Substrate processing method, substrate processing apparatus, and program

Abstract

To provide a technique capable of selectively forming a film onto a desired front surface with high accuracy.SOLUTION: A substrate processing method includes: a step of providing a substrate in which a conductive film and an insulation film are exposed to a front surface; a step of selectively forming an oxidant onto the front surface of the insulation film from the conductive film and the insulation film by supplying a material without halogen, the oxidant, and a catalyst to the substrate under an atmosphere of a non-plasma.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] This disclosure relates to a substrate processing method, a substrate processing apparatus, and a program. [Background technology]

[0002] As part of the manufacturing process for semiconductor devices, a process is sometimes performed in which a film is selectively grown and formed on the surface of a specific underlayment film from among several types of underlayment films with different materials exposed on the surface of a substrate (hereinafter this process is also referred to as selective growth or selective film formation) (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-155452 [Patent Document 2] Japanese Patent Publication No. 2020-155607 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the film-forming agents used during selective growth, as well as the by-products generated during the process, can react with the underlying film exposed on the substrate surface. Depending on the material of the underlying film, this can corrode it, making selective growth difficult.

[0005] The purpose of this disclosure is to provide a technology that enables the selective formation of a film on a desired surface with high precision. [Means for solving the problem]

[0006] According to one aspect of this disclosure, A process for providing a substrate in which a conductive film and an insulating film are exposed on the surface, A step of selectively forming an oxide film on the surface of the insulating film, among the conductive film and the insulating film, by supplying a halogen-free raw material, an oxidizing agent, and a catalyst to the substrate in a non-plasma atmosphere, Technology to perform this will be provided. [Effects of the Invention]

[0007] According to this disclosure, it is possible to selectively form a film on a desired surface with high precision. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion in a vertical cross-sectional view. [Figure 2] Figure 2 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion as a cross-sectional view along line AA in Figure 1. [Figure 3] Figure 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4] Figure 4 shows a processing sequence in one aspect of the present disclosure. [Figure 5]FIG. 5(a) is a schematic cross-sectional view showing a surface portion of a wafer having a conductive film and an insulating film on its surface, with a native oxide film formed on the surface of the conductive film. FIG. 5(b) is a schematic cross-sectional view showing a surface portion of the wafer after the native oxide film has been removed from the surface of the conductive film by performing a cleaning step from the state of FIG. 5(a). FIG. 5(c) is a schematic cross-sectional view showing a surface portion of the wafer after a film formation inhibiting layer has been formed on the surface of the conductive film by performing a modification step from the state of FIG. 5(b). FIG. 5(d) is a schematic cross-sectional view showing a surface portion of the wafer after a film has been selectively formed on the surface of the insulating film by performing a film formation step from the state of FIG. 5(c). FIG. 5(e) is a schematic cross-sectional view showing a surface portion of the wafer after the film formation inhibiting layer on the surface of the conductive film has been removed by performing a heat treatment step from the state of FIG. 5(d). [Figure 6] FIG. 6 is a diagram showing a processing sequence in Modification 1 of the present disclosure. [Figure 7] FIG. 7 is a diagram showing a processing sequence in Modification 2 of the present disclosure. [Figure 8] FIG. 8 is a graph showing the evaluation results in Example 1. [Figure 9] FIG. 9 is a graph showing the evaluation results in Example 2.

MODE FOR CARRYING OUT THE INVENTION

[0009] <One Aspect of the Present Disclosure> Hereinafter, one aspect of the present disclosure will be mainly described while referring to FIGS. 1 to 4 and FIGS. 5(a) to 5(e). Note that the drawings used in the following description are all schematic, and the dimensional relationships between the elements shown in the drawings, the ratios of the elements, etc. do not necessarily match the actual ones. Also, the dimensional relationships between the elements and the ratios of the elements do not necessarily match among the plurality of drawings.

[0010] (1) Configuration of the Substrate Processing Apparatus As shown in Figure 1, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas with heat.

[0011] 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 upper end and an open lower end. 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 open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction vessel (reaction vessel) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within this processing chamber 201.

[0012] Within the processing chamber 201, nozzles 249a to 249c, which serve as the first to third supply units, are provided so as to penetrate the side walls of the manifold 209. Nozzles 249a to 249c are also referred to as the first to third nozzles. Nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c, respectively. Nozzles 249a to 249c are all different nozzles, and nozzles 249a and 249c are each provided adjacent to nozzle 249b.

[0013] Gas supply pipes 232a to 232c are equipped with mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, respectively, in order from the upstream side of the gas flow. Downstream of valve 243a in gas supply pipe 232a, gas supply pipes 232d and 232f are connected, respectively. Downstream of valve 243b in gas supply pipe 232b, gas supply pipes 232e and 232g are connected, respectively. Downstream of valve 243c in gas supply pipe 232c, gas supply pipe 232h is connected. Gas supply pipes 232d to 232h are equipped with MFCs 241d to 241h and valves 243d to 243h, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0014] As shown in Figure 2, nozzles 249a to 249c are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, extending upward from the lower part of the inner wall of the reaction tube 203 towards the direction of wafer 200 arrangement. That is, nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region, on the side of the wafer arrangement region where the wafers 200 are arranged, and are provided along the wafer arrangement region. In plan view, nozzle 249b is positioned to be directly opposite the exhaust port 231a (described later) with the center of the wafer 200 being transported into the processing chamber 201 in between. Nozzles 249a and 249c are positioned to sandwich a straight line L passing through the center of nozzle 249b and the center of exhaust port 231a along the inner wall of the reaction tube 203 (outer periphery of the wafer 200) from both sides. Straight line L is also the straight line passing through nozzle 249b and the center of wafer 200. In other words, nozzle 249c is located on the opposite side of nozzle 249a, with respect to the straight line L. Nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250c are provided on the sides of nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c opens so as to face (oppose) the exhaust port 231a in a plan view, making it possible to supply gas toward the wafer 200. Multiple gas supply holes 250a to 250c are provided extending from the bottom to the top of the reaction tube 203.

[0015] From the gas supply pipe 232a, the reforming agent is supplied into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a.

[0016] From the gas supply pipe 232b, the raw material is supplied into the processing chamber 201 via the MFC 241b, valve 243b, and nozzle 249b. The raw material is used as one of the film-forming agents.

[0017] From the gas supply pipe 232c, an oxidizing agent is supplied into the processing chamber 201 via the MFC 241c, valve 243c, and nozzle 249c. The oxidizing agent is used as one of the film-forming agents.

[0018] From the gas supply pipe 232d, the catalyst is supplied into the processing chamber 201 via the MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a. The catalyst is used as one of the film-forming agents.

[0019] From the gas supply pipe 232e, the cleaning agent is supplied into the processing chamber 201 via the MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0020] Inert gas is supplied from gas supply pipes 232f to 232h into the processing chamber 201 via MFCs 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0021] The reformer supply system is mainly composed of gas supply pipe 232a, MFC 241a, and valve 243a. The raw material supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b. The oxidizer supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. The catalyst supply system is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d. The cleaning agent supply system is mainly composed of gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system is mainly composed of gas supply pipes 232f to 232h, MFC 241f to 241h, and valves 243f to 243h. Each or all of the raw material supply system, oxidizer supply system, and catalyst supply system are also referred to as the film-forming agent supply system.

[0022] Of the various supply systems described above, one or all of them may be configured as an integrated supply system 248, which is comprised of valves 243a to 243h and MFCs 241a to 241h. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232h, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232h, i.e., the opening and closing operation of valves 243a to 243h and the flow rate adjustment operation of MFCs 241a to 241h, is controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or segmented integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232h, etc., in units of the integrated unit, and is configured so that maintenance, replacement, and expansion of the integrated supply system 248 can be performed in units of the integrated unit.

[0023] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, the exhaust port 231a is located in a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between, in a plan view. The exhaust port 231a may also be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation in the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure in the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0024] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed outside the reaction tube 203 as a lifting mechanism. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219. The transport device functions as a supply device that provides the wafer 200 into the processing chamber 201.

[0025] Below the manifold 209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as lifting and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0026] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0027] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0028] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0029] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing device, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe functions as a program, combining the procedures for each step in the substrate processing described later, so that the controller 121 causes the substrate processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be referred to simply as "recipes." In this specification, the term "program" may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0030] I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotary mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0031] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241h, the opening and closing operation of valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0032] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, and semiconductor memory such as USB memory and SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0033] (2) Substrate processing process Using the substrate processing apparatus described above, a method for processing a substrate as one step in the manufacturing process of a semiconductor device, specifically, an example of a processing sequence for selectively forming a film on the surface of the insulating film, which is the second underlayment, among the conductive film as the first underlayment and the insulating film as the second underlayment exposed on the surface of the wafer 200 as the substrate, will be explained mainly using Figures 4 and 5(a) to 5(e). For convenience, in the following explanation, a typical example will be described in which the conductive film as the first underlayment is composed of, for example, a copper film (Cu film), and the insulating film as the second underlayment is composed of, for example, a silicon oxide film (SiO2 film, hereinafter also referred to as SiO film). In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0034] The processing sequence in this embodiment is: The steps include providing a wafer 200 in which a conductive film and an insulating film are exposed on the surface, The process involves supplying a halogen-free raw material, an oxidizing agent, and a catalyst to a wafer 200 in a non-plasma atmosphere to selectively form an oxide film on the surface of the insulating film among the conductive film and insulating film. It holds.

[0035] As shown in Figure 4, the step of forming the oxide film involves supplying raw materials to the wafer 200 and supplying an oxidizing agent to the wafer 200, and this cycle is performed a predetermined number of times. A catalyst may be supplied to the wafer 200 in at least one of the steps of supplying raw materials and supplying the oxidizing agent. In Figure 4, as a typical example, a catalyst is supplied in both the step of supplying raw materials and the step of supplying the oxidizing agent. Furthermore, as shown in Figure 4, before performing the step of forming the oxide film, a step may be performed in which a modifier is supplied to the wafer 200 to selectively form a film-forming inhibiting layer on the surface of the conductive film among the conductive film and insulating film. In the step of forming the film-forming inhibiting layer, it is preferable to supply the modifier in a non-plasma atmosphere.

[0036] In other words, the processing sequence shown in Figure 4 is performed under a non-plasma atmosphere. The process involves supplying a modifier to a wafer 200 to selectively form a film-forming inhibiting layer on the surface of the conductive film among the conductive film and insulating film, A step of selectively forming an oxide film on the surface of the insulating film among the conductive film and insulating film by performing a predetermined number of cycles (n times, where n is an integer of 1 or more) that include the steps of supplying raw materials and catalyst to wafer 200 and supplying oxidizing agent and catalyst to wafer 200, This shows an example of how to do it.

[0037] In this specification, the processing sequence described above may also be shown as follows for convenience. The same notation will be used in the following descriptions of modifications and other embodiments.

[0038] Modifier → (Raw material + Catalyst → Oxidizing agent + Catalyst) × n

[0039] Furthermore, as shown in the processing sequence below, the catalyst may be supplied to the wafer 200 in either the step of supplying the raw materials or the step of supplying the oxidizing agent.

[0040] Modifier → (Raw material → Oxidizing agent + Catalyst) × n Modifier → (Raw material + Catalyst → Oxidizing agent) × n

[0041] Furthermore, as shown in Figure 4 and the processing sequence below, a step may be performed to remove the native oxide film formed on the surface of the wafer 200 by supplying a cleaning agent to the wafer 200 before performing the step of forming the film-forming inhibiting layer.

[0042] Cleaning agent → Modifier → (Raw material + Catalyst → Oxidizing agent + Catalyst) × n Cleaning agent → Modifier → (Raw material → Oxidizing agent + Catalyst) × n Detergent → Modifier → (Raw material + Catalyst → Oxidizing agent) × n

[0043] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this specification, when it is stated that "a predetermined layer is formed on the wafer," it may mean that the predetermined layer is formed directly on the surface of the wafer itself or that the predetermined layer is formed on a layer already formed on the wafer. In this specification, the term "substrate" has the same meaning as when it is used with the term "wafer."

[0044] As used herein, the term "agent" includes at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, each of the modifier and film-forming agents (raw material, oxidizing agent, catalyst) may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0045] As used herein, the term "layer" includes at least one of a continuous layer and a discontinuous layer. For example, a film-forming inhibitory layer may include a continuous layer, a discontinuous layer, or both, as long as it is capable of producing a film-forming inhibitory effect.

[0046] (Wafer charge and boat load) When multiple wafers 200 are loaded into the boat 217 (wafer charging), the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the manifold 209 (shutter opening). Then, as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the boat elevator 115 and transported into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are provided into the processing chamber 201.

[0047] The wafer 200 loaded into the boat 217 has a conductive film as a first underlayer and an insulating film as a second underlayer on its surface, as shown in Figure 5(a). As described above, the conductive film is made of, for example, a Cu film, and the insulating film is made of, for example, an SiO film. In addition, a native oxide film is formed on the surface of the conductive film, as shown in Figure 5(a).

[0048] (Pressure adjustment and temperature adjustment) After the boat loading is complete, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by a vacuum pump 246 to achieve the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by a heater 207 to reach the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on the temperature information detected by a temperature sensor 263 to ensure that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0049] (Washing step) Subsequently, a cleaning agent is supplied to the wafer 200.

[0050] Specifically, valve 243e is opened to allow the cleaning agent to flow into the gas supply pipe 232e. The flow rate of the cleaning agent is regulated by MFC 241e and supplied into the processing chamber 201 via gas supply pipe 232b and nozzle 249b, and exhausted from exhaust port 231a. At this time, the cleaning agent is supplied to the wafer 200 from the side of the wafer 200 (cleaning agent supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0051] By supplying a cleaning agent to the wafer 200 under the processing conditions described later, the native oxide film formed on the surface of the conductive film can be removed (etched), as shown in Figure 5(b), and the surface of the conductive film can be exposed. Note that if the insulating film is not an oxide film such as an SiO film, a native oxide film may also be formed on the surface of the insulating film. In this case, the native oxide film formed on the surface of the insulating film can also be removed (etched), and the surface of the insulating film can also be exposed.

[0052] The processing conditions when supplying the cleaning agent in the cleaning step are as follows: Processing temperature: 50-200°C, preferably 70-150°C Processing pressure: 10-2000 Pa, preferably 100-1500 Pa Detergent supply flow rate: 0.05 to 1 slm, preferably 0.1 to 0.5 slm Detergent supply time: 10-60 minutes, preferably 30-60 minutes Inert gas supply flow rate (per gas supply pipe): 1 to 10 slm, preferably 2 to 10 slm Examples are given.

[0053] In this specification, numerical ranges such as "50~200°C" mean that the lower and upper limits are included within that range. For example, "50~200°C" means "50°C or more and 200°C or less." The same applies to other numerical ranges. In this specification, processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure refers to the pressure inside the processing chamber 201. Also, if 0 slm is included in the supply flow rate, 0 slm means the case in which the substance (gas) is not supplied. These also apply in the following explanations.

[0054] After removing the native oxide film from the surface of the conductive film and exposing the surface of the conductive film, valve 243e is closed to stop the supply of cleaning agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any remaining gaseous substances from the processing chamber 201. At this time, valves 243f to 243h are opened and inert gas is supplied into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201.

[0055] The processing conditions when purging in the washing step are as follows: Processing pressure: 1-30 Pa Inert gas supply flow rate (per gas supply pipe): 0.5~20 slm Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Examples include the following. It is preferable that the processing temperature during purging in this step be the same as the processing temperature when supplying the cleaning agent.

[0056] Examples of cleaning agents that can be used include acetic acid (CH3COOH) gas, formic acid (HCOOH) gas, hexafluoroacetylacetone (C5H2F6O2) gas, and hydrogen (H2) gas. In addition to these, other cleaning agents that can be used include aqueous solutions of acetic acid, formic acid, and hydrogen fluoride (HF). That is, the cleaning agent may be a gaseous substance or a liquid substance. Furthermore, the cleaning agent may be a liquid substance such as a mist. One or more of these can be used as the cleaning agent.

[0057] As the inert gas, nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, and other noble gases can be used. One or more of these can be used as the inert gas. This also applies to each of the steps described later.

[0058] Before bringing the wafer 200 into the processing chamber 201, a cleaning step may be performed on the wafer 200 in a substrate processing apparatus different from this substrate processing apparatus (ex-situ) to remove the native oxide film from the surface of the conductive film and expose the surface of the conductive film. In this case, if the insulating film is not an oxide film such as an SiO film, it is preferable to also remove the native oxide film formed on the surface of the insulating film and expose the surface of the insulating film. If the native oxide film has been removed from the surface of the conductive film and insulating film in advance and their surfaces are exposed, the cleaning step can be omitted.

[0059] (Modification step) After the cleaning step, the modifier is supplied to the wafer 200.

[0060] Specifically, valve 243a is opened, and the reforming agent is allowed to flow into the gas supply pipe 232a. The reforming agent's flow rate is adjusted by MFC 241a, and it is supplied into the processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this time, the reforming agent is supplied to the wafer 200 from the side of the wafer 200 (reforming agent supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0061] By supplying a modifier to the wafer 200 under the processing conditions described later, the surface of the conductive film can be modified to form a film formation inhibiting layer by adsorbing at least a portion of the molecular structure of the molecules constituting the modifier onto the surface of the conductive film, as shown in Figure 5(c). That is, by supplying a modifier that reacts with the conductive film to the wafer 200 under the processing conditions described later, the surface of the conductive film can be modified to form a film formation inhibiting layer (adsorption inhibiting layer) by chemically adsorbing at least a portion of the molecular structure of the molecules constituting the modifier onto the surface of the conductive film. This makes it possible to terminate the outermost surface of the conductive film with at least a portion of the molecular structure of the molecules constituting the modifier. For example, if the modifier contains hydrocarbon groups, the film formation inhibiting layer will contain hydrocarbon group terminations, and the outermost surface of the conductive film will be terminated by hydrocarbon groups. If the hydrocarbon group is, for example, an alkyl group, i.e., if the modifier contains an alkyl group, the film formation inhibiting layer will contain alkyl group terminations, and the outermost surface of the conductive film will be terminated by alkyl groups.

[0062] In this step, it is preferable that the reactivity between the modifier and the surface of the conductive film is higher than the reactivity between the modifier and the surface of the insulating film. That is, it is preferable to use a modifier that is more reactive to the surface of the conductive film than to the surface of the insulating film. This makes it possible to selectively form a film formation inhibiting layer on the surface of the conductive film among the conductive film and the insulating film.

[0063] The film-forming inhibitory layer formed in this step contains residues derived from the modifier, which include at least a portion of the molecular structure of the molecules constituting the modifier. In the film-forming step described later, the film-forming inhibitory layer prevents the adsorption of raw materials (film-forming agents) onto the surface of the conductive film and inhibits (suppresses) the progress of the film-forming reaction on the surface of the conductive film.

[0064] At least a portion of the molecular structure of the molecules constituting the modifier, i.e., residues derived from the modifier, can be exemplified by hydrocarbon groups. In this case, the outermost surface of the conductive film will be terminated by hydrocarbon groups. If the hydrocarbon group as a residue derived from the modifier is, for example, an alkyl group, the outermost surface of the conductive film will be terminated by an alkyl group. Hydrocarbon groups such as alkyl groups terminating the outermost surface of the conductive film constitute a film formation inhibiting layer, which in the film formation step described later prevents the adsorption of raw materials (film-forming agents) onto the surface of the conductive film and inhibits (suppresses) the progress of the film formation reaction on the surface of the conductive film.

[0065] Here, the film-forming inhibitory layer (also called the film-forming suppression layer) is sometimes called an inhibitor because it has a film-forming inhibiting effect. In this specification, the term "inhibitor" may refer to the film-forming inhibitory layer, a modifier, residues derived from the modifier, for example, at least a part of the molecular structure of the molecules constituting the modifier, or it may be used as a general term for all of these.

[0066] In this step, at least a portion of the molecular structure of the molecules constituting the modifier may be adsorbed onto a part of the surface of the insulating film, but the amount of adsorption is small, and the amount adsorbed onto the surface of the conductive film is overwhelmingly larger. Such selective (preferential) adsorption is possible because the processing conditions in this step are set so that the modifier does not undergo gas phase decomposition in the processing chamber 201. Also, a substance is used as the modifier that is more reactive with the surface of the conductive film than with the surface of the insulating film. In this step, since the modifier does not undergo gas phase decomposition in the processing chamber 201, at least a portion of the molecular structure of the molecules constituting the modifier does not accumulate on the surface of the insulating film. At least a portion of the molecular structure of the molecules constituting the modifier is selectively adsorbed onto the surface of the conductive film, and as a result the surface of the conductive film is selectively terminated by at least a portion of the molecular structure of the molecules constituting the modifier.

[0067] The processing conditions when supplying the modifier in the modification step are as follows: Processing temperature: Room temperature (25°C) to 300°C, preferably 60 to 100°C Processing pressure: 1 to 2000 Pa, preferably 10 to 1000 Pa Modifier supply flow rate: 0.001 to 2 slm, preferably 0.01 to 0.5 slm Modifier supply time: 1 second to 60 minutes, preferably 1 to 12 minutes Inert gas supply flow rate (per gas supply pipe): 0-20 slm Examples are given.

[0068] After selectively forming a film-forming inhibiting layer on the surface of the conductive film, valve 243a is closed to stop the supply of the modifier into the processing chamber 201. Then, using the same processing procedure and conditions as described above, any gaseous substances remaining in the processing chamber 201 are removed (purged). It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the modifier.

[0069] For example, thiol compounds can be used as modifiers. Thiol compounds are organic compounds having hydrogenated sulfur (S) and have a chemical structure represented by the general formula R-SH (where R is an organic group such as a hydrocarbon group). In R-SH, R is, for example, an alkyl group (-C n H 2n+1 (where n is an integer from 1 to 24) or alkylene group (-(CH2) n - (where n is an integer from 1 to 24), etc. Examples of thiol compounds include dodecanethiol (CH3(CH2) 11 SH, abbreviation: DDT), tetradecanethiol (CH3(CH2) 13 SH (abbreviation: TDT), hexadecanethiol (CH3(CH2) 15 SH, abbreviation: HDT), octadecanethiol (CH3(CH2) 17 SH (abbreviated as ODT), etc., can be used. One or more of these can be used as modifiers.

[0070] In addition, as the modifier, for example, a phosphonic acid compound can be used. The phosphonic acid compound is an organic phosphorus compound having an oxo acid of phosphorus (P) as a mother compound and has a chemical structure represented by the general formula R-PO(OH)2 (R is an organic group such as a hydrocarbon group). R in R-PO(OH)2 is, for example, an alkyl group (-C n H 2n+1 , n is an integer from 1 to 24) or an alkylene group (-(CH2) n -, n is an integer from 1 to 24), etc. Examples of the phosphonic acid compound include dodecylphosphonic acid (CH3(CH2) 11 PO(OH)2, abbreviation: DDPA), tetradecylphosphonic acid (CH3(CH2) 13 PO(OH)2, abbreviation: TDPA), hexadecylphosphonic acid (CH3(CH2) 15 PO(OH)2, abbreviation: HDPA), octadecylphosphonic acid (CH3(CH2) 17 PO(OH)2, abbreviation: ODPA), etc. As the modifier, one or more of these can be used.

[0071] (Film formation step) After performing the modification step, a halogen-free raw material, an oxidizing agent, and a catalyst are supplied to the wafer 200 as film-forming agents in a non-plasma atmosphere to form an oxide film on the surface of the insulating film. That is, a film-forming agent that reacts with the surface of the insulating film is supplied to the wafer 200, and a film is selectively (preferably) formed on the surface of the insulating film. Specifically, the following raw material supply step and oxidizing agent supply step are sequentially executed. In each step, the output of the heater 207 is adjusted, and the temperature of the wafer 200 is maintained at a state not higher than the temperature of the wafer 200 in the modification step, preferably, as shown in FIG. 4, at a state lower than the temperature of the wafer 200 in the modification step.

[0072] [Raw material supply step] In this step, a raw material (raw material gas) and a catalyst (catalyst gas) are supplied as film-forming agents to the wafer 200 after performing the modification step, that is, the wafer 200 after selectively forming a film formation inhibition layer on the surface of the conductive film.

[0073] Specifically, valves 243b and 243d are opened, and the raw material and catalyst are flowed into the gas supply pipes 232b and 232d, respectively. The flow rates of the raw material and catalyst are adjusted by MFCs 241b and 241d, respectively, and supplied into the processing chamber 201 via nozzles 249b and 249a. They are mixed in the processing chamber 201 and exhausted from the exhaust port 231a. At this time, the raw material and catalyst are supplied to the wafer 200 from the side of the wafer 200 (raw material + catalyst supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0074] By supplying the raw materials and catalyst to the wafer 200 under the processing conditions described later, it becomes possible to selectively chemically adsorb at least a portion of the molecular structure of the molecules constituting the raw materials onto the insulating film surface while suppressing the chemical adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the conductive film. As a result, a first layer is selectively formed on the surface of the insulating film. The first layer contains at least a portion of the molecular structure of the molecules constituting the raw materials, which are residues of the raw materials. That is, the first layer contains at least a portion of the atoms constituting the raw materials.

[0075] Furthermore, the selective chemical adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film is possible due to factors such as the formation of a film-forming inhibiting layer on the surface of the conductive film, the presence of Si-OH terminations (adsorption sites) on the surface of the insulating film, and the absence of Si-OH terminations (adsorption sites) on the surface of the conductive film. In other words, the presence of Si-OH terminations on the surface of the insulating film promotes the adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film. On the other hand, the formation of a film-forming inhibiting layer on the surface of the conductive film and the absence of Si-OH terminations on the surface of the conductive film suppress the adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the conductive film. Thus, the reactivity between the raw materials and the surface of the conductive film is lower than the reactivity between the raw materials and the surface of the insulating film, and this is one of the factors that allows for the selective chemical adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film. Furthermore, the first layer formed on the surface of the insulating film during the raw material supply step is transformed into the second layer during the oxidizing agent supply step. However, the surface of the second layer contains Si-OH terminations, while the surface of the conductive film remains Si-OH termination-free. Therefore, selective chemiadsorption proceeds in the second and subsequent cycles, just as in the first cycle.

[0076] In this step, by supplying the catalyst together with the raw materials, the above reaction can be carried out in a non-plasma atmosphere and under low temperature conditions as described later. By forming the first layer in a non-plasma atmosphere and under low temperature conditions as described later, it becomes possible to maintain the molecules and atoms constituting the film formation inhibiting layer formed on the surface of the conductive film without them disappearing (desorbing) from the surface of the conductive film.

[0077] Furthermore, by forming the first layer in a non-plasma atmosphere and under low temperature conditions as described later, the raw materials can be prevented from thermally decomposing (gas-phase decomposition), i.e., from self-decomposing, within the processing chamber 201. This makes it possible to suppress the destruction (desorption, removal, and deactivation) of the film-forming inhibitory layer by the decomposed active raw materials. In addition, this makes it possible to suppress the multiple deposition of at least a portion of the molecular structure of the molecules constituting the raw materials on the surface of the conductive film and the insulating film, and to selectively adsorb at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film. In other words, forming the first layer in a non-plasma atmosphere and under processing conditions that prevent self-decomposition of the raw materials is one of the factors that makes it possible to selectively chemically adsorb at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film.

[0078] In this step, at least a portion of the molecular structure of the molecules constituting the raw materials may be adsorbed onto a part of the surface of the conductive film, but the amount of adsorption is very small, far less than the amount of at least a portion of the molecular structure of the molecules constituting the raw materials adsorbed onto the surface of the insulating film. Such selective (preferential) adsorption is possible because the processing conditions in this step are non-plasma conditions and low temperature conditions as described later, so that the raw materials do not undergo gas phase decomposition in the processing chamber 201. Furthermore, a film formation inhibiting layer is formed over the entire surface of the conductive film, whereas a film formation inhibiting layer is not formed over many areas of the insulating film surface. Also, Si-OH terminations are formed over the entire surface of the insulating film, while Si-OH terminations are not formed over many areas of the conductive film surface.

[0079] The processing conditions when supplying the raw materials and catalyst in this step are as follows: Processing temperature: Room temperature (25°C) to 200°C, preferably 25 to 150°C Processing pressure: 13-13330 Pa, preferably 13-4000 Pa Raw material supply flow rate: 0.001~2slm Catalyst supply flow rate: 0.001~2slm Inert gas supply flow rate (per gas supply pipe): 0-20 slm Each gas supply time: 0.1 to 60 seconds, preferably 10 to 50 seconds Examples are given.

[0080] After selectively forming the first layer on the surface of the insulating film, valves 243b and 243d are closed to stop the supply of raw materials and catalyst to the processing chamber 201, respectively. Then, using the same processing procedure and conditions as described above, any remaining gaseous substances in the processing chamber 201 are removed (purged). It is preferable that the processing temperature during purging in this step is the same as the processing temperature when supplying the raw materials and catalyst.

[0081] As raw materials, halogen-free raw materials containing an alkoxy group, an alkoxy group and an amino group, or a hydride group (H group) and an amino group can be used. Here, halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc.

[0082] An alkoxy group is a monovalent functional group having a structure in which an alkyl group (R) is bonded to oxygen (O), and is represented by the structural formula -OR. Examples of alkoxy groups include methoxy groups (-OMe), ethoxy groups (-OEt), propoxy groups (-OPr), and butoxy groups (-OBu). The alkoxy group may be not only a linear alkoxy group, but also a branched alkoxy group such as an isopropoxy group (-OiPr) or an isobutoxy group (-OiBu). The alkyl groups mentioned above include methyl groups (-Me), ethyl groups (-Et), propyl groups (-Pr), and butyl groups (-Bu). The alkyl group may be not only a linear alkyl group, but also a branched alkyl group such as an isopropyl group (-iPr), an isobutyl group (-iBu), a secondary butyl group (-secBu), or a tertbutyl group (-tertBu).

[0083] An amino group is a monovalent functional group having a structure obtained by removing hydrogen (H) from ammonia (NH3), a primary amine, or a secondary amine, and represented by one of the structural formulas -NH2, -NHR, or -NRR'. In other words, the term "amino group" as used herein also includes substituted amino groups. R and R' shown in the structural formula are alkyl groups including methyl (-Me), ethyl (-Et), propyl (-Pr), and butyl (-Bu). R and R' may be linear alkyl groups as well as branched alkyl groups as described above. R and R' may be the same alkyl group or different alkyl groups.

[0084] For example, raw materials such as Si(OEt)4, Si(OMe)4, Si(NMe2)(OMe)3, Si(NMe2)2(OMe)2, Si(NMe2)3(OMe), Si(NMe2)(OEt)3, Si(NMe2)2(OEt)2, Si(NMe2)3(OEt), Si(NEt2)(OMe)3, Si(NEt2)(OEt)3, SiH(NMe2)3, SiH2(NEt2)2, SiH2(NHt-Bu)2, Si(pyrrolidine)(OMe)3, Si(pyrrolidine)2(OMe)2, Si(pyrrolidine)3(OMe), SiH3N(iPr)2, SiH3N(iBt)2, etc. can be used. One or more of these can be used as raw materials. Furthermore, if the raw materials contain not only alkoxy groups but also amino groups, the reaction described above can proceed without supplying a catalyst during the raw material supply step.

[0085] As a catalyst, a cyclic amine or chain-like amine containing carbon (C), nitrogen (N), and hydrogen (H), and having a conjugate acid dissociation constant (pKa) exceeding that of pyridine (C5H5N, pKa=5.67), can be used. Furthermore, it is more preferable to use a cyclic amine or chain-like amine as a catalyst, in which the conjugate acid dissociation constant is 10 or greater. The pKa values ​​for the various catalysts described herein are those at 25°C.

[0086] Examples of catalysts include piperazine (C4H 10 N2, pKa=9.80), pyrrolidine (C4H9N, pKa=11.3), piperidine (C5H 11 N, pKa=11.12), 1,1,3,3-tetramethylguanidine (C5H 13 N3, pKa=13.6), 1-methylpiperidine (C6H 13 N, pKa=10.08), diazabicyclononene (C7H 12 N2, pKa=12.7), 2,5-dimethylpyrrolidine(C6H 13 N, pKa=11.4), 1-methylpyrrolidine (C5H 11 N, pKa=10.3), tetramethylpyrrolidine (C8H 17 Examples of catalysts that can be used include N (pKa=12.2), triethylamine ((C2H5)3N, pKa=10.75), trimethylamine ((CH3)3N, pKa=9.8), diethylamine ((C2H5)2NH, pKa=10.9), dimethylamine ((CH3)2NH, pKa=10.73), monoethylamine ((C2H5)NH2, pKa=10.6), monomethylamine ((CH3)NH2, pKa=10.6), and their derivatives. Furthermore, for example, catalysts of the general formula NR can be used. 1 R 2 R 3 (R 1 =C n H 2n+1 (n≧1), R 2 ,R 3 =C m H 2m+1 Amines represented by (m≧0) can also be used. One or more of these can be used as catalysts. It is more preferable that the catalyst is a non-aromatic amine. These points also apply to the oxidizing agent supply step described later.

[0087] [Oxidizing agent supply step] After the raw material supply step is completed, an oxidizing agent (oxidizing gas) and a catalyst (catalytic gas) are supplied as film-forming agents to the wafer 200, that is, the wafer 200 after the first layer of the insulating film has been selectively formed on its surface.

[0088] Specifically, valves 243c and 243d are opened, and the oxidizer and catalyst are flowed into the gas supply pipes 232c and 232d, respectively. The flow rates of the oxidizer and catalyst are adjusted by MFCs 241c and 241d, respectively, and supplied into the processing chamber 201 via nozzles 249c and 249a. They are mixed in the processing chamber 201 and exhausted from the exhaust port 231a. At this time, the oxidizer and catalyst are supplied to the wafer 200 from the side of the wafer 200 (oxidizer + catalyst supply). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0089] By supplying the oxidizing agent and catalyst to the wafer 200 under the processing conditions described later, it becomes possible to oxidize at least a portion of the first layer formed on the surface of the insulating film in the raw material supply step. As a result, a second layer is formed on the surface of the insulating film, which is the first layer that has been oxidized.

[0090] In this step, by supplying the catalyst together with the oxidizing agent, the above reaction can be carried out in a non-plasma atmosphere and under low temperature conditions as described later. By forming the second layer in a non-plasma atmosphere and under low temperature conditions as described later, it is possible to maintain the molecules and atoms constituting the film formation inhibiting layer formed on the surface of the conductive film without them disappearing (desorbing) from the surface of the conductive film.

[0091] The processing conditions when supplying the oxidizing agent and catalyst in this step are as follows: Processing temperature: Room temperature (25°C) to 200°C, preferably 25 to 150°C Processing pressure: 13-13300 Pa, preferably 133-13332 Pa Oxidizer supply flow rate: 0.001~10 slm Catalyst supply flow rate: 0~2slm Inert gas supply flow rate (per gas supply pipe): 0-20 slm Each gas supply time: 10 to 300 seconds, preferably 30 to 200 seconds Examples are given.

[0092] Furthermore, it is preferable to make the time spent supplying the oxidizing agent to the wafer 200 in the oxidizing agent supply step longer than the time spent supplying the raw material to the wafer 200 in the raw material supply step. Also, it is preferable to make the processing pressure when supplying the oxidizing agent to the wafer 200 in the oxidizing agent supply step higher than the processing pressure when supplying the raw material to the wafer 200 in the raw material supply step. By controlling the balance between the processing conditions in the raw material supply step and the processing conditions in the oxidizing agent supply step in this way, the above-mentioned reactions that occur in the raw material supply step and the above-mentioned reactions that occur in the oxidizing agent supply step can be made to occur more effectively.

[0093] After oxidizing the first layer formed on the surface of the insulating film to transform it into the second layer, valves 243c and 243d are closed to stop the supply of the oxidizing agent and catalyst to the processing chamber 201, respectively. Then, using the same processing procedure and conditions as described above, any remaining gaseous substances in the processing chamber 201 are removed (purged). It is preferable that the processing temperature during purging in this step is the same as the processing temperature when supplying the oxidizing agent and catalyst.

[0094] As an oxidizing agent, for example, gases containing oxygen (O) and hydrogen (H) can be used. Examples of O and H-containing gases include water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, H2 gas + ozone (O3) gas, etc. One or more of these can be used as the O and H-containing gas.

[0095] In this specification, the joint mention of two gases, such as "H2 gas + O2 gas," refers to a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe before being supplied to the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0096] As a catalyst, for example, catalysts similar to those exemplified in the raw material supply step described above can be used.

[0097] [Perform the prescribed number of times] By performing the above-described raw material supply step and oxidizing agent supply step non-simultaneously, i.e., without synchronization, a predetermined number of cycles (n times, where n is an integer of 1 or more), an oxide film can be selectively (preferentially) formed on the surface of the insulating film, among the conductive film and insulating film, as shown in Figure 5(d). For example, when using the above-described raw materials, oxidizing agent, and catalyst, an SiO film can be selectively grown as an oxide film on the surface of the insulating film. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired film thickness, and to repeat the above cycle multiple times until the film thickness of the oxide film formed by stacking the second layer reaches the desired film thickness.

[0098] As described above, by performing the above cycle a predetermined number of times, an oxide film can be selectively grown on the surface of the insulating film. At this time, since a film formation inhibiting layer is formed on the surface of the conductive film, the growth of the oxide film on the surface of the conductive film can be suppressed. In other words, by repeating the above cycle multiple times, it is possible to suppress the growth of the oxide film on the surface of the conductive film while promoting the growth of the oxide film on the surface of the insulating film.

[0099] Furthermore, when performing each of the above steps, the film formation inhibiting layer formed on the surface of the conductive film is maintained on the surface of the conductive film as described above, thereby suppressing the growth of an oxide film on the surface of the conductive film. However, in cases where the formation of the film formation inhibiting layer on the surface of the conductive film is insufficient due to some factor, the formation and growth of an oxide film on the surface of the conductive film may occur to a very small extent. However, even in this case, the thickness of the oxide film formed on the surface of the conductive film will be far thinner than the thickness of the oxide film formed on the surface of the insulating film. In this specification, "high selectivity in selective growth" includes not only the case in which no oxide film is formed on the surface of the conductive film and an oxide film is formed only on the surface of the insulating film, but also the case in which a very thin oxide film is formed on the surface of the conductive film, but a much thicker oxide film is formed on the surface of the insulating film.

[0100] It is preferable to perform the cleaning step, modification step, and film deposition step in the same processing chamber (in situ). This allows the modification step and film deposition step to be performed without exposing the wafer 200 to the atmosphere, i.e., while keeping the wafer 200 surface clean, after the cleaning step (after removing the native oxide film formed on the surface of the wafer 200), making it possible to properly perform the selective formation of an oxide film on the surface of the insulating film. In other words, by performing each of the above steps in the same processing chamber (in situ), selective growth with high selectivity becomes possible. However, if the native oxide film has been removed from the surface of the wafer 200 in advance, the cleaning step can be omitted, and in this case, selective growth with high selectivity becomes possible by performing the modification step and film deposition step in the same processing chamber (in situ). Note that if it is possible to properly maintain the surface of the wafer 200 after each step, the cleaning step, modification step, and film deposition step can each be performed in different processing chambers (ex-situ).

[0101] (Heat treatment step) After the film deposition step, the wafer 200, that is, the wafer 200 after selectively forming an oxide film on the surface of the insulating film, is subjected to heat treatment. At this time, it is preferable to adjust the output of the heater 207 so that the temperature in the processing chamber 201, that is, the temperature of the wafer 200 after selectively forming an oxide film on the surface of the insulating film, is equal to or higher than the temperature of the wafer 200 in each of the above steps, and preferably higher than the temperature of the wafer 200 in each of the above steps.

[0102] By performing heat treatment (annealing) on ​​the wafer 200, impurities in the oxide film formed on the surface of the insulating film during the film deposition step can be removed, and defects can be repaired. Furthermore, by performing annealing on the wafer 200, the film deposition inhibiting layer formed on the surface of the conductive film can be removed or neutralized. Figure 5(e) shows the surface portion of the wafer 200 after the film deposition inhibiting layer on the surface of the conductive film has been removed.

[0103] This step may be performed with an inert gas supplied to the processing chamber 201, or with a reactive substance such as an oxidizing agent (oxidizing gas) supplied. In this case, the inert gas or reactive substance such as an oxidizing agent (oxidizing gas) is also called an assisting substance. By supplying an assisting substance, impurities contained in the oxide film formed on the surface of the insulating film can be removed and defects can be repaired efficiently and effectively, and the film formation inhibiting layer formed on the surface of the conductive film can be removed or neutralized efficiently and effectively. However, if the removal of impurities or repair of defects in the oxide film formed on the surface of the insulating film is not required, or if the removal or neutralization of the film formation inhibiting layer formed on the surface of the conductive film is not required, the annealing process can be omitted.

[0104] The processing conditions when performing heat treatment in the heat treatment step are as follows: Processing temperature: 120-500°C, preferably 300-400°C Processing pressure: 1~120000Pa Processing time: 1-18000 seconds Assist substance supply flow rate: 0-50 slm Examples are given. When the conductive film is a Cu film, it is preferable to set the processing temperature during heat treatment as described above, but when the conductive film is a film other than a Cu film, the processing temperature during heat treatment can be, for example, 120 to 800°C, preferably 300 to 650°C.

[0105] (After-purge and return to atmospheric pressure) After the heat treatment step is completed, inert gas is supplied as a purge gas into the processing chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purging). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (restoration to atmospheric pressure).

[0106] (Boat unloading and wafer discharge) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutters 219s are moved, and the lower end opening of the manifold 209 is sealed by the shutters 219s via the O-ring 220c (shutter closing). After the processed wafer 200 has been unloaded from the reaction tube 203, it is removed from the boat 217 (wafer discharge).

[0107] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0108] (a) In the film deposition step, by supplying halogen-free raw materials, an oxidizing agent, and a catalyst in a non-plasma atmosphere, it is possible to suppress the reaction of raw materials used during selective growth and by-products generated during selective growth with the conductive film exposed on the surface of the wafer 200, thereby preventing corrosion of the conductive film. This suppresses a decrease in the reliability of the device. Furthermore, it is possible to suppress the reaction of raw materials and by-products with the conductive film exposed on the surface of the wafer 200, which would make selective growth difficult.

[0109] (b) The inclusion of alkoxy groups in the raw material enables film formation on the insulating film under the low-temperature conditions described above. Furthermore, the inclusion of amino groups in the raw material allows for chemical adsorption of the raw material onto the insulating film without the use of a catalyst, enabling film formation on the insulating film under the low-temperature conditions described above.

[0110] (c) By using at least one of the following as raw materials: Si(OMe)4, Si(NMe2)(OMe)3, Si(NMe2)2(OMe)2, Si(NMe2)3(OMe), Si(NMe2)(OEt)3, Si(NMe2)2(OEt)2, Si(NMe2)3(OEt), Si(NEt2)(OMe)3, Si(NEt2)(OEt)3, SiH(NMe2)3, SiH2(NEt2)2, SiH2(NHt-Bu)2, Si(pyrrolidine)(OMe)3, Si(pyrrolidine)2(OMe)2, and Si(pyrrolidine)3(OMe), byproducts such as hydrogen chloride (HCl) can be prevented from being generated during selective growth. Furthermore, during selective growth, it becomes possible to suppress reactions between the raw materials and the conductive film, reactions between by-products such as HCl and the conductive film, and corrosion of the conductive film by the raw materials and by-products such as HCl.

[0111] (d) By using a cyclic amine or chain-like amine as a catalyst, which has an acid dissociation constant of the conjugate acid of pyridine that exceeds the acid dissociation constant of the conjugate acid of pyridine, it is possible to suppress the reaction between the catalyst and the conductive film, as well as corrosion of the conductive film by the catalyst. Furthermore, by using a cyclic amine or chain-like amine whose conjugate acid acid dissociation constant is 10 or higher, it is possible to sufficiently suppress the reaction between the catalyst and the conductive film, as well as corrosion of the conductive film by the catalyst.

[0112] (e) In the film formation step, a predetermined number of cycles are performed in which the raw material supply step and the oxidizer supply step are carried out non-simultaneously, and the catalyst is supplied to the wafer 200 in at least one of the raw material supply step and the oxidizer supply step, thereby enabling controlled selective growth under the low-temperature conditions described above.

[0113] (f) Even if a modification step is performed before the film deposition step to form a film deposition inhibiting layer on the surface of the conductive film among the conductive film and insulating film, raw materials used during selective growth and by-products generated during selective growth may reach the conductive film through the intermolecular gaps of the molecules constituting the film deposition inhibiting layer. In such cases, however, it is possible to suppress the reaction of raw materials and by-products that reach the conductive film through the intermolecular gaps of the molecules constituting the film deposition inhibiting layer with the conductive film and cause corrosion of the conductive film. This can suppress a decrease in the reliability of the device. Furthermore, even in such cases, it is possible to suppress the reaction of raw materials and by-products that reach the conductive film through the intermolecular gaps of the molecules constituting the film deposition inhibiting layer with the conductive film, causing the molecules constituting the film deposition inhibiting layer to detach from the surface of the conductive film and making selective growth difficult.

[0114] (g) In the modification step, by making the reactivity between the modifier and the surface of the conductive film higher than the reactivity between the modifier and the insulating film, it becomes possible to selectively form a film formation inhibiting layer on the surface of the conductive film among the conductive film and the insulating film.

[0115] (h) The effects described above can also be obtained when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the above-mentioned group of cleaning agents, modifiers, raw materials, oxidizing agents, catalysts, and inert gases.

[0116] (4) Variations The substrate processing sequence in this embodiment can be modified as shown in the following examples. These modifications can be combined in any way. Unless otherwise specified, the processing procedures and conditions in each step of each modification can be the same as those in each step of the substrate processing sequence described above.

[0117] (Variation 1) In the processing sequence shown in Figure 4, an example was described in which the catalyst is supplied together with the raw materials in the raw material supply step. However, as shown in Figure 6 and the processing sequence below, in the raw material supply step, the raw materials may be supplied alone as a reactive gas without supplying the catalyst to the wafer 200. In this case, an inert gas may be supplied together with the raw materials.

[0118] Cleaning agent → Modifier → (Raw material → Oxidizing agent + Catalyst) × n

[0119] In particular, when the raw material contains amino groups, even under the same processing conditions as in the above-described embodiment, it becomes possible to selectively chemically adsorb at least a portion of the molecular structure of the molecules constituting the raw material onto the insulating film surface, while suppressing the chemical adsorption of at least a portion of the molecular structure of the molecules constituting the raw material onto the surface of the conductive film, without supplying a catalyst.

[0120] In this case, it is particularly preferable to make the time spent supplying the oxidizing agent to the wafer 200 in the oxidizing agent supply step longer than the time spent supplying the raw materials to the wafer 200 in the raw materials supply step. Furthermore, in this case, it is particularly preferable to make the processing pressure when supplying the oxidizing agent to the wafer 200 in the oxidizing agent supply step higher than the processing pressure when supplying the raw materials to the wafer 200 in the raw materials supply step. By controlling the balance between the processing conditions in the raw materials supply step and the processing conditions in the oxidizing agent supply step in this way, the above-mentioned reactions occurring in the raw materials supply step and the above-mentioned reactions occurring in the oxidizing agent supply step can be produced more effectively, even when the catalyst is not supplied together with the raw materials. This effect is particularly pronounced when the raw materials contain both alkoxy groups and amino groups.

[0121] The same effects as those of the above-described embodiment can be obtained in Modification 1. Furthermore, according to Modification 1, it is possible to significantly reduce the amount of catalyst used in the film formation step. In addition, it is possible to further suppress the reaction between the catalyst and the conductive film, as well as the corrosion of the conductive film by the catalyst.

[0122] (Modification 2) In the processing sequence shown in Figure 4, an example was described in which a modification step is performed before the film deposition step. However, the modification step may be omitted, as shown in Figure 7 and the processing sequence below. Note that, similar to Modification 1, in the raw material supply step, the raw material is supplied alone as a reactive gas without supplying a catalyst to the wafer 200. In this case, an inert gas may be supplied together with the raw material.

[0123] Cleaning agent → (raw material → oxidizing agent + catalyst) × n

[0124] Even when the modification step is omitted, that is, even when a film formation inhibiting layer is not formed on the surface of the conductive film, by using the above-mentioned raw materials, catalyst, and oxidizing agent, an oxide film can be selectively formed on the surface of the insulating film, rather than the conductive film.

[0125] Even when no film formation inhibiting layer is formed on the surface of the conductive film, selective oxide film formation on the surface of the insulating film is possible because the surface of the insulating film contains Si-OH terminations (adsorption sites), while the surface of the conductive film does not contain Si-OH terminations (adsorption sites). In other words, the presence of Si-OH terminations on the surface of the insulating film promotes the adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film during the raw material supply step. On the other hand, the absence of Si-OH terminations on the surface of the conductive film suppresses the adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the conductive film during the raw material supply step. Thus, the reactivity between the raw materials and the surface of the conductive film is lower than the reactivity between the raw materials and the surface of the insulating film, and this is one of the factors that allows for the selective chemical adsorption of at least a portion of the molecular structure of the molecules constituting the raw materials onto the surface of the insulating film during the raw material supply step. Furthermore, the first layer formed on the surface of the insulating film during the raw material supply step is transformed into the second layer during the oxidizing agent supply step. However, the surface of the second layer contains Si-OH terminations, while the surface of the conductive film remains Si-OH termination-free. Therefore, selective chemiadsorption proceeds in the second and subsequent cycles, just as in the first cycle.

[0126] In this modified example, as shown in the processing sequence below, the catalyst may be supplied to the wafer 200 in both the step of supplying raw materials and the step of supplying oxidizing agents, or the catalyst may be supplied to the wafer 200 in the step of supplying raw materials.

[0127] Cleaning agent → (raw material + catalyst → oxidizing agent + catalyst) × n Cleaning agent → (raw material + catalyst → oxidizing agent) × n

[0128] The same effects as those of the above-described embodiment can be obtained in Modification 2. Furthermore, according to Modification 2, the modification step can be omitted, so the amount of modifying agent used can be reduced to zero. In addition, by omitting the modification step, the total processing time can be shortened, and throughput, i.e., the productivity of substrate processing can be greatly improved. However, as in the above-described embodiment, higher selectivity can be obtained by performing the modification step.

[0129] <Other aspects of this disclosure> The aspects of this disclosure have been specifically described above. However, this disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0130] For example, in the above-described embodiment, as a typical example, an example was described in which the conductive film as the first underlayment is composed of, for example, a Cu film, and the insulating film as the second underlayment is composed of, for example, an SiO film. In addition to the Cu film, the conductive film may also be a metal-containing film such as a cobalt film (Co film), ruthenium film (Ru film), titanium film (Ti film), aluminum film (Al film), molybdenum film (Mo film), tungsten film (W film), or titanium nitride film (TiN film). The conductive film may contain one or more of these. In addition to the SiO film, the insulating film may also be a metal-free film such as a silicon oxynitride film (SiOC film), silicon oxynitride film (SiOCN film), silicon oxynitride film (SiON film), silicon nitride film (SiN film), silicon borocarbonite film (SiBCN film), silicon boronitride film (SiBN film), silicon borocarbide film (SiBC film), or silicon carbide film (SiC film). The insulating film may contain one or more of these. When the conductive film as the first underlayment contains a metal-containing film and the insulating film as the second underlayment contains a metal-free film, the effects shown in the above-described embodiment become particularly pronounced. For example, when the conductive film as the first underlayment contains a Cu film and the insulating film as the second underlayment contains the above-described silicon-based insulating film, the effects shown in the above-described embodiment become particularly pronounced.

[0131] It is preferable that the recipes used for each process be prepared individually according to the processing content and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes stored in the storage device 121c according to the processing content. This makes it possible to form films of various film types, composition ratios, film quality, and film thickness with good reproducibility using a single substrate processing device. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0132] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed in the board processing device. When modifying a recipe, the modified recipe may be installed in the board processing device via a telecommunications line or a recording medium containing the recipe. Alternatively, existing recipes already installed in the board processing device may be directly modified by operating the input / output device 122 provided in the existing board processing device.

[0133] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0134] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above in the embodiments and modifications, and the same effects as described above can be obtained.

[0135] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions in the above-described embodiments and modifications. [Examples]

[0136] <Example 1> A wafer with a Cu film as a conductive film and an SiO film as an insulating film exposed on its surface was subjected to the following processing sequence: cleaning, modification, and film deposition. The cleaning agent, modifying agent, raw materials, oxidizing agent, catalyst, and inert gas were all substances usable in each step as described in the above embodiments. The processing conditions during each step were those that made each step as described in the above embodiments achievable.

[0137] Cleaning agent → Modifier → (Raw material → Oxidizing agent + Catalyst) × n

[0138] The thickness of the oxide film (SiO film) formed on the SiO film and on the Cu film (a Cu film with a film formation inhibiting layer formed on its surface) was then measured. The results are shown in Figure 8. In Figure 8, the vertical axis represents the thickness (nm) of the oxide film formed by the film formation step, and the horizontal axis represents the substrate (SiO film, Cu film) of the oxide film.

[0139] As shown in Figure 8, the thickness of the oxide film formed on the SiO film was approximately 14 nm. In contrast, no oxide film was formed on the Cu film. Thus, according to the film deposition sequence shown in Figure 6, it was confirmed that selective growth of an oxide film (SiO film) on the SiO film is possible with very high selectivity by performing a modification step before the film deposition step.

[0140] <Example 2> A wafer with a Cu film as a conductive film and an SiO film as an insulating film exposed on its surface was subjected to the following processing sequence: a cleaning step and a film deposition step (the modification step was not performed). The cleaning agent, raw materials, oxidizing agent, catalyst, and inert gas used were all substances that could be used in each step as described in the above embodiment. The processing conditions during each step were those that could be used to realize each step as described in the above embodiment.

[0141] Cleaning agent → (raw material → oxidizing agent + catalyst) × n

[0142] The thickness of the oxide film (SiO film) formed on the SiO film and on the Cu film (a Cu film without a film formation inhibiting layer formed on its surface) was then measured. The results are shown in Figure 9. In Figure 9, the vertical axis represents the thickness (nm) of the oxide film formed by the film formation step, and the horizontal axis represents the substrate (SiO film, Cu film) of the oxide film.

[0143] As shown in Figure 9, the thickness of the oxide film formed on the SiO film was approximately 14 nm. In contrast, the thickness of the oxide film formed on the Cu film was approximately 7 nm. Thus, even in Example 2, where the modification step was omitted, it was confirmed that selective growth of the oxide film (SiO film) on the SiO film was possible with a predetermined degree of selectivity. Furthermore, according to this example, when the thickness of the oxide film formed on the SiO film is relatively thin (for example, 7 nm or less), it can be inferred that even if the modification step is omitted, selective growth of the oxide film (SiO film) on the SiO film is possible with a high degree of selectivity comparable to that when the modification step is performed, that is, while avoiding the formation of an oxide film (SiO film) on the Cu film. [Explanation of Symbols]

[0144] 200 wafers (substrates)

Claims

1. A step of providing a substrate having a conductive film and an insulating film on its surface, A step of selectively forming an oxide film on the surface of the insulating film, among the conductive film and the insulating film, by supplying a halogen-free raw material, an oxidizing agent, and a catalyst to the substrate in a non-plasma atmosphere, It has, In the process of forming the oxide film, a predetermined number of cycles are performed including the step of supplying the raw materials to the substrate and the step of supplying the oxidizing agent to the substrate, and in at least one of the steps of supplying the raw materials and supplying the oxidizing agent, the catalyst is supplied to the substrate. A substrate processing method comprising: making the time for supplying the oxidizing agent to the substrate longer than the time for supplying the raw material to the substrate; and making the pressure in the space where the substrate is present during the step of supplying the oxidizing agent to the substrate higher than the pressure in the space where the substrate is present during the step of supplying the raw material to the substrate.

2. The substrate processing method according to claim 1, wherein the reactivity between the raw material and the surface of the conductive film in the step of forming the oxide film is lower than the reactivity between the raw material and the surface of the insulating film.

3. The substrate processing method according to claim 1 or 2, wherein the surface of the insulating film contains Si-OH terminations, and the surface of the conductive film does not contain Si-OH terminations.

4. The substrate processing method according to any one of claims 1 to 3, wherein the raw material contains an alkoxy group, an alkoxy group and an amino group, or a hydride group and an amino group.

5. The raw material is Si(OEt) ４ , Si(OMe) ４ , Si(NMe ２ )(OMe) ３ , Si(NMe ２ ), ２ (OMe) ２ , Si(NMe ２ ), ３ (OMe), Si(NMe ２ )(OEt) ３ , Si(NMe ２ ), ２ (OEt) ２ , Si(NMe ２ ), ３ (OEt), Si(NEt ２ )(OMe) ３ , Si(NEt ２ )(OEt) ３ , SiH(NMe ２ ),[[ID=四十三]] ３ , SiH ２ (NEt ２ ), ２ , SiH ２ (NHt-Bu) ２ , Si(pyrrolidine)(OMe) ３ , Si(pyrrolidine) ２ (OMe) ２ , and Si(pyrrolidine) ３ (OMe), SiH ３ N(iPr) ２ , SiH ３ N(iBt) ２ The substrate processing method according to any one of claims 1 to 3, comprising at least any one of these.

6. The substrate treatment method according to any one of claims 1 to 5, wherein the catalyst comprises a cyclic amine or a chain-like amine having an acid dissociation constant of a conjugate acid that exceeds the acid dissociation constant of the conjugate acid of pyridine.

7. The substrate treatment method according to any one of claims 1 to 5, wherein the catalyst comprises a cyclic amine or a chain-like amine whose conjugate acid has an acid dissociation constant of 10 or more.

8. The substrate treatment method according to any one of claims 1 to 7, wherein the catalyst comprises at least one of piperazine, pyrrolidine, piperidine, 1,1,3,3-tetramethylguanidine, 1-methylpiperidine, diazabicyclononene, 2,5-dimethylpyrrolidine, 1-methylpyrrolidine, tetramethylpyrrolidine, triethylamine, trimethylamine, diethylamine, dimethylamine, monoethylamine, monomethylamine, and derivatives thereof.

9. The substrate processing method according to any one of claims 1 to 8, further comprising the step of supplying a modifier to the substrate before performing the step of forming the oxide film, thereby forming a film formation inhibiting layer on the surface of the conductive film among the conductive film and the insulating film.

10. The substrate processing method according to claim 9, wherein the reactivity between the modifier and the surface of the conductive film in the step of forming the film-forming inhibiting layer is higher than the reactivity between the modifier and the surface of the insulating film.

11. The substrate treatment method according to claim 9, wherein the modifier contains hydrocarbon groups, and the film formation inhibiting layer contains hydrocarbon group terminations.

12. The substrate treatment method according to claim 9, wherein the modifying agent comprises at least one of a thiol compound and a phosphonic acid compound.

13. The substrate processing method according to any one of claims 1 to 8, wherein the conductive film includes a metal-containing film, and the insulating film includes a metal-free film.

14. The substrate processing method according to any one of claims 1 to 8, wherein the conductive film comprises a copper film and the insulating film comprises a silicon-based insulating film.

15. The processing chamber is the space in which the substrate is located when the substrate is processed, A supplying device that provides substrates into the processing chamber, A raw material supply system that supplies halogen-free raw materials to the substrate in the processing chamber, An oxidizing agent supply system that supplies an oxidizing agent to a substrate in the processing chamber, A catalyst supply system that supplies a catalyst to a substrate in the processing chamber, A pressure adjustment unit for adjusting the pressure inside the processing chamber, A processing chamber is provided with a substrate having a conductive film and an insulating film on its surface. The processing chamber is then used to supply the substrate with the halogen-free raw material, the oxidizing agent, and the catalyst under a non-plasma atmosphere, thereby selectively forming an oxide film on the surface of the insulating film among the conductive film and the insulating film. The processing chamber for forming the oxide film is used to perform a predetermined number of cycles including supplying the raw material to the substrate and supplying the oxidizing agent to the substrate. In at least one of the raw material supply process and the oxidizing agent supply process, the catalyst is supplied to the substrate. The time for supplying the oxidizing agent to the substrate is made longer than the time for supplying the raw material to the substrate. The pressure in the space where the substrate is located during the oxidizing agent supply process is higher than the pressure in the space where the substrate is located during the raw material supply process. A control unit is configured to control the supplying apparatus, the raw material supply system, the oxidizing agent supply system, the catalyst supply system, and the pressure adjustment unit. A substrate processing apparatus having

16. A procedure for providing a substrate having a conductive film and an insulating film on its surface, A procedure for selectively forming an oxide film on the surface of the insulating film, among the conductive film and the insulating film, by supplying a halogen-free raw material, an oxidizing agent, and a catalyst to the substrate in a non-plasma atmosphere, In the procedure for forming the oxide film, a predetermined number of cycles are performed including the step of supplying the raw materials to the substrate and the step of supplying the oxidizing agent to the substrate, and in at least one of the steps of supplying the raw materials and supplying the oxidizing agent, the step of supplying the catalyst to the substrate is included. A procedure in which the time for supplying the oxidizing agent to the substrate is made longer than the time for supplying the raw material to the substrate, and the pressure in the space where the substrate is located during the procedure for supplying the oxidizing agent to the substrate is made higher than the pressure in the space where the substrate is located during the procedure for supplying the raw material to the substrate, A program that causes a circuit board processing unit to execute commands via a computer.

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