Substrate processing method, semiconductor device production method, substrate processing device, and program

Abstract

The present invention comprises (A) a step for supplying an oxygen-containing fluid, and (B) a step for supplying a reducing agent after (A), to a substrate having a metal film and a non-metal film.

Description

Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and program

[0001] The present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a program.

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a treatment for modifying a film formed on the surface of a substrate may be performed (see, for example, Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2019-175920

[0004] The present disclosure provides a technique that can control the film quality of a metal film formed on a substrate.

[0005] According to one aspect of the present disclosure, there is provided a technique comprising: (A) supplying an oxygen-containing fluid to a substrate having a metal film and a non-metal film; and (B) after (A), supplying a reducing agent.

[0006] According to the present disclosure, it is possible to control the film quality of a metal film formed on a substrate.

[0007] FIG. 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in one embodiment of the present disclosure, showing a vertical cross-sectional view of a processing furnace 202. FIG. 2 is a schematic diagram of a controller 121 of a substrate processing apparatus suitable for use in one embodiment of the present disclosure, showing a control system of the controller 121 in block diagram form. FIG. 3( a) is a partially enlarged cross-sectional view of the surface of a wafer 200 having a non-metallic film 500 formed as a base on the surface and a metal film 400 formed within the non-metallic film 500. FIG. 3( b) is a partially enlarged cross-sectional view of the surface of the wafer 200 after supplying an oxygen-containing fluid to the wafer 200 to modify the metal film 400 and the non-metallic film 500 into a metal oxide film 410 and an oxidized non-metallic film 510, respectively. FIG. 3( c) is a partially enlarged cross-sectional view of the surface of the wafer 200 after supplying a reducing agent to the wafer 200 to reduce the metal oxide film 410 to the metal film 400. FIG. 4( a) is a partially enlarged cross-sectional view of a metal film 400 before oxidation treatment. FIG. 4( b) is a partially enlarged cross-sectional view of a metal oxide film 410 after oxidation treatment of the metal film 400. FIG. 4( c) is a partially enlarged cross-sectional view of a metal film 400 after reduction treatment of the metal oxide film 410. FIG. 5( a) is a cross-sectional TEM image of a target sample that is the subject of reduction treatment in the example. FIG. 5( b) is a cross-sectional TEM image of evaluation sample 1, which is the target sample in the example that is reduced at a treatment temperature of 200°C. FIG. 5( c) is a cross-sectional TEM image of evaluation sample 2, which is the target sample in the example that is reduced at a treatment temperature of 150°C. FIG. 5( d) is a cross-sectional TEM image of evaluation sample 3, which is the target sample in the example that is reduced at a treatment temperature of 250°C.

[0008] <One Aspect of the Present Disclosure> One aspect of the present disclosure will be described below with reference to Figures 1, 2, 3(a) to 3(c), and 4(a) to 4(c). Note that the drawings used in the following description are all schematic, and the dimensional relationships between elements, the ratios of elements, and the like shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships between elements, the ratios of elements, and the like between multiple drawings do not necessarily match.

[0009] (1) Configuration of the Substrate Processing Apparatus As shown in FIG. 1, a processing furnace 202 includes a reaction tube 203. The reaction tube 203 is made of, for example, quartz (SiO ２ The reaction tube 203 is made of a heat-resistant material such as silicon carbide (SiC) or the like, and is configured as a cylindrical member having a gas supply port 203p at the upper end and a furnace opening (opening) at the lower end. A processing chamber 201 is formed in the cylindrical hollow portion of the reaction tube 203. The processing chamber 201 is configured to be able to accommodate a plurality of wafers 200 as substrates.

[0010] A seal cap 219 is provided below the reaction tube 203 as a lid that can airtightly close the lower end opening of the reaction tube 203. The seal cap 219 is made of a non-metallic material such as quartz. A rotation mechanism 267 is provided below the seal cap 219. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217. The rotation mechanism 267 is configured to rotate the boat 217, thereby rotating the wafers 200. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115 that serves as a lifting mechanism.

[0011] The boat 217, which serves as a substrate support, is configured to support a plurality of wafers 200, for example, 25 to 200, in a horizontal position and aligned vertically in multiple stages, i.e., arranged with intervals between them. The boat 217 is made of a heat-resistant material such as quartz or SiC, and has a top plate 217a and a bottom plate 217b on the top and bottom. Insulators 218, which are supported in multiple stages in a horizontal position below the boat 217, are made of a heat-resistant material such as quartz or SiC.

[0012] A heater 207 serving as a heating unit is provided on the outside of the reaction tube 203. The heater 207 not only heats the wafers 200 accommodated in the wafer accommodation area to a predetermined temperature, but also functions as a liquefaction suppression mechanism that applies thermal energy to the gas supplied into the processing chamber 201 to suppress liquefaction, and as an excitation mechanism that thermally activates the gas. A temperature sensor 263 serving as a temperature detection unit is provided in the processing chamber 201 along the inner wall of the reaction tube 203.

[0013] A gas supply pipe 232a is connected to a gas supply port 203p provided at the upper end of the reaction tube 203. The gas supply pipe 232a is provided with a gas generator 250a serving as a first vaporizer, a mass flow controller (MFC) 241a serving as a flow rate controller (flow rate control section), and a valve 243a serving as an on-off valve.

[0014] A supply pipe 232c that supplies a liquid containing oxygen (O) (hereinafter, sometimes referred to as a "first liquid") is connected to the gas generator 250a. The supply pipe 232c is provided with a tank 250t that serves as a storage tank (reservoir tank) that stores the first liquid, an MFC 241c, and a valve 243c. The first liquid will be described in detail later.

[0015] A gas supply pipe 232g that supplies a first pressurized gas into the tank 250t is connected to the tank 250t. The gas supply pipe 232g is provided with an MFC 241g and a valve 243g. The first pressurized gas is used to push the first liquid in the tank 250t into the supply pipe 232c. For example, a gas similar to the inert gas described below can be used as the first pressurized gas. The tank 250t is also provided with a drain pipe 232h that discharges the first liquid from the tank 250t. The drain pipe 232h is provided with a valve 243h.

[0016] A gas supply pipe 232d is connected to the gas generator 250a, and supplies a first vaporization carrier gas to the inside of the gas generator 250a. The gas supply pipe 232d is provided with an MFC 241d and a valve 243d. The first vaporization carrier gas is used to atomize the first liquid supplied from the supply pipe 232c to the gas generator 250a, thereby facilitating vaporization.

[0017] A gas supply pipe 232b is connected to the gas supply pipe 232a downstream of the valve 243a. The gas supply pipe 232b is provided with a gas generator 250b as a second vaporizer, an MFC 241b, and a valve 243b.

[0018] A supply pipe 232e that supplies a predetermined liquid (hereinafter, sometimes referred to as the "second liquid") that constitutes the reducing agent is connected to the gas generator 250b. The supply pipe 232e is provided with a tank 250u that serves as a storage tank for storing the second liquid, an MFC 241e, and a valve 243e. The second liquid will be described in detail later.

[0019] A gas supply pipe 232i that supplies a second pressurized gas into the tank 250u is connected to the tank 250u. The gas supply pipe 232i is provided with an MFC 241i and a valve 243i. The second pressurized gas is used to push the second liquid in the tank 250u to the supply pipe 232e. For example, a gas similar to the inert gas described below can be used as the second pressurized gas. The tank 250u is also provided with a drain pipe 232j that discharges the second liquid from the tank 250u. The drain pipe 232j is provided with a valve 243j.

[0020] A gas supply pipe 232f is connected to the gas generator 250b, and supplies a second vaporization carrier gas to the gas generator 250b. The gas supply pipe 232f is provided with an MFC 241f and a valve 243f. The second vaporization carrier gas is used to atomize the solution (second liquid) supplied from the supply pipe 232e to the gas generator 250b, facilitating vaporization.

[0021] The gas generator 250a is configured to generate an oxygen-containing fluid (also referred to as an O-containing fluid) that is a vaporized gas of the first liquid, for example, by heating the first liquid to a predetermined temperature under approximately atmospheric pressure and vaporizing or misting the first liquid. In this aspect, when vaporizing or misting the first liquid, a first vaporization carrier gas is supplied to the gas generator 250a together with the first liquid, thereby atomizing the first liquid.

[0022] The gas generator 250b is configured to generate a reducing agent, which is a vaporized gas of the second liquid, by, for example, heating the second liquid to a predetermined temperature under approximately atmospheric pressure and vaporizing or misting it. In this aspect, when vaporizing or misting the second liquid, a second vaporization carrier gas is supplied to the gas generator 250b together with the second liquid, thereby atomizing the second liquid.

[0023] A gas supply pipe 232k for supplying an inert gas is connected to the gas supply pipe 232b downstream of the valve 243b. The gas supply pipe 232k is provided with an MFC 241k and a valve 243k. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0024] An O-containing fluid supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. The O-containing fluid supply system may also include a gas generator 250a. A reducing agent supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. The gas generator 250b may also be included in the reducing agent supply system. A first liquid supply system is mainly configured by the tank 250t, the supply pipe 232c, the MFC 241c, and the valve 243c. A first vaporization carrier gas supply system is mainly configured by the gas supply pipe 232d, the MFC 241d, and the valve 243d. A second liquid supply system is mainly configured by the tank 250u, the supply pipe 232e, the MFC 241e, and the valve 243e. A second vaporization carrier gas supply system is mainly constituted by gas supply pipe 232f, MFC 241f, and valve 243f. A first compressed gas supply system is mainly constituted by gas supply pipe 232g, MFC 241g, and valve 243g. A second compressed gas supply system is mainly constituted by gas supply pipe 232i, MFC 241i, and valve 243i. An inert gas supply system is mainly constituted by gas supply pipe 232k, MFC 241k, and valve 243k.

[0025] An exhaust pipe 231 that exhausts the atmosphere inside the processing chamber 201 is connected to the lower sidewall of the reaction tube 203. A vacuum pump 246 serving as an exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector that detects the pressure inside the processing chamber 201 and an APC valve 244 serving as a pressure regulator. An exhaust system is mainly configured by the exhaust pipe 231 and the APC valve 244. The vacuum pump 246 may be considered to be included in the exhaust system.

[0026] As shown in FIG. 2 , the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121. The substrate processing apparatus may be configured to include one control unit or multiple control units. That is, the control for performing the processing sequence described below may be performed using one control unit or multiple control units. Furthermore, the multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and the control for carrying out the processing sequence described below may be performed by the entire control system. When the term "control unit" is used in this specification, it may include not only one control unit but also multiple control units or a control system configured by multiple control units.

[0027] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. Control programs for controlling the operation of the substrate processing apparatus, process recipes describing procedures and conditions for substrate processing (described later), etc., are readably recorded and stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (described later) that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipes, control programs, etc. are collectively referred to simply as programs. The process recipes are also simply referred to as recipes. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0028] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241g, 241k, valves 243a to 243k, gas generators 250a, 250b, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0029] 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 an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the gas generation operation by the gas generators 250a and 250b, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241g and 241k, the opening and closing operation of the valves 243a to 243k, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop 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 rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0030] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to as recording media. When the term recording medium is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] (2) Substrate Processing Step Using the substrate processing apparatus described above, a substrate processing method as one step in the semiconductor device manufacturing process, specifically, an example of a processing sequence for processing a wafer 200 as a substrate having a metal film 400 and a non-metal film 500 formed on its surface, will be described primarily with reference to FIGS. 3( a) to 3( c) and 4( a) to 4( c). This embodiment also describes, as an example, a case in which a wafer 200 having a three-dimensional recessed structure such as a trench, groove, or hole formed on its surface is used. Furthermore, this embodiment also describes, as an example, a case in which a non-metallic film 500 is formed as an underlayer on the surface of the wafer 200, and a metal film 400 is formed as wiring within the recessed portion of the non-metallic film 500 formed in the wafer 200 (see FIG. 3( a)). The metal film 400 is formed, for example, so as to fill the recessed portion from the top to the bottom of the recessed portion of the wafer 200. This embodiment also describes a case in which the metal film 400 has a structure including multiple crystal grains. In the following description, the operation of each component constituting the substrate processing apparatus is controlled by a controller 121.

[0032] The processing sequence in this embodiment mainly includes a step of supplying an O-containing fluid (hereinafter sometimes referred to as "Step A") and a step of supplying a reducing agent (hereinafter sometimes referred to as "Step B") to a wafer 200 having a metal film 400 and a non-metal film 500. The term "fluid" used herein includes at least one of a gas, a liquid, and a vapor. The term "agent" used herein includes at least one of a gaseous substance and a liquid substance. Liquid substances include mist-like substances. That is, the reducing agent may include a gaseous substance, a liquid substance such as a mist-like substance, or both. Below, as an example, a case where the O-containing fluid is a gas (gas) obtained by vaporizing the first liquid described above and a case where the reducing agent is a gas (gas) obtained by vaporizing the second liquid described above will be described.

[0033] (Substrate Loading Process) A plurality of wafers 200 having a metal film 400 and a non-metal film 500 formed on their surfaces are loaded into the boat 217. Thereafter, as shown in Fig. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201. In this state, the seal cap 219 seals the lower end of the reaction tube 203.

[0034] (Pressure / Temperature Adjustment Process) The processing chamber 201, i.e., the space in which the wafer 200 is present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so as to reach a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The wafer 200 is also heated by the heater 207 so as to reach a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so as to achieve a desired temperature distribution inside the processing chamber 201. The rotation mechanism 267 also starts to rotate the wafer 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0035] (O2-containing fluid supplying process: step A) In this process, generation of vaporized gas is started in the gas generator 250a to supply the O2-containing fluid to the wafer 200. In this embodiment, the O2-containing fluid (vaporized gas) is generated by vaporizing the first liquid. As the O2-containing fluid, for example, hydrogen peroxide solution is used.

[0036] Specifically, first, valves 243c and 243d are opened, and the supply of the first liquid and the first vaporization carrier gas to gas generator 250a is started while the flow rates are controlled by MFCs 241c and 241d, and a vaporized gas of the first liquid (O-containing fluid) is generated by gas generator 250a. At this time, controller 121 controls MFC 241c to adjust the flow rate and other parameters of the O-containing fluid generated by gas generator 250a. The first liquid stored in tank 250t is forced out of tank 250t into supply pipe 232c by opening valve 243g and supplying a first compressed gas to tank 250t while the flow rate is controlled by MFC 241g. This process may be started during or before the pressure and temperature adjustment process.

[0037] When the amount of O-containing fluid generated becomes stable, the valve 243a is opened to start supplying the O-containing fluid into the processing chamber 201 via the MFC 241a, the gas supply pipe 232a, and the gas supply port 203p.

[0038] The O-containing fluid supplied into the processing chamber 201 flows downward within the processing chamber 201 and is exhausted to the outside of the processing chamber 201 via the exhaust pipe 231. At this time, the O-containing fluid is supplied to the wafer 200. At this time, an inert gas may be supplied into the processing chamber 201 via the gas supply pipes 232b and 232a and the gas supply port 203p while the valve 243k is opened and the flow rate is adjusted by the MFC 241k.

[0039] Examples of treatment conditions for supplying the O-containing fluid in this step include: treatment temperature: higher than 150°C and lower than 250°C, preferably 170 to 230°C; treatment pressure: 700 to 1000 hPa, preferably 800 to 980 hPa; supply flow rate of O-containing fluid: 5 to 20 ccm, preferably 10 to 15 ccm; supply time of O-containing fluid: 100 to 250 minutes, preferably 120 to 180 minutes; supply flow rate of first vaporization carrier gas: 3 to 10 ccm; supply flow rate of inert gas: 0 to 10 ccm.

[0040] In this specification, when a numerical range such as "170 to 230°C" is expressed, both the lower and upper limits are included in the range. Thus, for example, "170 to 230°C" means "170°C or higher and 230°C or lower." The same applies to other numerical ranges. In this specification, the processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201, in other words, the pressure in the space in which the wafer 200 is present. In addition, the processing time refers to the time the processing continues. In addition, when the supply flow rate includes 0 ccm, 0 ccm means that the substance is not supplied. These terms also apply to the following description.

[0041] By supplying the O-containing fluid to the wafer 200 under the above-described conditions, the metal film 400 and the non-metal film 500 formed on the wafer 200 can be modified (oxidized) into a metal oxide film 410 and a non-metal oxide film 510, respectively (see FIGS. 3( a) and 3(b)).

[0042] By supplying the O-containing fluid to the wafer 200 under the above-described conditions, the O component contained in the O-containing fluid can be permeated into the interior of the metal film 400 and the interior of the non-metal film 500 formed on the wafer 200.

[0043] By supplying the O-containing fluid to the wafer 200 under the above conditions, the O component can be penetrated between the crystal grains in the metal film 400 formed on the wafer 200. Furthermore, when an O-containing fluid containing hydrogen (H) is used, hydroxyl groups (—OH) can be formed on the surfaces of these crystal grains. In Figures 4(a) to 4(c), the regions surrounded by the crystal grain boundaries 600 are shown as crystal grains.

[0044] By supplying the O-containing fluid to the wafer 200 under the above conditions, the O component contained in the O-containing fluid can be made to permeate the entire metal film 400, that is, from the top to the bottom of the recesses.

[0045] By supplying the O-containing fluid to the wafer 200 under the above conditions, an amount of O component that can be desorbed from the metal oxide film 410 in step B described below can be allowed to permeate into the metal film 400.

[0046] If the treatment temperature is 150° C. or lower, oxidation of the metal film 400 and the non-metallic film 500 may be insufficient, making it difficult to cause the O component to penetrate deep into the metal film 400 and the non-metallic film 500. If the treatment temperature is set to a temperature higher than 150° C., the metal film 400 and the non-metallic film 500 are sufficiently oxidized, making it possible to cause the O component to penetrate deep into the metal film 400 and the non-metallic film 500.

[0047] If the treatment temperature is 250° C. or higher, the metal film 400 may be excessively oxidized, and an amount of O component that cannot be desorbed from the metal oxide film 410 in a reducing agent supply step (step B) described later may permeate into the metal film 400. By setting the treatment temperature to a temperature lower than 250° C. (a temperature less than 250° C.), excessive oxidation of the metal film 400 can be avoided, and an amount of O component that can be desorbed from the metal oxide film 410 in step B described later can permeate into the metal film 400.

[0048] The first liquid may be, for example, hydrogen peroxide solution. Here, hydrogen peroxide solution is hydrogen peroxide (H ２ O ２ ) with water (H ２ The aqueous solution obtained by dissolving the H in the first liquid. ２ O ２ is a type of active oxygen that is unstable and easily releases oxygen (O), generating hydroxyl radicals (OH radicals) with very strong oxidizing power. Therefore, when hydrogen peroxide is used as the first liquid, the O-containing fluid, which is the hydrogen peroxide fluid (vaporized gas), acts as a strong oxidizing agent in step A.

[0049] The inert gas is nitrogen (N ２Inert gases that can be used include rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas. One or more of these gases can be used as the inert gas. This also applies to the processes described below.

[0050] As the first vaporization carrier gas, for example, a gas similar to the inert gas described above can be used.

[0051] (Drying Process: Removal Process) After a predetermined time has elapsed and the oxidation process of the metal film 400 and the like is completed, the valve 243a is closed to stop the supply of the O-containing fluid to the wafer 200. Then, the heater 207 heats the inside of the processing chamber 201 to remove excess H remaining in the processing chamber 201. ２ O and H ２ O ２ In this way, the excess H attached to the inner wall of the processing chamber 201, the wafer 200, the inside or surface of the metal film 400, etc. ２ O and H ２ O ２ and the like can be vaporized and removed from the wafer 200. Note that the term "heating" used here refers to, for example, raising the temperature to a level at which impurities attached to the inside of the processing chamber 201 are vaporized. At this time, the vaporized impurities may be discharged (purged) to the outside of the processing chamber 201 by the vacuum pump 246.

[0052] (First Purge Step: Removal Step) After a predetermined time has elapsed and the drying step has been completed, the O-containing fluid, by-products, atmosphere, and the like remaining in the processing chamber 201 are discharged (purged) to the outside of the processing chamber 201 by the vacuum pump 246. Specifically, impurities attached to the inner wall of the processing chamber 201 or the wafer 200, for example, are discharged (purged) to the outside of the processing chamber 201 by the vacuum pump 246. At this time, the valve 243k is opened to supply an inert gas as a purge gas into the processing chamber 201, and the impurities remaining in the processing chamber 201 are discharged (purged) to the outside of the processing chamber 201. Specifically, by supplying the inert gas into the processing chamber 201, for example, excess H attached to the inner wall of the processing chamber 201 or the wafer 200 is removed. ２ O and H ２ O ２The impurities such as the above are discharged (purged) to the outside of the processing chamber 201. Specifically, the impurities are collided with the inner wall of the processing chamber 201 and the impurities attached to the wafers 200, for example, the inside or surface of the metal film 400, to physically remove the impurities from the wafers 200. By performing this process (first purging process) after the drying process, it is possible to reliably remove the impurities attached to the wafers 200. Note that in this process, it is preferable to adjust the heater 207 so that the temperature inside the processing chamber 201 is lower than the temperature inside the processing chamber 201 in the drying process.

[0053] (Reducing Agent Supply Process: Step B) In this process, the gas generator 250b starts generating vaporized gas to supply the reducing agent to the wafer 200. In this embodiment, the reducing agent (vaporized gas) is generated by vaporizing the second liquid. For example, formic acid is used as the reducing agent.

[0054] Specifically, first, valves 243e and 243f are opened, and while the flow rates are controlled by MFCs 241e and 241f, supply of the second liquid and the second vaporization carrier gas to gas generator 250b is started, and a vaporized gas (reducing agent) of the second liquid is generated by gas generator 250b. At this time, MFC 241e is controlled by controller 121 to adjust the flow rate and the like of the reducing agent generated by gas generator 250b. Note that the second liquid stored in tank 250u is forced out of tank 250u into supply pipe 232e by opening valve 243i and supplying a second compressed gas to tank 250u while the flow rate is controlled by MFC 241i.

[0055] When the amount of generated reducing agent and the like become stable, the valve 243b is opened to start supplying the reducing agent into the processing chamber 201 via the MFC 241b, the gas supply pipes 232b and 232a, and the gas supply port 203p.

[0056] The reducing agent supplied into the processing chamber 201 flows downward within the processing chamber 201 and is discharged to the outside of the processing chamber 201 via the exhaust pipe 231. In this process (step B), as in step A, an inert gas may be supplied into the processing chamber 201.

[0057] Examples of treatment conditions for supplying the reducing agent in this step include: treatment temperature: higher than 150°C and lower than 250°C, preferably 170 to 230°C; treatment pressure: 400 to 900 hPa, preferably 500 to 780 hPa; supply flow rate of reducing agent: 5 to 20 ccm, preferably 10 to 15 ccm; supply time of reducing agent: 100 to 250 minutes, preferably 120 to 180 minutes; supply flow rate of second vaporization carrier gas: 3 to 10 ccm; supply flow rate of inert gas: 0 to 10 ccm.

[0058] By supplying a reducing agent to the wafer 200 under the above-described processing conditions, the metal oxide film 410 of the metal oxide film 410 and the non-metal oxide film 510 formed on the wafer 200 can be reduced to the metal film 400 (see Figures 3(b) and 3(c)).

[0059] By supplying a reducing agent to the wafer 200 under the above-described processing conditions, the O component that has penetrated into the metal oxide film 410 is desorbed from the interior of the metal oxide film 410, and the size of the crystal grains in the metal film 400 can be made larger than the size of the crystal grains in the metal oxide film 410 in step A (see FIGS. 4(b) and 4(c)).

[0060] The second liquid may be an aqueous solution containing a carboxy group (—COOH), such as a formic acid (HCOOH) solution. ２ The reducing agent is an aqueous solution obtained by dissolving a —COOH-containing fluid in O. As the reducing agent, a —COOH-containing fluid, specifically, for example, a formic acid-containing fluid, can be used.

[0061] By supplying a -COOH-containing fluid, specifically a formic acid-containing fluid, as a reducing agent to the wafer 200 under the above-described processing conditions, the -COOH contained in the reducing agent reacts with -OH groups formed on the surfaces of the crystal grains in the metal oxide film 410, thereby cleaving the -OH groups. By cleaving the -OH groups, O components are desorbed from the metal oxide film 410, and the size of the crystal grains in the metal film 400 can be increased compared to the size of the crystal grains in the metal oxide film 410 in step A (see FIGS. 4B and 4C). Specifically, as described above, in step A, an amount of O components that can be desorbed from the metal oxide film 410 in step B is penetrated into the interior of the metal film 400. Therefore, in step B, most of the -OH groups formed on the surfaces of the crystal grains in the metal oxide film 410 are cleaved, and at this time, adjacent crystal grains in the metal oxide film 410 are bonded (aggregated). As a result, the crystal grains in the metal film 400 grow into larger crystal grains.

[0062] By supplying a reducing agent to wafer 200 under the above-described processing conditions, O components are desorbed from the entire metal film 400 formed so as to fill the recess from the top surface to the bottom surface of the recess of wafer 200, and the size of the crystal grains in the entire metal film 400 can be made larger than the size of the crystal grains in metal oxide film 410 in step A.

[0063] As described above, by setting the process pressure in step B (the pressure inside the process chamber 201) to a pressure lower than the process pressure in step A described above, the desorption action of the O component that has penetrated into the metal oxide film 410 can be enhanced.

[0064] If the treatment temperature is 150°C or lower, the reduction of the metal oxide film 410 may be insufficient, making it difficult to aggregate adjacent crystal grains in the metal oxide film 410. Therefore, it may be difficult to make the size of the crystal grains in the metal film 400 larger than the size of the crystal grains in the metal oxide film 410 in step A. In other words, it may be difficult to enlarge the crystal grains constituting the metal film 400 in step B. By setting the treatment temperature to a temperature higher than 150°C, the metal oxide film 410 is sufficiently reduced, making it possible to aggregate adjacent crystal grains in the metal film 400. Therefore, it is possible to make the size of the crystal grains in the metal film 400 in step B larger than the size of the crystal grains in the metal oxide film 410 in step A. In other words, it is difficult to enlarge the crystal grains constituting the metal film 400 in step B.

[0065] If the treatment temperature is 250° C. or higher, the metal oxide film 410 may be excessively reduced, causing excessive aggregation of crystal grains in the metal oxide film 410, and the metal film 400 formed on the wafer 200 to become discontinuous. By setting the treatment temperature to a temperature lower than 250° C. (a temperature less than 250° C.), it is possible to avoid excessive reduction of the metal oxide film 410 and prevent the metal film 400 formed on the wafer 200 from becoming discontinuous. In this specification, "the metal film 400 becomes discontinuous" includes, for example, a state in which at least a portion of the metal film 400 becomes bead-shaped, a state in which at least a portion of the metal film 400 is discontinued to expose the underlying layer, and a state in which the surface roughness of at least a portion of the metal film 400 is reduced.

[0066] As the second vaporization carrier gas, for example, a gas similar to the inert gas described above can be used.

[0067] (Second Purge Process: Removal Process) After a predetermined time has elapsed and the reduction process of the metal oxide film 410 using the reducing agent has been completed, the vacuum pump 246 is used to discharge (purge) the reducing agent, by-products, and the like remaining in the process chamber 201 to the outside of the process chamber 201. Specifically, the vacuum pump 246 is used to discharge (purge) impurities, such as excess reducing agent, adhering to the inner wall of the process chamber 201 or the wafer 200 to the outside of the process chamber 201. At this time, the valve 243k is opened to supply an inert gas as a purge gas into the process chamber 201, thereby discharging (purging) the reducing agent, by-products, and the like remaining in the process chamber 201 to the outside of the process chamber 201. Specifically, by supplying the inert gas into the process chamber 201, impurities, such as excess reducing agent, adhering to the inner wall of the process chamber 201 or the wafer 200 to the outside of the process chamber 201, for example. In this manner, the inert gas is caused to collide with impurities such as excess reducing agent adhering to the inner wall of the processing chamber 201 and the wafers 200 , thereby physically removing the impurities from the wafers 200 .

[0068] [Performance Predetermined Number of Times] By performing the above-described steps A and B asynchronously, i.e., in this order, a cycle is performed a predetermined number of times (n times, where n is an integer of 1 or 2 or greater), the O component that has penetrated into the metal oxide film 410 is desorbed from the interior of the metal oxide film 410, and the size (crystal grain shape) of the crystal grains in the metal film 400 in step B can be made larger than the size of the crystal grains in the metal oxide film 410 in step A (see FIGS. 4(b) and 4(c)). The above-described cycle is preferably repeated multiple times. By repeating the cycle multiple times, the O component inside the metal oxide film 410 can be reliably desorbed, and the crystal grain shape of the metal film 400 in step B can be reliably made larger than the crystal grain shape of the metal oxide film 410 in step A.

[0069] (Heating Step: Annealing Step) Thereafter, the temperature of the heater 207 is adjusted appropriately, and the metal film 400 formed on the wafer 200 is heat-treated.

[0070] This process may be performed while the valve 243k is opened and an inert gas is being supplied into the processing chamber 201, or may be performed while the valve 243k is closed and the supply of the inert gas into the processing chamber 201 is stopped.

[0071] Examples of the treatment conditions in this step include: treatment temperature: 300 to 400° C. treatment pressure: 1 to 20 hPa, preferably 1 to 10 Pa inert gas supply flow rate: 0 to 1000 ccm.

[0072] (Atmospheric Pressure Return Process) Thereafter, the inside of the processing chamber 201 is evacuated by the vacuum pump 246. Then, an inert gas is supplied into the processing chamber 201 to return the interior to atmospheric pressure, thereby increasing the heat capacity inside the processing chamber 201. This makes it possible to uniformly heat the wafers 200 and components inside the processing chamber 201, and to remove particles, impurities, outgassing, etc. that could not be removed by the vacuum evacuation from inside the processing chamber 201. After a predetermined time has elapsed, the temperature inside the processing chamber 201 is lowered to a predetermined temperature at which the processing chamber 201 can be removed.

[0073] (Substrate Unloading Process) The seal cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203. Then, the processed wafers 200, supported by the boat 217, are unloaded from the lower end of the reaction tube 203 to the outside of the reaction tube 203. After being unloaded to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217.

[0074] (3) Effects of this Aspect According to this aspect, one or more of the following effects can be obtained.

[0075] (a) By carrying out step A of supplying an O-containing fluid and step B of supplying a reducing agent to a wafer 200 having a metal film 400 and a non-metal film 500 on its surface, the resistivity of the metal film 400 can be reduced. This will be described below.

[0076] When the O component that penetrated the interior of the metal film 400 in step A is desorbed from the interior of the metal oxide film 410 in step B, adjacent crystal grains in the metal oxide film 410 aggregate. The aggregation of adjacent crystal grains allows the crystal grain size of the metal film 400 in step B to be larger than the crystal grain size of the metal oxide film 410 in step A (see FIGS. 4( b) and 4(c)). As the crystal grain size increases, the number of crystal grain boundaries 600 per unit volume in the metal film 400 decreases, thereby reducing electron scattering at the crystal grain boundaries 600. This facilitates electron flow in the metal film 400, thereby reducing the resistivity of the metal film 400. As a result, device characteristics can be improved.

[0077] (b) In step B, the wafer 200 is heated so as to expand the crystal grains that make up the metal oxide film 410. As described above, this reduces the number of crystal grain boundaries 600 per unit volume in the metal film 400, thereby lowering the resistivity of the metal film 400. Furthermore, in step B, the wafer 200 is heated so as to prevent the metal film 400 from becoming discontinuous. This prevents variations in density in the metal film 400 and improves the flatness of the metal film 400. As a result, the resistance value of the metal film 400 can be made uniform.

[0078] (c) In step A, an amount of O component that can be desorbed in step B is allowed to penetrate into the metal film 400. Specifically, for example, in step A, the wafer 200 is heated to a temperature that allows an amount of O component that can be desorbed in step B to penetrate into the metal film 400. This makes it possible to suppress excessive oxidation of the metal film 400 in step A.

[0079] (d) In step A, by using a hydrogen peroxide solution as the O-containing fluid, it is possible to prevent the metal film 400 from being excessively oxidized or altered. Specifically, the O-containing fluid, which is a hydrogen peroxide solution, is an O-containing fluid that is generally used as an oxidizing agent. ２ Since the oxidizing power is stronger than that of gas, the processing temperature can be relatively low and the processing time can be shortened, thereby preventing excessive oxidation and deterioration of the metal film 400.

[0080] (e) In step A, the O component is infiltrated into the metal film 400, and in step B, the O component is desorbed from the metal oxide film 410, so that the size of the crystals in the metal film 400 can be made larger than the size of the crystal grains in the metal oxide film 410 in step A. This ensures that the resistivity of the metal film 400 can be reduced.

[0081] (f) In step A, the O component is allowed to penetrate between the crystal grains in the metal film 400, forming —OH on the surfaces of these crystal grains, and in step B, the O component is desorbed from the metal oxide film 410, making it possible to make the size of the crystals in the metal film 400 larger than the size of the crystal grains in the metal oxide film 410 in step A. This ensures that the resistivity of the metal film 400 can be reduced.

[0082] (g) In step A, the O component is permeated into the entire metal film 400 from the top surface to the bottom surface of the recessed portion of the wafer 200, and in step B, the O component is desorbed from the entire metal oxide film 410, so that the size of the crystal grains in the entire metal oxide film 410 can be made larger than the size of the crystal grains in the metal oxide film 410 in step A. This makes it possible to more reliably reduce the resistivity of the metal film 400.

[0083] (i) After step B is performed, the wafer 200 is heated (annealed), thereby making the density of the metal film 400 uniform, and therefore making the resistivity of the metal film 400 uniform.

[0084] (4) Modifications The substrate processing sequence in this embodiment can be modified as shown in the following modifications. These modifications can be combined as desired. Unless otherwise specified, the processing procedures and processing conditions in each step of each modification can be the same as the processing procedures and processing conditions in each step of the substrate processing sequence described above.

[0085] (Variation 1) Step B may include step B-1 of supplying a reducing agent under a predetermined pressure, and step B-2 of supplying at least a reducing agent or an inert gas under a pressure lower than the predetermined pressure after a predetermined time has elapsed.

[0086] Examples of processing conditions for supplying the reducing agent in step B-1 include: processing temperature: higher than 150°C and lower than 250°C, preferably 170 to 230°C processing pressure: 400 to 900 hPa, preferably 500 to 780 hPa supply flow rate of reducing agent: 2 to 10 ccm, preferably 5 to 8 ccm supply time of reducing agent: 50 to 200 minutes, preferably 100 to 150 minutes supply flow rate of second vaporization carrier gas: 3 to 10 slm inert gas supply flow rate: 0 to 10 slm

[0087] Examples of processing conditions for supplying the reducing agent and inert gas in step B-2 include: Processing temperature: higher than 150°C and lower than 250°C, preferably 170 to 230°C Processing pressure: 300 to 800 hPa, preferably 400 to 700 hPa Reducing agent supply flow rate: 2 to 10 ccm, preferably 5 to 8 ccm Reducing agent supply time: 50 to 200 minutes, preferably 100 to 150 minutes Second vaporization carrier gas supply flow rate: 3 to 10 slm Inert gas supply flow rate: 2 to 10 ccm, preferably 5 to 8 ccm Inert gas supply time: 50 to 200 minutes, preferably 100 to 150 minutes Although this modified example illustrates the case where both the reducing agent and the inert gas are supplied in step B-2, only one of the reducing agent and the inert gas may be supplied.

[0088] This modification also provides the same effects as those of the above-described embodiment. In this modification, the O component that has penetrated into the metal oxide film 410 is desorbed in two stages, steps B-1 and B-2, thereby further enhancing the desorption effect of the O component that has penetrated into the metal oxide film 410. In this modification, the processing pressure in step B-2 is further set lower than the processing pressure in step B-1, thereby further enhancing the desorption effect of the O component that has penetrated into the metal oxide film 410.

[0089] Other Aspects of the Present Disclosure The above describes specific aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0090] For example, in the above-described embodiment, the O-containing fluid is a gas. However, the present disclosure is not limited to such an embodiment. The O-containing fluid may be, for example, H ２ O ２ The vapor containing hydrogen peroxide or hydrogen peroxide solution (liquid) may be used. In this embodiment, the same effects as those in the above-mentioned embodiment can be obtained.

[0091] For example, in the above-described embodiment, the reducing agent is a gas containing -COOH, specifically, a gas containing HCOOH, as an example. However, the present disclosure is not limited to such an embodiment. The reducing agent may be, for example, a vapor or liquid containing HCOOH. In this embodiment, the same effects as those in the above-described embodiment can be obtained. In addition, the reducing agent may be acetic acid (CH ３ In this embodiment, the same effects as those in the above-mentioned embodiment can be obtained. However, the present invention is not limited to the above-mentioned embodiment. ３ The COOH-containing fluid contains a large amount of C (carbon) components. If there is a possibility that this C component may have an unintended effect on the metal oxide film 410 formed on the wafer 200, CH ３ It is preferable to use an HCOOH-containing fluid which has a lower C component content than a COOH-containing fluid.

[0092] For example, although not described in the above embodiment, the non-metallic film 500 formed on the surface of the wafer 200 may be, for example, a Si film, a silicon oxide film (SiO film), or a silicon nitride film (SiN film).

[0093] For example, although not described in the above embodiment, the metal material constituting the metal film 400 may be, for example, cobalt (Co), copper (Cu), tungsten (W), or ruthenium (Ru).

[0094] For example, in the above-described embodiment, the substrate processing apparatus includes one processing chamber 201, and both steps A and B are performed in this processing chamber 201. However, the present disclosure is not limited to this embodiment. For example, the substrate processing apparatus may include multiple processing chambers, and steps A and B may be performed in different processing chambers. This embodiment also provides the same effects as the above-described embodiment.

[0095] It is preferable that the recipes used for each process are individually prepared according to the process content and recorded and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from among the multiple recipes recorded and stored in the storage device 121c. This makes it possible to reproducibly form films with various film types, composition ratios, film qualities, and film thicknesses using a single substrate processing apparatus. It also reduces the burden on the operator, avoids operational errors, and enables each process to be started quickly.

[0096] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe already installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the modified recipe is recorded. Alternatively, an existing recipe already installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0097] In the above-described embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied, for example, to a case where a film is formed using a single-wafer substrate processing apparatus that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied to a case where a film is formed using a substrate processing apparatus having a cold-wall processing furnace.

[0098] When using these substrate processing apparatuses, each process can be performed using the same processing procedures and conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0099] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example.

[0100] A wafer having a Si film as a base on its surface and a Cu film formed on the Si film was subjected to an oxidation treatment to modify the Cu film formed on the wafer into a copper oxide film (CuO film), thereby preparing a target sample to be subjected to a reduction treatment. A cross-sectional transmission electron microscope image (cross-sectional TEM image) of the target sample was then taken. Figure 5(a) shows the cross-sectional TEM image of the target sample. The open line at the bottom left of the TEM image is a scale bar, representing 20 μm. The processing conditions in the oxidation treatment step for preparing the target sample were set to predetermined conditions within the range of the processing conditions in step A of the above-described embodiment. The substance exemplified in the above-described embodiment was used as the O-containing fluid.

[0101] The target sample was subjected to a reduction treatment to prepare evaluation sample 1. Thereafter, a cross-sectional TEM image of evaluation sample 1 was taken. FIG. 5(b) shows the cross-sectional TEM image of evaluation sample 1. The open line at the bottom left of the TEM image is a scale bar, representing 10 μm. The treatment conditions in the reduction treatment step when preparing evaluation sample 1 were predetermined conditions within the range of the treatment conditions in step B of the above-mentioned embodiment. The treatment temperature in the reduction treatment step was 200° C. The substance exemplified in the above-mentioned embodiment was used as the reducing agent.

[0102] The target sample was subjected to a reduction treatment to prepare evaluation sample 2. Thereafter, a cross-sectional TEM image of evaluation sample 2 was taken. FIG. 5(c) shows the cross-sectional TEM image of evaluation sample 2. The open line at the bottom left of the TEM image is a scale bar, representing 20 μm. The treatment conditions in the reduction treatment step when preparing evaluation sample 2 were predetermined conditions within the range of the treatment conditions in step B of the above-mentioned embodiment, except for the treatment temperature. The treatment temperature in the reduction treatment step was 150° C. The substance exemplified in the above-mentioned embodiment was used as the reducing agent.

[0103] The target sample was subjected to a reduction treatment to prepare evaluation sample 3. Thereafter, a cross-sectional TEM image of evaluation sample 3 was taken. FIG. 5( d ) shows the cross-sectional TEM image of evaluation sample 3. The open line at the bottom left of the TEM image is a scale bar, representing 50 μm. The treatment conditions in the reduction treatment step when preparing evaluation sample 3 were predetermined conditions within the range of the treatment conditions in step B of the above-described embodiment, except for the treatment temperature. The treatment temperature in the reduction treatment step was 250° C. The substance exemplified in the above-described embodiment was used as the reducing agent.

[0104] As shown in Fig. 5(a), it can be seen that in the target sample, a CuO film is formed on a Si film, and the Cu crystals in the CuO film are oxidized.

[0105] As shown in FIG. 5( b), in evaluation sample 1, the Cu crystals in the CuO film were almost completely reduced, and adjacent Cu crystals aggregated and grew into large crystal grains, resulting in a decrease in the number of crystal grain boundaries to the point where they were no longer visible.

[0106] 5C, in the evaluation sample 2, the Cu crystals in the CuO film are slightly reduced, and the O component is released from the CuO film, which results in the grain size of the Cu crystals in the CuO film being smaller than that of the CuO film of the control sample. It can also be seen that the thickness of the CuO film is thinner than that of the control sample.

[0107] As shown in FIG. 5( d ), in evaluation sample 3, the Cu crystals in the CuO film were excessively reduced, which caused excessive aggregation of the Cu crystals, resulting in the growth of large balls.

[0108] 200 wafers (substrates)

Claims

1. A substrate processing method for a substrate having a metal film and a non-metal film, the method comprising: (A) supplying an oxygen-containing fluid; and (B) after (A), supplying a reducing agent.

2. The substrate processing method according to claim 1, wherein in (B), the substrate is heated so that the crystal grains constituting the metal film are enlarged and the metal film does not become discontinuous.

3. The substrate processing method according to claim 2, wherein in (A), an amount of oxygen component that can be desorbed in (B) is permeated into the interior of the metal film.

4. The substrate processing method according to claim 2, wherein in (A), the substrate is heated to a temperature at which an amount of oxygen component that can be desorbed in (B) is permeated into the interior of the metal film.

5. The substrate processing method according to claim 1, wherein the oxygen-containing fluid is a fluid of hydrogen peroxide solution.

6. The substrate processing method according to claim 1 or claim 5, wherein the reducing agent is a fluid containing a carboxy group.

7. The substrate processing method according to claim 1 or claim 5, wherein the reducing agent is a fluid containing formic acid.

8. The metal material constituting the metal film is copper, the metal film includes a plurality of crystal grains, the oxygen-containing fluid is a fluid of hydrogen peroxide solution, the reducing agent is a fluid containing formic acid, and in (A) and (B), the substrate is heated in a temperature range higher than 150 °C and lower than 250 °C. The substrate processing method according to claim 1.

9. The metal film has a structure including a plurality of crystal grains. In (A), an oxygen component is permeated into the interior of the metal film. In (B), the oxygen component is desorbed from the interior of the metal film, and the size of the crystal grains in the metal film is made larger than the size of the crystal grains in the metal film in (A). The substrate processing method according to claim 1.

10. The metal film has a structure including a plurality of crystal grains. In (A), an oxygen component is permeated between the crystal grains to form hydroxy groups on the surfaces of the crystal grains. In (B), the oxygen component is desorbed from the metal film by cleaving the hydroxy groups formed on the surfaces of the crystal grains, and the size of the crystal grains in the metal film is made larger than the size of the crystal grains in the metal film in (A). The substrate processing method according to claim 1.

11. The metal film has a structure including a plurality of crystal grains, the metal film is formed in a concave portion of the substrate, in (A), an oxygen component is permeated through the entire metal film from the upper surface to the bottom surface of the concave portion, and in (B), in the entire metal film, the oxygen component is desorbed from the metal film, and the size of the crystal grains in the metal film is made larger than the size of the crystal grains in the metal film in (A). The substrate processing method according to claim 1.

12. Between (A) and (B), there is a removing step of removing impurities adhering to the substrate. The substrate processing method according to claim 1.

13. After (A), there is a removing step of supplying a purge gas to the substrate to remove impurities adhering to the substrate. The substrate processing method according to claim 11.

14. (A) and (B) are performed in a processing chamber, and in the removing step, the processing chamber is heated. The substrate processing method according to claim 12 or claim 13.

15. In the removing step, after heating the processing chamber for a predetermined time, there is further a removing step of removing the atmosphere in the processing chamber. The substrate processing method according to claim 14.

16. (A) and (B) are performed in a processing chamber, and the pressure in the processing chamber in (B) is lower than the pressure in the processing chamber in (A). The substrate processing method according to claim 1.

17. In (B), (B-1) the reducing agent is supplied under a predetermined pressure, and after a predetermined time has elapsed, (B-2) at least the reducing agent or an inert gas is supplied under a pressure lower than the predetermined pressure. The substrate processing method according to claim 1.

18. (A) and (B) are performed a predetermined number of times. The substrate processing method according to claim 1.

19. A method for manufacturing a semiconductor device, including, for a substrate having a metal film and a non-metal film, (A) a step of supplying an oxygen-containing fluid, and (B) a step of supplying a reducing agent after (A).

20. An O-containing fluid supply system for supplying an oxygen-containing fluid to a substrate, a reducing agent supply system for supplying a reducing agent to the substrate, and (A) a process of supplying the oxygen-containing fluid to a substrate having a metal film and a non-metal film, and (B) a process of supplying the reducing agent after (A). A control unit configured to be able to control the O-containing fluid supply system and the reducing agent supply system so as to perform the processes. A substrate processing apparatus having the control unit.

21. A program that causes a substrate processing apparatus to execute, by a computer, procedures of: (A) supplying an oxygen-containing fluid to a substrate having a metal film and a non-metal film; and (B) supplying a reducing agent after (A).

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