A substrate treatment method according to claim 1, further comprising: (c) raising the temperature of the substrate on which a film is formed on the surface of the second lower portion to a higher temperature than the temperature of the substrate in (b), and performing at least one of removing the hydrocarbon group terminating the surface of the first lower portion and neutralizing the function as an inhibitor.
A substrate treatment method according to claim 1, further comprising, before performing (a), (d) a process of terminating the surface of the first lower body with a hydroxyl group.
A substrate treatment method according to claim 1, further comprising, before performing (a), (d) a process of removing a natural oxide film formed on the surface of at least one of the first substrate and the second substrate.
A substrate treatment method according to any one of claims 1 to 11, wherein the hydrocarbon group comprises an alkyl group.
A substrate treatment method according to any one of claims 1 to 11, wherein the hydrocarbon group comprises an alkylsilyl group.
A substrate treatment method according to any one of claims 1 to 11, wherein the hydrocarbon group-containing gas also comprises an amino group.
A substrate treatment method according to any one of claims 1 to 11, wherein the oxygen and hydrogen-containing gas is H₂O gas.
A substrate treatment method according to any one of claims 1 to 11, wherein the first substrate is an oxide film and the second substrate is a film other than an oxide film.
A substrate treatment method according to any one of claims 1 to 11, wherein (a1) the hydrocarbon-containing gas is sealed in the space where the substrate is present.
A substrate processing method according to any one of claims 1 to 11, wherein in (a), (a1) and (a2) are repeated alternately multiple times.
A substrate treatment method according to any one of claims 1 to 11, wherein (a) and (b) are performed under a non-plasma atmosphere.
(a) (a1) A process of supplying a hydrocarbon-containing gas to a substrate having a first lower layer and a second lower layer on its surface to terminate the surface of the first lower layer with a hydrocarbon group, and (a2) a process of exhausting the space in which the substrate exists, and (b) (b1) a process of forming a first layer at room temperature (25°C) to 120°C by supplying a silicon-containing gas and a catalyst to the substrate having the surface of the first substrate terminated by a hydrocarbon group, and (b2) a process of forming a film on the surface of the second substrate by supplying an oxygen and hydrogen-containing gas and a catalyst to the substrate to oxidize the first layer and form a second layer, by performing these processes a predetermined number of times. having, A method for manufacturing a semiconductor device in which the temperature of the substrate in (b) is lower than or equal to the temperature of the substrate in (a).

Description

Substrate processing method, method of manufacturing a semiconductor device, substrate processing apparatus, and program The present disclosure relates to a method for manufacturing a semiconductor device, a substrate processing device, and a program. As a process of manufacturing a semiconductor device, a treatment is performed to selectively grow and form a film on the surface of a specific substrate among a plurality of substrates exposed on the surface of a substrate (hereinafter, this treatment is also referred to as selective growth or selective film formation) (see, for example, Patent Document 1). FIG. 1 is a schematic diagram of a longitudinal processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a drawing showing the processing furnace (202) portion as a longitudinal cross-sectional view. FIG. 2 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a diagram showing the processing furnace (202) portion as a cross-sectional view along line AA of FIG. 1. FIG. 3 is a schematic diagram of a controller (121) of a substrate processing device suitablely used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller (121). FIG. 4 is a diagram illustrating a processing sequence in selective growth of one embodiment of the present disclosure. Figure 5(a) is a diagram illustrating the chemical structural formula of DMATMS. Figure 5(b) is a diagram illustrating the chemical structural formula of a hydrocarbon-containing gas having a trialkylsilyl group and an amino group. Figure 5(c) is a diagram illustrating the chemical structural formula of a hydrocarbon-containing gas having a dialkylsilyl group and an amino group. FIG. 6(a) is an enlarged cross-sectional view of the surface of a wafer (200) in which a substrate (200a) containing a silicon oxide film and a substrate (200b) containing a silicon nitride film are respectively exposed on the surface. FIG. 6(b) is an enlarged cross-sectional view of the surface of the wafer (200) after the surface of the substrate (200a) is modified to terminate with hydrocarbons by supplying a hydrocarbon-containing gas. FIG. 6(c) is an enlarged cross-sectional view of the surface of the wafer (200) after a first layer containing silicon and carbon is selectively formed on the surface of the substrate (200b) by supplying a silicon and halogen-containing gas. FIG. 6(d) is an enlarged cross-sectional view of the surface of the wafer (200) after the first layer selectively formed on the surface of the substrate (200b) is oxidized and modified into a second layer containing silicon, oxygen, and carbon by supplying an oxygen and hydrogen-containing gas. FIG. 6(e) is an enlarged cross-sectional view of the surface of a wafer (200) after selectively forming a silicon oxycarbon film on the surface of the substrate (200b). FIG. 6(f) is an enlarged cross-sectional view of the surface of a wafer (200) after removing hydrocarbon groups terminating the surface of the substrate (200a) from the surface of the substrate (200a) by post-processing the wafer (200) shown in FIG. 6(e). Figure 7 is a diagram showing the measurement results of the thickness of a silicon oxycarbon film formed on the surface of various substrates exposed on the surface of a wafer. <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described with reference mainly to FIGS. 1 to 4. (1) Configuration of the substrate processing device As illustrated in FIG. 1, the processing furnace (202) has a heater (207) as a temperature regulator (heating part). The heater (207) is cylindrical in shape and is mounted vertically by being supported on a holding support plate. The heater (207) also functions as an activation mechanism (excitation part) that activates (excites) gas with heat. Inside the heater (207), a reaction tube (203) is arranged concentrically with the heater (207). The reaction tube (203) is made of a heat-resistant material, such as quartz ( SiO2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed top and an open bottom. Below the reaction tube (203), a manifold (209) is arranged concentrically with the reaction tube (203). The manifold (209) is made of a metal material, such as stainless steel (SUS), and is formed in a cylindrical shape with an open top and bottom. The upper part of the manifold (209) is connected to the lower part of the reaction tube (203) to support the reaction tube (203). An O-ring (220a) serving as a sealing member is provided between the manifold (209) and the reaction tube (203). The reaction tube (203) is mounted vertically, similar to the heater (207). The processing vessel (reaction vessel) is mainly formed by the reaction tube (203) and the manifold (209). A processing chamber (201) is f