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

Abstract

This invention relates to a substrate processing method, a substrate processing apparatus, a process, and a method for manufacturing a semiconductor device. It provides a technique for controlling the quality of a metal-containing film formed on a substrate. The method includes: (a) supplying a carboxyl-containing fluid to the substrate at a first temperature while the pressure inside a processing chamber containing the metal-containing film is set to a first pressure, thereby removing impurities from the metal-containing film; (b) venting the atmosphere inside the processing chamber after the supply of the carboxyl-containing fluid has been stopped, thereby reducing the pressure inside the processing chamber to a second pressure lower than the first pressure; and (c) maintaining the pressure inside the processing chamber at the second pressure and, while the metal-containing film with the impurities removed is exposed, heating the substrate to a second temperature higher than the first temperature, thereby increasing the crystal grain size of the metal component in the metal-containing film.

Description

Technical Field

[0001] This invention relates to substrate processing methods, substrate processing apparatus, processes, and methods for manufacturing semiconductor devices. Background Technology

[0002] As a step in the manufacturing process of semiconductor devices, sometimes a modification process is performed on the film formed on the substrate (see, for example, Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2019-175920 Summary of the Invention

[0004] The problem that the invention aims to solve This disclosure provides a technique for controlling the quality of a metal-containing film formed on a substrate.

[0005] Methods for solving problems According to one aspect of this disclosure, a technology is provided that has: (a) A process of supplying a carboxyl-containing fluid to the substrate at a first temperature while the pressure in a processing chamber containing a substrate with a metal film is set to a first pressure, thereby removing impurities from the metal film. (b) A step of venting the atmosphere in the processing chamber while the supply of the carboxyl-containing fluid has been stopped, thereby reducing the pressure in the processing chamber to a second pressure lower than the first pressure; and (c) A process of maintaining the pressure in the processing chamber at the second pressure and, with the metal-containing film exposed after the impurities have been removed, heating the substrate to a second temperature higher than the first temperature, thereby increasing the crystal size of the metal component in the metal-containing film.

[0006] Invention Effects According to this disclosure, the quality of the metal-containing film formed on the substrate can be controlled. Attached Figure Description

[0007] Figure 1 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferred in one embodiment of the present disclosure, showing the processing furnace 202 portion in a longitudinal cross-sectional view.

[0008] Figure 2 This is a schematic configuration diagram of the controller 121 of a substrate processing apparatus preferably used in one aspect of this disclosure, and a block diagram showing the control system of the controller 121.

[0009] Figure 3This is a diagram illustrating the processing sequence in one embodiment of this disclosure.

[0010] Figure 4 (a) is a partially enlarged cross-sectional view of a wafer 200 containing a metal film 400 within a recess; Figure 4 (b) is a partially enlarged cross-sectional view of the wafer 200 after impurities 305 are removed from the metal-containing film 400 by supplying a carboxyl-containing fluid to the metal-containing film 400 at a first temperature. Figure 4 (c) is a partial enlarged cross-sectional view of the wafer 200 after the metal film 410 containing impurities 305 has been removed has been heated to a second temperature under depressurized conditions in the processing chamber 201.

[0011] Figure 5 (a) is a magnified view of the grains 300 in the metal film 400 before step A is performed; Figure 5 (b) is a magnified view of a portion of the grains 310 in the metal film 410 after step A has been performed; Figure 5 (c) is a magnified view of the grains 320 in the metal film 420 after steps B and C are performed.

[0012] Figure 6 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferred in other embodiments of this disclosure, showing the processing furnace 302 portion in a longitudinal cross-sectional view.

[0013] Explanation of reference numerals in the attached figures 200 wafers (substrates) 305 Impurities 400, 410 containing metal film Detailed Implementation

[0014] <One way this disclosure> The present disclosure will now be described with reference to the accompanying drawings. Furthermore, the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown may not necessarily correspond to reality. Additionally, the dimensional relationships and ratios of the elements may not be consistent between different drawings.

[0015] (1) Composition of substrate processing device like Figure 1 As shown, the processing furnace 202 includes a reaction tube 203. The reaction tube 203 is configured as a cylindrical component with 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 hollow portion of the reaction tube 203. The processing chamber 201 is configured to accommodate multiple wafers 200 used as substrates.

[0016] A sealing cover 219, serving as a cap, is provided below the reaction tube 203 to hermetically seal the lower opening of the reaction tube 203. A rotating mechanism 267 is provided below the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 is connected to the crystal boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. The sealing cover 219 is configured to move vertically via a crystal boat lift 115, which serves as a lifting mechanism.

[0017] The crystal boat 217, serving as a substrate support, is configured to support multiple wafers 200, for example, 25 to 200 wafers 200, arranged horizontally and vertically in multiple layers, i.e., arranged at intervals. The crystal boat 217 has a top plate 217a and a bottom plate 217b at the top and bottom. At the bottom of the crystal boat 217, a heat insulation body 218 is supported in multiple layers in a horizontal orientation.

[0018] A heater 207, serving as a heating element, is provided on the outside of the reaction tube 203. In addition to heating the wafer 200 housed in the wafer housing area to a predetermined temperature, the heater 207 also functions as a liquefaction suppression mechanism that imparts heat energy to the gas supplied to the processing chamber 201 to suppress its liquefaction, and as an activation mechanism that uses heat to activate the gas. Inside the processing chamber 201 where the wafer 200 is housed, a temperature sensor 263, serving as a temperature detection element, is provided along the inner wall of the reaction tube 203.

[0019] A gas supply pipe 232a is connected to a gas supply port 203p located at the upper end of the reaction pipe 203. A gas generator 250a, which serves as a vaporizer, a mass flow controller (MFC) 241a, which serves as a flow controller (flow control unit), and a valve 243a, which serves as a switching valve, are installed on the gas supply pipe 232a.

[0020] A supply pipe 232c is connected to the gas generator 250a to supply a liquid containing carboxyl groups (-COOH) (hereinafter, sometimes referred to as "the first liquid"). A tank 250t, an MFC 241c, and a valve 243c for storing the first liquid are provided on the supply pipe 232c. Details regarding the first liquid will be described later.

[0021] A gas supply pipe 232e is connected to tank 250t to supply pressurized gas into tank 250t. An MFC 241e and a valve 243e are installed on the gas supply pipe 232e. The pressurized gas is used to expel the first liquid in tank 250t into the supply pipe 232e. For example, the same gas as the inactive gas described later can be used as the pressurized gas. Additionally, a discharge pipe 232f is provided in tank 250t to discharge the first liquid from its interior. A valve 243f is installed on the discharge pipe 232f.

[0022] A gas supply pipe 232d is connected to the gas generator 250a to supply a carrier gas for vaporization. An MFC 241d and a valve 243d are provided on the gas supply pipe 232d. The carrier gas for vaporization is used to atomize the first liquid supplied from the supply pipe 232c to the gas generator 250a, making it easier to vaporize.

[0023] A gas supply pipe 232b for supplying inactive gas is connected downstream of the valve 243a in the gas supply pipe 232a. An MFC 241b and valve 243b are installed on the gas supply pipe 232b. The inactive gas functions as a purge gas, carrier gas, or dilution gas.

[0024] The gas generator 250a is configured to heat the first liquid, for example, to a predetermined temperature at approximately atmospheric pressure, and vaporize or atomize it, thereby generating a COOH-containing fluid, such as a vaporized gas of the first liquid. In this method, when vaporizing or atomizing the first liquid, the first liquid is atomized by supplying a carrier gas for vaporization together with the first liquid to the gas generator 250a.

[0025] The system mainly consists of a gas supply pipe 232a, an MFC 241a, and a valve 243a, forming a COOH-containing fluid supply system. Alternatively, the gas generator 250a can be included in the COOH-containing fluid supply system. The system mainly consists of a gas supply pipe 232b, an MFC 241b, and a valve 243b, forming a non-reactive gas supply system. The system mainly consists of a tank 250t, a supply pipe 232c, an MFC 241c, and a valve 243c, forming a first liquid supply system. The system mainly consists of a gas supply pipe 232d, an MFC 241d, and a valve 243d, forming a vaporization carrier gas supply system. The system mainly consists of a gas supply pipe 232e, an MFC 241e, and a valve 243e, forming a pressurized gas supply system. The COOH-containing fluid supply system, the first liquid supply system, the vaporization carrier gas supply system, and the pressurized gas supply system are collectively referred to as the supply unit.

[0026] An exhaust pipe 231 is connected to the lower side wall of the reaction tube 203 to exhaust the atmosphere inside the processing chamber 201. A vacuum pump 246, serving as an exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245 (which acts as a pressure detector to monitor the pressure inside the processing chamber 201) and an APC valve 244 (which acts as a pressure regulator). The exhaust system (exhaust section) is mainly composed of the exhaust pipe 231 and the APC valve 244. It is also possible to include the vacuum pump 246 within the exhaust system.

[0027] like Figure 2As shown, the controller 121, serving as the control unit (control unit), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an 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, such as a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121. It should be noted that the substrate processing apparatus can be configured to have one control unit or multiple control units. That is, one control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. Furthermore, multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or the entire control system can control the processing sequence described later. When the term "control unit" is used in this specification, in addition to the case of having one control unit, there are also cases of having multiple control units, and cases of having a control system composed of multiple control units.

[0028] The storage device 121c is configured such as flash memory, HDD (Hard Disk Drive), or SSD (Solid State Drive). The storage device 121c contains, in a readable manner, a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions (described later). The process flow is a combination of steps in the substrate processing described later, executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process flow, control program, etc., will be collectively referred to as a program (program product). The process flow will also be referred to simply as a process. When the term "program" is used in this specification, it may include only the process flow, only the control program, or both. RAM 121b is configured as a memory area (working area) that temporarily holds the program, data, etc., read by the CPU 121a.

[0029] I / O port 121d is connected to the aforementioned MFC241a~241e, valves 243a~243f, gas generator 250a, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, crystal boat elevator 115, gate opening and closing mechanism 115s, etc.

[0030] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on inputs such as operation commands from input / output device 122. CPU 121a is configured to control the following according to the content of the read processes: gas generation operation based on gas generator 250a, flow regulation operation of various substances (various gases) based on MFC 241a to 241e, opening and closing operation of valves 243a to 243f, opening and closing operation of APC valve 244, pressure regulation operation based on pressure sensor 245 and using APC valve 244, starting and stopping vacuum pump 246, temperature regulation operation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation operation of crystal boat 217 based on rotation mechanism 267, lifting operation of crystal boat 217 based on crystal boat elevator 115, opening and closing operation of gate 219s based on gate opening and closing mechanism 115s, etc.

[0031] The controller 121 can be configured to install the aforementioned program, recorded and stored in the external storage device 123, into a computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a USB memory, or a semiconductor memory such as an SSD. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium. Hereinafter, they 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, only the external storage device 123, or both. It should be noted that the program can also be provided to the computer without using the external storage device 123, but instead using communication units such as the Internet or dedicated lines.

[0032] (2) Substrate processing process Main use Figure 3 , Figure 4 (a) in Figure 4 In section (c), a method for processing a substrate using the aforementioned substrate processing apparatus as a step in the manufacturing process of a semiconductor device will be described. Specifically, an example of a processing sequence for processing a wafer 200 on which a metal film 400 is formed is described. Furthermore, in this approach, as an example, the case of using a wafer 200 with recesses such as trenches, grooves, and holes formed on its surface as three-dimensional structures will be described.

[0033] It should be noted that, in this specification, the term "recess" is not limited to a shape with a bottom surface; for example, it also includes structures such as gaps or through holes that do not have a bottom surface. In the case of a structure without a bottom surface, "bottom side" sometimes means the direction (side) from each opening toward the inside of the structure when viewed from two or more openings.

[0034] Furthermore, in this approach, as an example, the case where a metal film 400 is formed within a recess on the wafer 200 as a wiring will be described (see [link]). Figure 4 (a) ). The metal film 400 is formed, for example, by filling the recess from the upper part (opening side) to the lower part (deep side, bottom side) of the recess. Furthermore, in this embodiment, the case where the metal film 400 is exposed at the upper part of the recess and the metal film 400 has a structure having multiple grains 300 will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0035] In the processing order of this method, the following steps are performed: (a) Step A: In a state where the pressure inside the processing chamber 201, in which a wafer 200 containing a metal film 400 is disposed, is set to a first pressure, a -COOH-containing fluid is supplied to the wafer 200 at a first temperature to remove impurities 305 from the metal film 400. (b) Step B, in which the atmosphere inside the treatment chamber 201 is vented while the supply of the -COOH-containing fluid is stopped, so that the pressure inside the treatment chamber 201 becomes a second pressure lower than the first pressure; and (c) Maintaining the pressure in the processing chamber 201 at a second pressure, and exposing the metal-containing film 410 after the impurities 305 have been removed, heating the wafer 200 to a second temperature higher than the first temperature, thereby reducing the crystal grain size (diameter of the grains 310) of the metal component in the metal-containing film 410 to step C.

[0036] In the following examples, such as Figure 3 The following situations are explained as shown: In step A, a carrier gas containing -COOH fluid is supplied. In step B, the supply of carrier gas is stopped.

[0037] It should be noted that, in Figure 3 In the diagram, the implementation periods of steps A, B, and C are represented as A, B, and C, respectively.

[0038] Regarding the impurities 305 contained in the metal film 400, examples include oxygen (O) trapped by grain boundaries (grain boundaries) when the wafer 200 containing the metal film 400 is exposed to the atmosphere. Additionally, examples include O and carbon (C) contained in the residue of the electroplating solution used in the electroplating process during the formation of the metal film 400 in the recess of the wafer 200. Hereinafter, as an example, the case where the impurity 305 contained in the metal film 400 is O will be explained.

[0039] The term "fluid" as used in this specification includes at least one of gas, liquid, and vapor. Hereinafter, as an example, the case where the -COOH-containing fluid is a gas (gas, gaseous state) formed by vaporizing the first liquid described above will be explained.

[0040] The term "wafer" as used in this specification can refer to the wafer itself, or to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" can refer to the surface of the wafer itself, or to the surface of a specified layer, etc., formed on the wafer. When described as "forming a specified layer on the wafer," it can mean forming the specified layer directly on the surface of the wafer itself, or forming the specified layer on top of a layer, etc., formed on the wafer. In this specification, the use of "substrate" is synonymous with the use of "wafer."

[0041] (Substrate preparation process) Multiple wafers 200, each containing a metal film 400 and impurities 305, are loaded into a crystal boat 217. Then, as... Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat elevator 115 and moved into the processing chamber 201. In this state, the sealing cap 219 seals the lower end of the reaction tube 203.

[0042] (Pressure and temperature control process) Vacuum pump 246 is used to perform vacuum venting (pressure reduction venting) to bring the processing chamber 201, i.e., the space where the wafer 200 is located (arranged), to the desired pressure (vacuum level). At this time, the pressure within the processing chamber 201 is measured by pressure sensor 245, and the APC valve 244 is controlled based on this measured pressure information. Additionally, heater 207 is used to heat the wafer 200 to the desired processing temperature. At this time, the energization of heater 207 is controlled based on temperature information detected by temperature sensor 263 to achieve the desired temperature distribution within the processing chamber 201. Furthermore, rotation of the wafer 200 is initiated by rotation mechanism 267. Venting of the processing chamber 201, heating of the wafer 200, and rotation are all performed continuously, at least until the processing of the wafer 200 is completed.

[0043] (Preparation process for step A) In order to supply the -COOH-containing fluid to the wafer 200 in step A, a vaporized gas is generated in the gas generator 250a. In this manner, the -COOH-containing fluid (vaporized gas) is generated by vaporizing the first liquid.

[0044] Specifically, firstly, valves 243c and 243d are opened, and while using MFCs 241c and 241d for flow control, the first liquid and a carrier gas for vaporization are supplied to the gas generator 250a. The gas generator 250a generates vaporized gas (containing -COOH fluid) of the first liquid. At this time, the controller 121 controls MFC 241c to adjust the flow rate of the -COOH fluid generated by the gas generator 250a. It should be noted that by opening valve 243e and using MFC 241e for flow control while supplying pressurized gas to tank 250t, the first liquid stored in tank 250t is forced from tank 250t into supply pipe 232c. This step can also begin during or before the pressure and temperature regulation process.

[0045] (Step A: Impurity removal process) In this step, a -COOH-containing fluid is supplied to the metal-containing membrane 400 at the first temperature to remove impurities 305 from the metal-containing membrane 400.

[0046] Specifically, valve 243a is opened, and the -COOH-containing fluid generated in gas generator 250a is supplied to processing chamber 201 through MFC 241a, gas supply pipe 232a, and gas supply port 203p.

[0047] The -COOH-containing fluid supplied into the processing chamber 201 flows downwards into the processing chamber 201 and is discharged to the outside of the processing chamber 201 via the exhaust pipe 231. At this time, the -COOH-containing fluid is supplied to the wafer 200. Meanwhile, valve 243b is opened, and while the flow rate is regulated using MFC 241b, an inactive gas is supplied into the processing chamber 201 via gas supply pipes 232b and 232a and gas supply port 203p. The inactive gas serves as the carrier gas for the -COOH-containing fluid.

[0048] Examples of processing conditions for supplying -COOH-containing fluid in this step include: Processing temperature (first temperature): 80–120℃, preferably 90–100℃ Processing pressure (initial pressure): 700–1400 hPa, preferably 800–1100 hPa Supply flow rate of fluid containing -COOH: 5–400 ccm, preferably 50–300 ccm Supply time of fluid containing -COOH: 10–120 minutes, preferably 30–60 minutes Carrier gas supply flow rate for gasification: 0.5 slm to 10 slm, preferably 1 slm to 5 slm.

[0049] Carrier gas (inactive gas) supply flow rate: 1-10 slm.

[0050] It should be noted that the processing temperature (first temperature) in this step is preferably set to the temperature at which the fluid containing -COOH does not liquefy.

[0051] It should be noted that the numerical ranges expressed in this specification, such as "80~120℃", refer to the inclusion of both the lower and upper limits within that range. Therefore, for example, "80~120℃" means "above 80℃ and below 120℃". The same applies to other numerical ranges. Furthermore, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature within the processing chamber 201, and the processing pressure refers to the pressure within the processing chamber 201; in other words, it refers to the pressure of the space in which the wafer 200 exists. Additionally, the processing time refers to the duration of the processing. Furthermore, when the supply flow rate includes 0ccm, 0ccm means that the substance is not supplied. These same principles apply to the following descriptions.

[0052] By supplying a -COOH-containing fluid to wafer 200 under the above conditions, the metal-containing film 400 can be modified into a metal-containing film 410. (See...) Figure 4 (a) Figure 4 Specifically, (b) of the above describes the removal of impurities 305 from the metal-containing film 400 formed on the wafer 200. More specifically, by supplying the wafer 200 with a -COOH-containing fluid as a reducing agent under the above conditions, for example, the O component present in the interior of the metal-containing film 400 (e.g., grain boundaries) can react with the components of the -COOH-containing fluid that has penetrated into the interior of the metal-containing film 400, causing the O component to detach from the interior of the metal-containing film 400. The removed impurities sometimes diffuse into the processing chamber 201.

[0053] By supplying a COOH-containing fluid to the wafer 200 under the above conditions, the COOH-containing fluid can penetrate the entire metal film 400, specifically penetrating from the upper to the lower part of the recess.

[0054] By supplying a COOH-containing fluid to the wafer 200 under the above conditions, specifically by setting the processing temperature (first temperature) to a relatively low temperature, the diameter (size of the grains 310) contained in the metal film 410 can be maintained below a specified value (see [reference]). Figure 5 (a) Figure 5 (b)). At this time, the diameter of the grain 310 can be maintained below a predetermined value in both the upper and lower parts of the recess, specifically throughout the range from the upper to the lower part of the recess. In this way, by maintaining the diameter of the grain 310 below the predetermined value, the grain boundary energy between adjacent grains 310 can be maintained to a higher extent.

[0055] It should be noted that when the processing temperature is below 80℃, the -COOH-containing fluid may condense in the processing chamber 201. Consequently, the -COOH-containing fluid may not permeate the entire metal-containing membrane 400, making it difficult to remove impurities 305 from the metal-containing membrane 400. By setting the processing temperature above 80℃, condensation of the -COOH-containing fluid can be avoided, allowing it to permeate the entire metal-containing membrane 400 and remove impurities 305 from it.

[0056] When the processing temperature exceeds 120°C, the crystallization rate of the metal-containing film 400 may be greater than the rate at which the impurities 305 contained in the metal-containing film 400 are removed (the impurity removal rate). Specifically, for example, there is a risk that the diameter of the grains 300 contained in the metal-containing film 400 may become larger than a predetermined value before the impurities 305 are removed from the metal-containing film 400 and the concentration of the impurities 305 becomes the desired concentration. As a result, it is sometimes difficult to maintain a high grain boundary energy between adjacent grains. By setting the processing temperature to below 120°C, it is possible to make the impurity removal rate of the metal-containing film 400 greater than the crystallization rate of the metal-containing film 400. That is, it is possible to achieve the desired concentration of impurities 305 in the metal-containing film 400 before the diameter of the grains 300 becomes larger than the predetermined value. As a result, it is possible to remove impurities 305 from the metal-containing film 400 before the diameter of the grains 300 contained in the metal-containing film 400 becomes larger than the predetermined value, and it is possible to maintain a high grain boundary energy between adjacent grains.

[0057] Furthermore, when the temperature is rapidly increased, the crystallization rate of the metal-containing film 400 may become greater than the rate at which the impurities 305 contained in the metal-containing film 400 are removed (the impurity removal rate). Therefore, it is preferable to raise the temperature at a first heating rate that removes the impurities 305 in a manner that prevents the diameter of the grains 300 from becoming greater than a predetermined value before the impurities are removed. As the first liquid, liquids containing -COOH, such as formic acid (HCOOH) and acetic acid (CH3COOH), can be used. For example, a -COOH-containing fluid, such as a vaporized HCOOH or CH3COOH, functions as a reducing agent to remove impurities 305 (e.g., O components) from the metal-containing film 400. As the first liquid, a liquid containing HCOOH with higher reducing power is preferred. Because -COOH contains carbon, oxygen, and hydrogen, a -COOH-containing fluid is also called a carbon-oxygen-hydrogen-containing fluid. Similarly, a -COOH-containing gas is also called a carbon-oxygen-hydrogen-containing gas.

[0058] As used in this specification, the term "agent" includes at least one of gaseous and liquid substances. Liquid substances include mists. That is, a reducing agent may include gaseous substances, liquid substances such as mists, or both.

[0059] As a carrier gas (inactive gas), rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. More than one of these inactive gases can be used. This also applies to the steps described later.

[0060] For example, the same gas as the aforementioned inactive gas can be used as the carrier gas for gasification.

[0061] (Step B: Indoor air exhaust treatment process) After a specified time has elapsed and impurities 305 have been removed from the metal-containing film 400, valves 243a and 243b are closed to stop supplying the wafer 200 with -COOH-containing fluid and carrier gas. Then, the atmosphere in the processing chamber 201 is vented (vacuum venting) to remove residual fluids, reaction byproducts, etc., from the processing chamber 201.

[0062] Examples of processing conditions for vacuum degassing in this step include: Processing temperature (first temperature): 80–120℃, preferably 90–100℃ Processing pressure (second pressure lower than the first pressure): 100–3000 hPa Processing time: 5-60 minutes, preferably 5-10 minutes.

[0063] As described above, since the processing pressure (second pressure) in step B is lower than the processing pressure (first pressure) in step A, the exhaust flow rate to the outside of the processing chamber 201 in step B can be greater than the exhaust flow rate to the outside of the processing chamber 201 in step A.

[0064] By exhausting the atmosphere inside the processing chamber 201 under the above conditions, impurities 305, intermediates containing -COOH fluid, carrier gas, and natural oxide film formed on the surface of the wafer 200 when it is moved into the processing chamber 201 (specifically, the space and inner wall of the processing chamber 201) that are floating or attached to the processing chamber 201 can be discharged to the outside of the processing chamber 201.

[0065] (Step C: Heat treatment and annealing) After step B is completed, with the metal-containing film 410 exposed after the impurities 305 have been removed, the wafer 200 is heated to a second temperature higher than the first temperature (annealing). This step, for example, is performed sequentially as described later in steps c1 and c2.

[0066] [Step c1: Heating Step] In this step, the output of heater 207 is adjusted to perform annealing while the temperature of the metal film 410 rises from the first temperature to the second temperature.

[0067] Examples of processing conditions for annealing while raising the temperature of the metal-containing film 410 in this step include: Processing pressure (secondary pressure): 100–3000 hPa Processing time: 20-40 minutes, preferably 25-35 minutes.

[0068] In this step, the decompression state (second pressure) from step B is also maintained.

[0069] The second heating rate in step c1 is preferably greater than the aforementioned first heating rate. Assuming that the wafer 200 is gradually heated in step c1, it is believed that many crystals within the metal film 400 simultaneously and gradually increase in size. As a result, for example, the number of crystals of similar size increases, and consequently, the crystal grain size is not considered to be the desired size. In contrast, if the wafer 200 is rapidly heated at a second heating rate, for example, greater than the first heating rate, then there are crystals whose grain size increases with the heating, and crystals whose grain size does not increase because they do not follow the heating. Therefore, the former, the larger crystals, are able to grow without being hindered by impurities or surrounding crystals. Therefore, by setting the second heating rate, compared to gradual heating, it is possible to produce crystals with larger grain sizes.

[0070] [Step c2: Temperature maintenance process] If the temperature of the metal-containing film 410 reaches the second temperature, then an annealing process is performed while maintaining the metal-containing film 410 (specifically, the metal-containing film 420) at the second temperature (see [reference]). Figure 5 (b) Figure 5(c) in the middle.

[0071] Examples of processing conditions for annealing the metal-containing film 420 at a second temperature in this step include: Processing temperature (second temperature): 150–400℃, preferably 160–300℃ Processing pressure (secondary pressure): 100–3000 hPa Processing time: 30-300 minutes, preferably 60-180 minutes.

[0072] By raising the processing temperature (specifically, the temperature of the metal-containing film 410) from the first temperature to the second temperature and maintaining it at the second temperature under the above conditions, the metal-containing film 410 can be modified into a metal-containing film 420 (see...). Figure 4 (b) Figure 4 (c)). Specifically, it enables the grains 310 contained in the metal film 410 to grow into larger grains 320 (see (c)). Figure 5 (b) Figure 5 (c)). Thus, the diameter (crystal size) of the grains 320 containing the metal component in the metal film 420 in this step can be made larger (enlarged) than the diameter (crystal size) of the grains 310 in the metal film 410 in step B.

[0073] By raising the processing temperature from the first temperature to the second temperature and maintaining it at the second temperature under the above conditions, it is possible to make the diameter of the grains 320 contained in the metal film 420 larger than a specified value (see [reference]). Figure 5 (c)). At this time, in each of the upper and lower parts of the recess, specifically in the range from the upper to the lower part of the recess, the diameter of the grain 320 can be made to be a desired value larger than the specified value.

[0074] Furthermore, by raising the processing temperature from the first temperature to the second temperature and maintaining it at the second temperature under the above conditions, it is possible to remove the impurities 305 that remained in the metal-containing film 410 that could not be removed in step B (see Figure 5 (b) Figure 5 (c) is removed. In this step, since the depressurization state (second pressure) in step B is maintained, impurities such as intermediates containing -COOH fluid that were not discharged in step B can also be discharged out of the processing chamber 201, in addition to the impurities 305 removed from the metal membrane 410.

[0075] As described above, by making the diameter of grain 320 larger than the diameter of grain 310, the number of grain boundaries per unit volume in the metal-containing film 420 is less than the number of grain boundaries per unit volume in the metal-containing film 410. Therefore, the grain boundary energy between adjacent grains 320 in step C becomes lower than the grain boundary energy between adjacent grains 310 in step B.

[0076] It should be noted that if the processing temperature is below 150°C, the crystallization of the metal film 410 sometimes becomes difficult, and consequently, the increase in the diameter of the grains 320 is suppressed. Furthermore, if the processing temperature is below 150°C, there is a risk of condensation droplets remaining in the processing chamber 201, and consequently, after step C, a vacuum venting process to remove the atmosphere from the processing chamber 201 may be necessary. By setting the processing temperature to 150°C or higher, the metal film 410 can be crystallized, thus allowing the diameter of the grains 320 to increase to the desired value. Additionally, by setting the processing temperature to 150°C or higher, the retention of condensation droplets in the processing chamber 201 can be suppressed, thus eliminating the need for a vacuum venting process after step C.

[0077] If the processing temperature exceeds 400°C, the diameter of the grains 320 may become too large, and as a result, pores may sometimes form in the metal-containing film 420. By setting the processing temperature below 400°C, it is possible to suppress the excessive growth of the grain diameter 320, thereby forming a metal-containing film 420 with excellent film quality that does not produce pores.

[0078] (Atmospheric pressure recovery process) Next, vacuum pump 246 is used to exhaust the vacuum from the processing chamber 201. Additionally, inactive gas is supplied to the processing chamber 201 to restore its internal pressure to atmospheric pressure, increasing the heat capacity within the chamber. This allows for uniform heating of the wafer 200 and the components within the processing chamber 201, and removes particles, impurities 305, outgassing, etc., that could not be removed by vacuum exhaust. After a predetermined time, the processing chamber 201 is cooled to a predetermined removable temperature.

[0079] (Substrate removal process) The sealing cover 219 is lowered by the crystal boat lift 115, opening the lower end of the reaction tube 203. The processed wafer 200, supported by the crystal boat 217, is then moved from the lower end of the reaction tube 203 to the outside of the reaction tube 203. After being moved outside the reaction tube 203, the processed wafer 200 is removed from the crystal boat 217.

[0080] (3) The effect of this method According to this method, one or more of the following effects can be obtained.

[0081] (a) By performing steps A, B, and C, the resistivity of the metal film 420 can be reduced. This will be explained below.

[0082] In step A, by setting the temperature of wafer 200 (processing temperature) to a relatively low first temperature, impurities 305 can be removed from the metal-containing film 400 while suppressing the growth of grains 300 in the metal-containing film 400. Therefore, by setting the processing temperature to a relatively low first temperature in step A, the growth of grains 300 in the metal-containing film 400 can be suppressed, and the diameter of the grown grains 310 can be maintained below a predetermined value (see [reference]). Figure 5 (a) Figure 5 (b)). Therefore, a decrease in the number of grain boundaries per unit volume in the metal-containing film 410 can be avoided, thus maintaining a high grain boundary energy. Therefore, in step C, the atomic migration speed can be increased, thereby increasing the diameter of the grain 320. Furthermore, in step B, by removing impurities 305 from the metal-containing film 400 (specifically, impurities 305 present at the grain boundaries), the grain boundary energy can be increased. Therefore, in step C, the atomic migration speed can be increased, thereby increasing the diameter of the grain 320.

[0083] In step C, the diameter of the grain 320 can be increased by heating (annealing) the wafer 200 at a second temperature higher than the first temperature.

[0084] It should be noted that after step A, for example, apart from the natural oxide film (e.g., O component) formed on the surface of the wafer 200 when the wafer 200 is moved into the processing chamber 201, and the impurities 305 (e.g., O component) removed from the metal-containing film 400, impurities such as intermediates of the -COOH-containing fluid (e.g., C component) and components of the carrier gas (e.g., N component) supplied in step A float in the space within the processing chamber 201 or adhere to the inner wall of the processing chamber 201. When step C is performed in this state, impurities may penetrate into the metal-containing film 420, thereby potentially hindering the expansion of the diameter (crystal size) of the grains 320 containing the metal component in the metal-containing film 420.

[0085] In this invention, step B is performed after step A and before step C, in which the atmosphere inside the processing chamber 201 is vented, and impurities remaining in the processing chamber 201 are discharged outside the processing chamber 201. Therefore, in step C, the penetration of impurities that hinder the diameter expansion of the grains 320 into the metal-containing film 420 can be suppressed.

[0086] Furthermore, in step C, since the reduced pressure state (second pressure) of step B is maintained, the impurities 305 removed from the metal-containing film 410 during the execution of step C, as well as the impurities remaining in the processing chamber 201, can be discharged outside the processing chamber 201. Thus, in step C, the penetration of impurities that hinder the diameter expansion of the grains 320 into the metal-containing film 420 can be suppressed.

[0087] In step C, if the diameter of the grain 320 increases, the number of grain boundaries per unit volume in the metal-containing film 420 decreases, thereby reducing electron scattering at the grain boundaries. Consequently, electrons can more easily flow within the metal-containing film 420, reducing its resistivity. This, in turn, improves device characteristics.

[0088] (b) In step C, after stopping the supply of the -COOH-containing fluid in step A, the wafer 200 is heated from the first temperature to the second temperature. Thus, in step C, the metal-containing film 410 can be crystallized under conditions where the re-permeation of the -COOH-containing fluid intermediate is suppressed, thereby effectively increasing the diameter of the metal grains 320.

[0089] (c) In step C, after the venting of the atmosphere in step B is completed, the wafer 200 is heated from the first temperature to the second temperature. As a result, the metal-containing film 410 can be crystallized while the residual impurities in the processing chamber 201 are discharged outside the processing chamber 201, thus effectively increasing the diameter of the metal grains 320 while suppressing the influence of impurities.

[0090] (d) By supplying a carrier gas containing the -COOH fluid in step A, the -COOH fluid can permeate the entire metal-containing membrane 400. This effectively removes impurities 305 from the metal-containing membrane 400. In step B, the supply of carrier gas is stopped, and the processing chamber 201 is vented (vacuum venting) to create a reduced pressure state (second pressure), thereby effectively removing impurities remaining in the processing chamber 201. Furthermore, since the reduced pressure state (second pressure) is maintained in step C, impurities remaining in the processing chamber 201 are suppressed. Therefore, the vacuum treatment (vacuum venting) after step C can be omitted, thus improving productivity.

[0091] (e) The second temperature is the temperature at which the diameter of the grain 320 reaches a desired value. Therefore, in step C, the diameter of the grain 320 can be grown to the desired value. As a result, the resistivity of the metal-containing film 420 can be effectively reduced. Furthermore, by setting the second temperature to the temperature at which the diameter of the grain 320 reaches the desired value, excessive growth of the grain 320 diameter can be prevented in step C. Therefore, the formation of pores, etc., in the metal-containing film 420 can be suppressed.

[0092] (f) The amount of impurities present in the processing chamber 201 after step B is less than the amount of impurities present in the processing chamber 201 after step A. Therefore, in step C, by reducing the amount of impurities, the influence of impurities on the diameter expansion of the grain 320 can be suppressed, thus enabling more reliable diameter expansion of the grain 320.

[0093] (g) The processing temperature (first temperature) in step A is the temperature at which the -COOH-containing fluid does not liquefy. Therefore, in step A, it is possible to suppress the adhesion of substances formed by the liquefaction of the -COOH-containing fluid to the inner wall of the processing chamber 201. As a result, in step C, it is possible to suppress the penetration of liquefied components of the -COOH-containing fluid (e.g., component C) into the metal-containing membrane 420, thus enabling an increase in the diameter of the grains 320.

[0094] (h) The exhaust flow rate to the outside of the processing chamber 201 in step B is greater than the exhaust flow rate to the outside of the processing chamber 201 in step A. Therefore, the above-mentioned effect can be reliably obtained.

[0095] (i) The same effect can be obtained when using the above-mentioned -COOH-containing fluid and the above-mentioned various inactive gases.

[0096] <Other methods of this disclosure> The above description illustrates an example of supplying fluid to the wafer 200 from above the wafer housing region. However, this disclosure is not limited to the above aspects. For example, other methods may also be used. Figure 6 The substrate processing apparatus shown supplies fluid to the wafer 200 from the side of the wafer receiving area.

[0097] Figure 6 This is a longitudinal cross-sectional view of the processing furnace 302 portion of a substrate processing apparatus that uses nozzle 269 instead of gas supply port 203p to supply fluid to processing chamber 201. (See diagram below.) Figure 6As shown, the nozzle 269 is positioned vertically above the inner wall of the reaction tube 203 and the wafer 200, in the space between them, and is arranged along the inner wall of the reaction tube 203 from bottom to top in the direction of wafer arrangement. Gas supply holes 270 are provided on the side of the nozzle 269 to supply fluid from the outer periphery of the wafer 200, i.e., from the side of the wafer 200 towards its in-plane. Multiple gas supply holes 270 are provided from the bottom to the top of the reaction tube 203 at positions opposite to the wafer arrangement area. The nozzle 269 is connected to the gas supply pipe 232a. Fluid is supplied from the gas supply pipe 232a to the processing chamber 201 via the nozzle 269. The -COOH-containing fluid supply system mainly consists of the gas supply pipe 232a, MFC 241a, and valve 243a. The nozzle 269 can also be considered as part of the -COOH-containing fluid supply system. Other configurations are similar to... Figure 1 The substrate processing apparatus shown is the same as that used for... Figure 1 Elements that are substantially the same as those described in the figures are labeled with the same reference numerals, and their descriptions are omitted.

[0098] When using a substrate processing apparatus with this configuration, the same effect as described above can be obtained.

[0099] Furthermore, in this approach, with Figure 1 The apparatus shown differs in that it can bring the distance between the wafer 200 and the gas supply hole 270 closer not only in the upper part of the wafer housing area, but also in the middle and lower parts. This allows for consistent supply conditions (flow rate, velocity) of the fluid and inactive gas to the wafer 200 across the upper and lower portions. Therefore, in step B, fluid can be supplied to the wafer 200 under uniform conditions throughout the entire upper and lower portions of the wafer housing area, improving substrate uniformity in the removal of impurities from the metal film. Furthermore, in the purging process and step C, inactive gas can be supplied to the wafer 200 under uniform conditions throughout the entire upper and lower portions of the wafer housing area, improving substrate uniformity in the processing performed in each step (residue removal, film modification).

[0100] It should be noted that when the metal contained in the metal film is a metal that is less prone to migration than copper (Cu) (e.g., cobalt (Co), ruthenium (Ru), tungsten (W)), the processing temperature in step B needs to be set to a high temperature exceeding 150°C. Under such temperature conditions, the fluid is prone to thermal decomposition, which can lead to problems when using... Figure 1 When the apparatus shown supplies fluid from the upper part of the wafer housing region, the impurity removal effect is sometimes uneven between the upper and lower parts of the wafer housing region. In contrast, if using... Figure 6 The device shown supplies fluid from the side of the wafer housing area, thus reducing the likelihood of such high-temperature-specific problems.

[0101] Furthermore, in the above-described manner, if steps A, B, and C are performed consecutively within the same processing chamber, step B is preferred. This allows for the reliable removal of impurities generated in step A during step B, thus suppressing the adhesion of impurities generated in step C to the wafer 200 during step C.

[0102] Furthermore, the above method illustrates an example of performing steps A, B, and C once each, but it is not limited to this. For example, step C can be performed after combining steps A and B more than twice. By repeating the combination of steps A and B in this way, impurities can be removed more reliably. Since step C is performed thereafter, the crystal grain size can be increased in a state free of impurities. That is, the crystal grain size can be increased more reliably.

[0103] Furthermore, the above method illustrates an example of performing steps A, B, and C once each, but it is not limited to this. For example, steps A, B, and C can be combined and performed more than twice. In this way, the operation of increasing the crystal grain size can be repeated while removing impurities from the metal film, thus increasing the crystal grain size more reliably.

[0104] <Other embodiments of this disclosure> The foregoing has detailed the manner in which this disclosure is made. However, this disclosure is not limited to the manner described above, and various modifications can be made without departing from its spirit.

[0105] In the above description, the case where the -COOH-containing fluid is in gaseous form was used as an example, but this disclosure is not limited to this method. The -COOH-containing fluid can also be, for example, vapor or liquid. In this method, at least some of the effects described in the above method can also be obtained.

[0106] Although not described in the above embodiments, for example, a Cu-containing film, a Co-containing film, a W-containing film, or a Ru-containing film can be used as the metal-containing film 400. More than one of these can be used as the metal-containing film 400. In other words, as the metal material (metal composition) constituting the metal-containing film 400, for example, Cu, Co, W, and Ru can be used. In this method, the same effects as described above can be obtained.

[0107] The above description uses the case where the carrier gas supply is stopped in step B as an example, but this disclosure is not limited to this method. For example, the carrier gas supply can also be reduced in step B. The same effect as described above can be obtained in this method.

[0108] Although not described in the above, for example, when a silicon (Si) film (e.g., a SiO film) is formed as a substrate on the inner surface of the recess formed in the wafer 200, it is preferable to form a liner between the metal film 400 and the SiO film to prevent the metal atoms contained in the metal film 400 from diffusing into the SiO film.

[0109] For example, the above description illustrates a case where the substrate processing apparatus has one processing chamber 201, and all steps A, B, and C are performed within this processing chamber 201. However, this disclosure is not limited to this configuration. For instance, the substrate processing apparatus may have multiple processing chambers (cavities), with steps A, B, and C performed in different cavities. However, in this case, when the wafer 200 is transferred to the cavity for step B after step A, or when the wafer 200 is transferred to the cavity for step C after step B, impurities 305 may sometimes intrude into the wafer 200 due to exposure to the atmosphere. In these cases, it is preferable to perform a process to remove impurities 305 from the wafer 200 before starting steps B and C.

[0110] The processing steps for each step are preferably prepared separately according to the processing content, and are pre-recorded and stored in the storage device 121c via an electrical communication line and an external storage device 123. Furthermore, when starting each process, the CPU 121a preferably selects an appropriate process from the multiple processes recorded and stored in the storage device 121c according to the processing content. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses using a single substrate processing device. Additionally, it reduces the operator's workload, enabling rapid initiation of each process while minimizing operational errors.

[0111] The aforementioned process is not limited to newly generated cases; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can also be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the process. Alternatively, the existing process already installed in the substrate processing apparatus can be directly modified by operating the input / output device 122 of the existing substrate processing apparatus.

[0112] In the above-described method, an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time has been explained. This disclosure is not limited to the above-described method; for example, it can also be suitably applied to forming films using a single-sheet substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described method, an example of forming a film using a substrate processing apparatus with a hot-wall type furnace has been explained. This disclosure is not limited to the above-described method; it can also be suitably applied when forming films using a substrate processing apparatus with a cold-wall type furnace.

[0113] When using these substrate processing apparatuses, each processing step and processing condition can be performed in the same manner and with the same processing conditions as described above and in the modified examples, and the same effect as described above and in the modified examples can be obtained.

[0114] The methods and variations described above can be used in appropriate combinations. The processing steps and conditions can be set to be the same as those in the methods and variations described above.

Claims

1. A substrate processing method, which has the following characteristics: (a) A process of supplying a carboxyl-containing fluid to a substrate having a metal film at a first pressure and a first temperature to remove impurities from the metal film; (b) The process of stopping the supply of the carboxyl-containing fluid and venting the atmosphere around the substrate to make the pressure on the substrate a second pressure lower than the first pressure; and (c) A process of setting the pressure on the substrate to the second pressure and, with the metal-containing film exposed after the impurities have been removed, heating the substrate to a second temperature higher than the first temperature, thereby increasing the crystal size of the metal component in the metal-containing film.

2. The substrate processing method according to claim 1, wherein, In (c), after the supply of the carboxyl-containing fluid in (a) is stopped, the process of heating the substrate from the first temperature to the second temperature begins.

3. The substrate processing method according to claim 1, wherein, In (c), after the venting of the atmosphere described in (b) is completed, the process of heating the substrate from the first temperature to the second temperature begins.

4. The substrate processing method according to claim 1, wherein, In (a), a carrier gas is supplied to the carboxyl-containing fluid. In (b), the supply of the carrier gas is stopped or the amount of carrier gas supplied is reduced.

5. The substrate processing method according to claim 1, wherein, The temperature of the substrate in (c) is higher than the temperature of the substrate in (a).

6. The substrate processing method according to claim 1, wherein, The second temperature is the temperature at which the crystal grain size becomes the desired value.

7. The substrate processing method according to claim 1, wherein, (b) The amount of the impurities present in the processing chamber after the end of the process is less than the amount of the impurities present in the processing chamber after the end of the process in (a).

8. The substrate processing method according to claim 1, wherein, The first temperature in (a) is the temperature at which the carboxyl-containing fluid does not liquefy.

9. The substrate processing method according to claim 1, wherein, (a) and (b) are carried out in the same processing chamber, wherein the exhaust flow rate to the outside of the processing chamber in (b) is greater than the exhaust flow rate to the outside of the processing chamber in (a).

10. The substrate processing method according to claim 1, wherein, The carboxyl-containing fluid is formic acid or acetic acid.

11. The substrate processing method according to claim 1, wherein, The metal-containing film is at least one of a copper-containing film, a cobalt-containing film, or a tungsten-containing film.

12. The substrate processing method according to claim 1, wherein, (a), (b) and (c) were carried out continuously in the same treatment chamber.

13. The substrate processing method according to claim 1, wherein, The substrate in (c) is processed in such a way that the heating rate of the substrate in (a) becomes greater than the heating rate of the substrate in (a).

14. The substrate processing method according to claim 1, wherein, In (c), the grains are heated to the second temperature in such a way that the growth rates of adjacent grains are different from each other.

15. The substrate processing method according to claim 1, wherein, After combining (a) and (b) more than once, execute (c).

16. The substrate processing method according to claim 1, wherein, After combining (a) and (b) more than twice, execute (c).

17. The substrate processing method according to claim 1, wherein, Perform the combination of (a), (b), and (c) more than twice.

18. A method for manufacturing a semiconductor device, comprising: (a) A process of supplying a carboxyl-containing fluid to the substrate at a first temperature while the pressure in a processing chamber containing a substrate with a metal film is set to a first pressure, thereby removing impurities from the metal film. (b) A process of venting the atmosphere in the processing chamber while the supply of the carboxyl-containing fluid is stopped, so that the pressure in the processing chamber becomes a second pressure lower than the first pressure. and (c) A process of maintaining the pressure in the processing chamber at the second pressure and, with the metal-containing film exposed after the impurities have been removed, heating the substrate to a second temperature higher than the first temperature, thereby increasing the crystal size of the metal component in the metal-containing film.

19. A substrate processing apparatus, comprising: The supply unit is capable of supplying a carboxyl-containing fluid to a substrate containing a metal film disposed in the processing chamber; An exhaust unit is provided to exhaust the atmosphere inside the processing chamber. A heating element capable of heating the substrate; and The control unit is configured to control the supply unit, the exhaust unit, and the heating unit to perform the following processes: (a) A process of removing impurities from a metal-containing film by supplying the carboxyl-containing fluid to the substrate at a first temperature while the pressure in the processing chamber is set to a first pressure; (b) A process in which the atmosphere in the processing chamber is vented while the supply of the carboxyl-containing fluid is stopped, so that the pressure in the processing chamber becomes a second pressure lower than the first pressure. and (c) A process in which the pressure in the processing chamber is maintained at the second pressure and the metal-containing film is exposed after the impurities have been removed, and the substrate is heated to a second temperature higher than the first temperature, thereby increasing the crystal size of the metal component in the metal-containing film.

20. A procedure for using a computer to cause the substrate processing apparatus to perform the following steps: (a) A step of supplying a carboxyl-containing fluid to the substrate at a first temperature while the pressure in a processing chamber containing a substrate with a metal film is set to a first pressure, thereby removing impurities from the metal film. (b) The step of venting the atmosphere in the processing chamber while the supply of the carboxyl-containing fluid has been stopped, so that the pressure in the processing chamber becomes a second pressure lower than the first pressure; and (c) Maintaining the pressure in the processing chamber at the second pressure and exposing the metal-containing film after the impurities have been removed, heating the substrate to a second temperature higher than the first temperature to expand the crystal grain size of the metal component in the metal-containing film.

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