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

Abstract

To provide a technique that allows for selective formation of a metal-containing film from a specific region on a substrate.SOLUTION: A method includes a step (a) of forming an adsorption-promoting layer on a substrate by supplying a halogen-containing agent to the substrate, the adsorption-promoting layer promoting the adsorption of an organic-containing agent, a step (b) of forming a modified layer on the substrate by supplying the organic-containing agent to the substrate, a step (c) of supplying a raw material containing a metal element to the substrate, a step (d) of supplying a reactant to the substrate, and a step (e) of forming a metal-containing film in an area of the substrate where the modified layer is not formed by performing the steps of (b), (c), and (d) N times after the step (a).SELECTED DRAWING: Figure 3

Description

[Technical Field]

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

[0002] BACKGROUND ART As one step in the manufacturing process of a semiconductor device, a process of forming a film on a substrate accommodated in a processing chamber may be performed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 073924 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it can be difficult to selectively form a metal-containing film from a particular area on a substrate.

[0005] The present disclosure provides techniques that allow for selective formation of metal-containing films from specific regions on a substrate. [Means for solving the problem]

[0006] According to one aspect of the present disclosure, (a) forming an adsorption-promoting layer on a substrate by supplying a halogen-containing agent to the substrate, the adsorption-promoting layer promoting adsorption of an organic-containing agent; (b) forming a modified layer on the substrate by applying the organic containing agent to the substrate; (c) supplying a raw material containing a metal element to the substrate; (d) providing reactants to the substrate; (e) after (a), performing (b), (c), and (d) N times to form a metal-containing film in an area of ​​the substrate where the modified layer is not formed; The present invention provides a technique having the following. [Effects of the Invention]

[0007] According to the present disclosure, it is possible to selectively form a metal-containing film in a specific region on a substrate. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a longitudinal cross-sectional view showing an outline of a vertical processing furnace of a substrate processing apparatus according to one embodiment. [Figure 2] FIG. 2 is a schematic diagram of a controller of a substrate processing apparatus according to one embodiment, showing a control system of the controller in a block diagram. [Figure 3] FIG. 3 is a flow chart illustrating a substrate processing process according to one embodiment. [Figure 4] FIG. 4 is a cross-sectional view showing a state in which a metal-containing film has been formed in a recess of a substrate. [Figure 5] Figure 5(A) is a cross-sectional view showing a state in which a metal oxide film 500 has been formed on a first film 300 of a substrate, Figure 5(B) is a cross-sectional view showing a state in which the metal oxide film 500 on the first film 300 of the substrate has been removed and an adsorption-promoting layer 600 has been formed on a second film 400, Figure 5(C) is a cross-sectional view showing a state in which the adsorption-promoting layer 600 on the second film 400 of the substrate has been modified into a modified layer 700, Figure 5(D) is a cross-sectional view showing a state in which a metal-containing layer 800 has been adsorbed onto the first film 300 of the substrate, and Figure 5(E) is a cross-sectional view showing a state in which a metal-containing film 900 has been formed on the first film 300 of the substrate. [Figure 6] FIG. 6 is a diagram showing a modified example of a substrate processing step according to one embodiment. [Figure 7] FIG. 7 is a diagram showing a modified example of a substrate processing step according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, one embodiment of the present disclosure will be described mainly with reference to FIGS. 1 to 7. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships, ratios, etc. of the elements shown in the drawings do not necessarily correspond to the actual ones. Furthermore, the dimensional relationships, ratios, etc. of the elements between the multiple drawings do not necessarily correspond to the actual ones. Furthermore, substantially identical elements between multiple drawings are denoted by the same reference numerals, and each element is described in the drawing in which it first appears, and its description is omitted in subsequent drawings unless particularly necessary. Furthermore, the present disclosure is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the present disclosure.

[0010] (1) Configuration of the substrate processing equipment The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating unit. The heater 207 has a cylindrical shape and is installed vertically by being supported by a holding plate.

[0011] An outer tube 203 constituting a reaction vessel (processing vessel) is disposed inside the heater 207 and concentrically with the heater 207. The outer tube 203 is also referred to as an outer tube. The outer tube 203 is made of a heat-resistant material such as quartz or silicon carbide, and is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 (hereinafter referred to as MF 209) is disposed below the outer tube 203 and concentrically with the outer tube 203. The MF 209 is made of a metal material such as stainless steel, and is formed in a cylindrical shape with open upper and lower ends. An O-ring 220a is provided as a sealing member between the upper end of the MF 209 and the outer tube 203. The outer tube 203 is installed vertically, similar to the heater 207.

[0012] An inner tube 204 that constitutes a reaction vessel is disposed inside the outer tube 203. The inner tube 204 is also referred to as an inner tube. The inner tube 204 is made of a heat-resistant material such as quartz or silicon carbide, and is formed in a cylindrical shape with a closed upper end and an open lower end. The outer tube 203, the inner tube 204, and the MF 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel (inside the inner tube 204).

[0013] The processing chamber 201 is configured to accommodate wafers 200 as substrates arranged in multiple stages in the vertical direction in a horizontal position using a boat 217 (described later).

[0014] Nozzles 410, 420, 430, and 440 are provided in the processing chamber 201 so as to penetrate the sidewall of the MF 209 and the inner pipe 204. Gas supply pipes 310, 320, 330, and 340 are connected to the nozzles 410, 420, 430, and 440, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned configuration.

[0015] Gas supply pipes 310, 320, 330, 340 are respectively provided, from the upstream side, with mass flow controllers (MFCs) 312, 322, 332, 342 which are flow rate controllers (flow rate control parts) and valves 314, 324, 334, 344 which are on-off valves. Gas supply pipes 510, 520, 530, 540 which supply inert gas are connected to the downstream sides of valves 314, 324, 334, 344 of gas supply pipes 310, 320, 330, 340. Gas supply pipes 510, 520, 530, 540 are respectively provided, from the upstream side, with MFCs 512, 522, 532, 542 and valves 514, 524, 534, 544.

[0016] Nozzles 410, 420, 430, and 440 are respectively connected to the tip ends of the gas supply pipes 310, 320, 330, and 340. The nozzles 410, 420, 430, and 440 are configured as L-shaped nozzles, and their horizontal portions are provided so as to penetrate the side wall of the MF 209 and the inner pipe 204. The vertical portions of the nozzles 410, 420, 430, and 440 are provided inside the channel-shaped (groove-shaped) preliminary chamber 201a that protrudes radially outward from the inner pipe 204 and extends vertically, and are provided inside the preliminary chamber 201a facing upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner pipe 204.

[0017] The nozzles 410, 420, 430, and 440 are provided so as to extend from the lower region of the processing chamber 201 to the upper region of the processing chamber 201, and are provided with a plurality of gas supply holes 410a, 420a, 430a, and 440a at positions facing the wafer 200, respectively.

[0018] A source gas containing a metal element is supplied as a processing gas from the gas supply pipe 310 into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410.

[0019] A reaction gas, which is a reactant of the raw material, is supplied as a processing gas from the gas supply pipe 320 into the processing chamber 201 via the MFC 322 , the valve 324 , and the nozzle 420 .

[0020] From the gas supply pipe 330, an organic-containing gas, which is an organic-containing agent containing silicon (Si), an amino group, and an alkyl group, is supplied as a processing gas into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 430.

[0021] A halogen-containing gas, which is a halogen-containing agent containing a halogen element, is supplied as a processing gas from the gas supply pipe 340 into the processing chamber 201 via the MFC 342, the valve 344, and the nozzle 440.

[0022] Inert gas is supplied from gas supply pipes 510, 520, 530, and 540 into the processing chamber 201 via MFCs 512, 522, 532, and 542, valves 514, 524, 534, and 544, and nozzles 410, 420, 430, and 440, respectively.

[0023] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. Liquid substances include mist-like substances. That is, the halogen-containing agent and the organic-containing agent may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0024] The process gas supply unit is mainly composed of the gas supply pipes 310, 320, 330, and 340, the MFCs 312, 322, 332, and 342, the valves 314, 324, 334, and 344, and the nozzles 410, 420, 430, and 440, but the nozzles 410, 420, 430, and 440 alone may be considered to be the process gas supply unit. The process gas supply unit may simply be referred to as the gas supply unit. The gas supply pipe 310, the MFC 312, and the valve 314 mainly compose a first supply unit (also referred to as a source supply unit or source gas supply unit), but the nozzle 410 may be considered to be included in the first supply unit. The gas supply pipe 320, the MFC 322, and the valve 324 mainly compose a second supply unit (also referred to as a reactant supply unit or reactant gas supply unit), but the nozzle 420 may be considered to be included in the second supply unit. A third supply unit (also referred to as an organic-containing agent supply unit or an organic-containing gas supply unit) is mainly composed of gas supply pipe 330, MFC 332, and valve 334, but nozzle 430 may also be included in the third supply unit. A fourth supply unit (also referred to as a halogen-containing agent supply unit or a halogen-containing gas supply unit) is mainly composed of gas supply pipe 340, MFC 342, and valve 344, but nozzle 440 may also be included in the fourth supply unit. An inert gas supply unit is mainly composed of gas supply pipes 510, 520, 530, and 540, MFCs 512, 522, 532, and 542, and valves 514, 524, 534, and 544.

[0025] The exhaust hole 204a is provided at a position facing the plurality of wafers 200. Gas supplied from the gas supply holes 410a, 420a, 430a, and 440a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally and then flows into the exhaust path 206 through the exhaust hole 204a. The exhaust hole 204a is not limited to being configured as a slit-shaped through-hole, and may be configured as a plurality of holes.

[0026] The MF 209 is provided with an exhaust pipe 231 that exhausts the atmosphere inside the processing chamber 201. The exhaust pipe 231 is connected to, in order from upstream, a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 (hereinafter referred to as the pump 246) as a vacuum exhaust device. The APC valve 243 can evacuate and stop the vacuum exhaust inside the processing chamber 201 by opening and closing the valve while the pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening while the pump 246 is operating. An exhaust system is mainly composed of the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The pump 246 may be included in the exhaust system.

[0027] A seal cap 219 (hereinafter referred to as the cap 219) is provided below the MF 209 as a furnace port cover capable of airtightly closing the lower end opening of the MF 209. The cap 219 is configured to abut against the lower end of the MF 209 from below in the vertical direction. The cap 219 is made of a metal such as SUS and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the cap 219 as a sealing member that abuts against the lower end of the MF 209. A rotation mechanism 267 is provided on the opposite side of the cap 219 from the processing chamber 201 to rotate a boat 217 that accommodates wafers 200. A rotation shaft 255 of the rotation mechanism 267 passes through the cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafers 200. The cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 (hereinafter referred to as the elevator 115) as an elevating mechanism installed vertically outside the outer tube 203. The elevator 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by lifting and lowering the cap 219. The elevator 115 is configured as a transfer device (transfer system) that transfers the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

[0028] The boat 217, serving as a substrate support, is configured to hold a plurality of wafers 200, for example, 25 to 200, arranged horizontally and with their centers aligned at intervals in the vertical direction. The boat 217 is made of a heat-resistant material such as quartz or SiC. The lower part of the boat 217 is supported by a heat-insulating cylinder 218, which is a cylindrical member made of a heat-resistant material such as quartz or SiC. This configuration makes it difficult for heat from the heater 207 to be transmitted to the cap 219. However, this embodiment is not limited to the above. For example, instead of providing the heat-insulating cylinder 218, multiple heat-insulating plates made of a heat-resistant material such as quartz or SiC may be supported horizontally in multiple stages (not shown) at the lower part of the boat 217.

[0029] A temperature sensor 263 serving as a temperature detector is installed inside the inner pipe 204. The amount of power supplied to the heater 207 is adjusted based on temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution inside the processing chamber 201. The temperature sensor 263 is installed along the inner wall of the inner pipe 204.

[0030] 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 be able to exchange data with the CPU 121a via an internal bus. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. The controller 121 is also configured to be able to connect to an external storage device 123.

[0031] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. The storage device 121c readably stores a control program for controlling the operation of the substrate processing apparatus, a process recipe describing the procedures and conditions of a semiconductor device manufacturing method (substrate processing method) described later, and the like. The process recipe is a combination of processes (steps) in a semiconductor device manufacturing method (substrate processing method) described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc. are collectively referred to simply as a program. In this specification, the term "program" may refer to a process recipe alone, a control program alone, or a combination of a process recipe and a control program. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0032] The I / O port 121d is connected to the above-mentioned MFCs 312, 322, 332, 342, 512, 522, 532, 542, valves 314, 324, 334, 344, 514, 524, 534, 544, pressure sensor 245, APC valve 243, pump 246, heater 207, temperature sensor 263, rotation mechanism 267, elevator 115, etc.

[0033] The CPU 121a is configured to read and execute a control program from the storage device 121c, and also to read a recipe or the like from the storage device 121c in response to an input of an operation command from the input / output device 122. The CPU 121a is configured to be able to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 342, 512, 522, 532, and 542, the opening and closing operations of the valves 314, 324, 334, 344, 514, 524, 534, and 544, the opening and closing operation of the APC valve 243 and the pressure adjustment operation by the APC valve 243 based on the pressure sensor 245, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the start and stop of the pump 246, 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 elevator 115, the operation of storing the wafers 200 in the boat 217, and the like.

[0034] The controller 121 can be configured by installing the above-described program stored in an external storage device 123 (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, or a semiconductor memory such as a USB memory or a memory card) and installing the stored program on a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the recording medium may include only the storage device 121c, only the external storage device 123, or both. The program (program product) may be provided to a computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0035] (2) Substrate processing process (substrate processing method) As one step in the manufacturing process of a semiconductor device, an example of a process for selectively forming a metal-containing film 900 containing a metal element from the first film 300 of a wafer 200 having a first film 300 and a second film 400 formed on its surface will be described with reference to Figures 3 to 5. This process is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operation of each component constituting the substrate processing apparatus 10 is controlled by a controller 121.

[0036] The first film 300 is a metal-containing film. As the metal-containing film, a film containing at least one of a metal element and a transition metal (also called a transition element), such as tungsten (W), molybdenum (Mo), copper (Cu), cobalt (Co), etc. can be used. The first film 300 can be used as metal wiring, and may be metal wiring M1 in the bottom layer of a wiring layer or metal wiring My in an intermediate layer (y is a natural number).

[0037] The second film 400 is a non-metal oxide film. As the non-metal oxide film, an insulating film such as a silicon oxide (SiO2) film can be used.

[0038] Here, as shown in FIG. 4, for example, a first film 300, which is a metal-containing film, is formed on a wafer 200. A second film 400, which is an insulating film, is then formed on the first film 300. A recess, such as a trench or a hole, is then formed in the second film 400, and a metal-containing film 900, such as ruthenium (Ru), is formed in the recess. Before the metal-containing film 900 is formed in the recess, a metal oxide film 500, which is a native oxide film, may be formed on the surface of the first film 300. In particular, the first film 300, which is made of a transition metal such as W, Mo, Cu, or Co, is easily oxidized. As shown in FIG. 4, if the metal-containing film 900 is formed in the recess while the metal oxide film 500 remains, the contact resistance of the metal-containing film 900 may increase. Furthermore, when a Ru film, for example, is formed as the metal-containing film 900, reducing the contact resistance is essential to take advantage of the low resistance of the Ru film. Furthermore, when a Ru film is formed, the Ru film has the characteristic of being difficult to grow on the metal oxide film 500.

[0039] In the substrate processing step (semiconductor device manufacturing step) according to this embodiment, a metal-containing film 900 is selectively formed on a wafer 200 having a first film 300 on which a metal oxide film 500 is formed and a second film 400, while at least a portion of the metal oxide film 500 formed on the first film 300 is removed. This promotes the growth of the metal-containing film 900 formed in the recesses of the wafer 200, thereby reducing the contact resistance of the metal-containing film 900.

[0040] Figures 5(A) to 5(E) show plan views of the first film 300 and the second film 400 on the wafer 200 as shown in Figure 4. As shown in Figure 5(A), a metal oxide film 500, which is a native oxide film, is formed on the first film 300.

[0041] In this specification, for convenience, the substrate processing steps shown in Fig. 3 may be expressed as follows: Similar notations will be used in the following explanations of modified examples.

[0042] Halogen-containing gas → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 N1 and N2 are integers of 1 or greater

[0043] That is, when N1=1, it can be shown as follows: The same applies below. Halogen-containing gas → (organic-containing gas → raw material gas → reactive gas) × N2

[0044] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0045] (Wafer loading) 1, the boat 217 supporting the wafers 200 is lifted by the elevator 115, carried into the processing chamber 201, and accommodated in the processing vessel. In this state, the cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0046] (pressure and temperature regulation) The processing chamber 201, i.e., the space in which the wafer 200 is present, is evacuated by the pump 246 to a desired pressure. At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled (pressure adjustment) based on this measured pressure information. The pump 246 is kept in a constantly operating state at least until the processing of the wafer 200 is completed.

[0047] The inside of the processing chamber 201 is heated by the heater 207 to a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled (temperature adjustment) based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Heating of the inside of the processing chamber 201 by the heater 207 continues at least until processing of the wafer 200 is completed.

[0048] A. First pre-treatment step (Halogen-containing gas supply process, step S1) Valve 344 is opened to allow a halogen-containing gas to flow into gas supply pipe 340. The flow rate of the halogen-containing gas is adjusted by MFC 342, and the halogen-containing gas is supplied into processing chamber 201 through gas supply holes 440a of nozzle 440 and exhausted through exhaust pipe 231. At this time, the halogen-containing gas is supplied to wafer 200. At the same time, valve 544 is opened to allow an inert gas to flow into gas supply pipe 540. The inert gas flowing through gas supply pipe 540 has its flow rate adjusted by MFC 542, and is supplied into processing chamber 201 together with the halogen-containing gas and exhausted through exhaust pipe 231. At this time, in order to prevent the halogen-containing gas from entering nozzles 410, 420, and 430, valves 514, 524, and 534 are opened to allow the inert gas to flow into gas supply pipes 510, 520, and 530. The inert gas is supplied into the processing chamber 201 through gas supply pipes 310 , 320 , and 330 and nozzles 410 , 420 , and 430 , and is exhausted from an exhaust pipe 231 .

[0049] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 to a pressure within a range of, for example, 1 to 3990 Pa. The supply flow rate of the halogen-containing gas controlled by the MFC 342 is set to a flow rate within a range of, for example, 0.05 to 20 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, 532, and 542 are each set to a flow rate within a range of, for example, 0.1 to 50 slm. Note that in this disclosure, the notation of a numerical range such as "1 to 3990 Pa" means that the lower limit and the upper limit are included in the range. Thus, for example, "1 to 3990 Pa" means "1 Pa or more and 3990 Pa or less." The same applies to other numerical ranges.

[0050] The halogen-containing gas undergoes a substitution reaction with at least a portion of the metal oxide film 500 formed on the first film 300. That is, as shown in FIGS. 5A and 5B, oxygen atoms (O) in the metal oxide film 500 react with halogen elements contained in the halogen-containing gas, are desorbed from the metal oxide film 500, and are discharged from the processing chamber 201 as reaction by-products. As a result, at least a portion of the metal oxide film 500 is removed (etched). At this time, halogen elements contained in the halogen-containing gas are adsorbed onto the second film 400, and an adsorption-promoting layer 600 is formed on the second film 400, which is a layer that promotes adsorption of the organic-containing gas in the organic-containing gas supplying step S2.

[0051] As the halogen-containing gas, for example, a gas capable of selectively etching the metal oxide film 500 and adsorbing a halogen element onto the non-metal oxide film is used. As the halogen-containing gas, for example, a Cl-containing gas containing chlorine (Cl) can be used. As the Cl-containing gas, for example, a gas containing one or more Cl atoms and one or more O atoms can be used. In other words, as the Cl-containing gas, a gas having a molecular structure of MO x Cl y An oxyhalide (also called oxyhalide) having the formula: M can be used. Here, M includes at least one of Group 14, Group 15, and Group 16 elements, such as phosphorus (P), silicon (Si), germanium (Ge), sulfur (S), and carbon (C). As the oxyhalide, a gas containing any of Group 14, Group 15, and Group 16 elements, O, and Cl, such as POCl3, SOCl2, or COCl2, can be used. As the halogen-containing gas, one or more of these can be used.

[0052] As the inert gas, for example, N2 gas or a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used. One or more of these can be used as the inert gas. This also applies to other inert gases described later.

[0053] Specifically, by supplying an oxyhalide, which is an example of a halogen-containing gas, to a wafer 200 having a W film, which is an example of a first film 300, and a SiO film, which is an example of a second film 400, the O contained in a tungsten oxide (WOx) film, which is a metal oxide film formed on the surface of the W film, reacts with Cl and O contained in the oxyhalide to generate WOCl, which is desorbed from the WOx film. This etches the WOx film. Meanwhile, Cl desorbed from the oxyhalide is adsorbed onto the SiO2 film. That is, a Cl termination is formed on the SiO2 film, forming a Cl layer, which is an example of an adsorption-promoting layer 600 and an adsorption layer of Cl.

[0054] That is, by supplying a halogen-containing gas to the wafer 200, the metal oxide film 500 formed on the first film 300 is etched, while an adsorption-promoting layer 600 that promotes adsorption of an organic-containing gas (described later) is formed on the second film 400. The halogen-containing gas can be referred to as an etching gas that etches the metal oxide film 500, or as an adsorption-promoting gas that promotes adsorption of the organic-containing gas onto the second film 400.

[0055] After a predetermined time has elapsed since the start of the supply of the halogen-containing gas, the valve 344 of the gas supply pipe 340 is closed to stop the supply of the halogen-containing gas. At this time, the APC valve 243 of the exhaust pipe 231 is left open, and the processing chamber 201 is evacuated by the pump 246 to remove any unreacted halogen-containing gas remaining in the processing chamber 201 or that has contributed to etching the metal oxide film 500 and forming the adsorption promoting layer 600 on the second film 400 from the processing chamber 201 (evacuating the space where the wafer 200 is present). In other words, the processing chamber 201 is purged. At this time, the valves 514, 524, 534, and 544 are left open to maintain the supply of the inert gas into the processing chamber 201.

[0056] B. Second pre-treatment process (Organic-containing gas supply process, step S2) Next, valve 334 is opened, and an organic-containing gas is allowed to flow into gas supply pipe 330. The flow rate of the organic-containing gas is adjusted by MFC 332, and the organic-containing gas is supplied into processing chamber 201 through gas supply holes 430a of nozzle 430, and is exhausted through exhaust pipe 231. At this time, the organic-containing gas is supplied to wafer 200. At the same time, valve 534 is opened, and an inert gas is allowed to flow into gas supply pipe 530. The inert gas flowing through gas supply pipe 530 has its flow rate adjusted by MFC 532, and is supplied into processing chamber 201 together with the organic-containing gas, and is exhausted through exhaust pipe 231. At this time, in order to prevent intrusion of the organic-containing gas into nozzles 410, 420, and 440, valves 514, 524, and 544 are opened, and the inert gas is allowed to flow into gas supply pipes 510, 520, and 540. The inert gas is supplied into the processing chamber 201 through gas supply pipes 310 , 320 , and 340 and nozzles 410 , 420 , and 440 , and is exhausted from an exhaust pipe 231 .

[0057] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 2000 Pa. The supply flow rate of the organic-containing gas controlled by the MFC 332 is set within a range of, for example, 0.001 to 3 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, 532, and 542 are each set within a range of, for example, 0.1 to 20 slm.

[0058] The organic-containing gas is a gas that is preferentially (also referred to as actively) adsorbed to the adsorption-promoting layer 600 on the second film 400 compared to the first film 300. Therefore, as shown in FIGS. 5B and 5C, the supply of the organic-containing gas causes at least a portion of the Si(CH) and other elements contained in the organic-containing gas to be adsorbed to the halogen elements (e.g., Cl termination) contained in the adsorption-promoting layer 600 on the second film 400, thereby modifying the adsorption-promoting layer 600 on the second film 400 into a modified layer 700. Furthermore, the halogen elements (e.g., Cl termination) contained in the adsorption-promoting layer 600 on the second film 400 are substituted with at least a portion of the Si(CH) and other elements contained in the organic-containing gas, thereby modifying the adsorption-promoting layer 600 on the second film 400 into a modified layer 700. That is, the supply of the organic-containing gas modifies the adsorption-promoting layer 600 on the second film 400 into a modified layer 700, and Si alkyl termination is formed on the modified layer 700.

[0059] That is, for example, Si(CH3)3 contained in the organic-containing gas is not adsorbed onto the first film 300, but is adsorbed or substituted by the halogen element adsorbed to the adsorption-promoting layer 600 on the second film 400. Then, the adsorption-promoting layer 600 on the second film 400 is modified into a modified layer 700 having an Si alkyl terminus. This modified layer 700 can also be called an inhibitor layer that inhibits the formation of a metal-containing film 900 in the next film formation step.

[0060] The organic-containing gas contains one or more amino groups and an alkyl group. Preferably, it is a gas of a material containing organosilicon. For example, an aminosilane-based aminosilane-containing gas is used. More preferably, a silyl-based, silylamine-based silylamine-containing gas is used. The silyl-based gas is a material containing a -SiRx group. Here, R is, for example, an alkyl group or an amino group. x is, for example, an integer of 1 or more. Examples of such materials include (CH3)2NSi(CH3)3, (C2H5)HNSi(CH3)3, (C3H7)2HNSi(CH3)3, (C4H9)2HNSi(CH3)3, (C2H5)2NSi(CH3)3, (C3H7)2NSi(CH3)3, (CH3)2NSiH(CH3)2, (C2H5)HNSiH(CH3)2, (C2H5)2NSiH(CH3), (C3H7 Gases such as )NSiH(CH3)2, (CH3)2NSiH2(CH3), (C2H5)HNSiH2(CH3), (CH3)2NSiH(C2H5)2, (C2H5)HNSiH(C2H5)2, (C2H5)2NSiH(C2H5)2, (CH3)2NSiH2(C2H5), (C2H5)HNSiH2(C2H5), and (C2H5)2NSiH2(C2H5) can be used. One or more of these can be used as the organic-containing gas. Preferably, an organic-containing gas containing two or more alkyl groups is used. The more R (e.g., alkyl groups) bonded to Si, the more effective it may be in inhibiting the formation of the metal-containing film 900.

[0061] Specifically, when a silylamine-containing gas is supplied to a wafer 200 having a W film and a SiO film with Cl adsorbed on its surface, the silylamine-containing gas is not adsorbed onto the W film but is adsorbed onto the Cl terminations on the SiO film or is replaced by Cl terminations on the SiO film. That is, at least a portion of the Si-alkyl groups, etc. contained in the silylamine-containing gas forms, on the SiO film, an adsorption layer of Si-alkyl groups containing Cl, an adsorption layer of Si-alkyl groups from which Cl has been desorbed, etc. That is, the Cl layer on the SiO film is modified into a silylamine layer. The silylamine layer may be a silylamine layer containing Cl, a silylamine layer not containing Cl, or both.

[0062] That is, by supplying an organic-containing gas to the wafer 200 having the first film 300 and the adsorption-promoting layer 600, the adsorption-promoting layer 600 on the second film 400 on the wafer 200 is modified into a modified layer 700, which is an inhibitor layer that inhibits the formation of a metal-containing film 900 in the next film-forming step. The organic-containing gas can also be called a modifying gas or a modifying agent that modifies the adsorption-promoting layer 600.

[0063] After a predetermined time has elapsed since the start of the supply of the organic-containing gas, the valve 334 of the gas supply pipe 330 is closed to stop the supply of the organic-containing gas. At this time, the APC valve 243 of the exhaust pipe 231 is left open, and the processing chamber 201 is evacuated by the pump 246 to remove any unreacted organic-containing gas remaining in the processing chamber 201 or that has contributed to the modification of the adsorption promoting layer 600 from the processing chamber 201 (evacuating the space where the wafers 200 are present). In other words, the processing chamber 201 is purged. At this time, the valves 514, 524, 534, and 544 are left open to maintain the supply of the inert gas into the processing chamber 201.

[0064] The halogen-containing gas supplying process in step S1 and the organic-containing gas supplying process in step S2 may be performed cyclically, thereby improving the efficiency of discharging reaction by-products.

[0065] C. Metal-containing film formation process (film formation process) (Source gas supply process, step S3) Valve 314 is opened to allow the source gas to flow into the gas supply pipe 310. The flow rate of the source gas is adjusted by MFC 312, and the source gas is supplied into the processing chamber 201 through the gas supply holes 410a of the nozzle 410 and exhausted through the exhaust pipe 231. At this time, valve 514 is simultaneously opened to allow the inert gas to flow into the gas supply pipe 510. The inert gas flowing through the gas supply pipe 510 has its flow rate adjusted by MFC 512 and is supplied into the processing chamber 201 together with the source gas and exhausted through the exhaust pipe 231. At this time, in order to prevent the source gas from entering the nozzles 420, 430, and 440, valves 524, 534, and 544 are opened to allow the inert gas to flow into the gas supply pipes 520, 530, and 540. The inert gas is supplied into the processing chamber 201 through the gas supply pipes 320, 330, and 340 and the nozzles 420, 430, and 440 and is exhausted through the exhaust pipe 231.

[0066] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 3990 Pa. The supply flow rate of the source gas controlled by the MFC 312 is set within a range of, for example, 0.05 to 1 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, 532, and 542 are each set within a range of, for example, 0.1 to 50 slm.

[0067] At this time, since the modified layer 700 having Si alkyl termination is formed on the second film 400, at least some of the atoms and molecules contained in the source gas are less likely to be adsorbed thereon than on the first film 300.

[0068] 5(C) and 5(D), when the source gas is supplied to the wafer 200, at least some of the atoms and molecules contained in the source gas are adsorbed onto the first film 300 of the wafer 200, forming a metal-containing layer 800. The metal-containing layer 800 may be a metal layer containing other elements or may be an adsorption layer of the source gas. Note that, because the modified layer 700 is formed on the second film 400 of the wafer 200, the metal-containing layer 800 is unlikely to form.

[0069] A metal-containing gas can be used as the source gas. As the metal-containing gas, a gas containing, for example, a transition metal (transition element) as the metal element can be used, and preferably, a gas containing a platinum group element and a group 8 element can be used. As the metal-containing gas, for example, a Ru-containing gas can be used. In this way, by using a gas containing a transition metal, a platinum group element, and a group 8 element, it is possible to form a metal-containing film with low resistance. Furthermore, as the metal-containing gas, a gas containing a metal element and a carbonyl group can be used. This can improve the film formation rate.

[0070] Examples of metal-containing gases include Ru(C2H5C5H4)2, Ru(C5H5)(C4H9C5H4), Ru[CH3COCHCO(CH2)3CH3]3, Ru(C2H5C5H4)((CH3)C5H5), and Ru(C7H8)(C7H 11 O2), C 16 H 22 O6Ru, Ru3(CO) 12 , (DMBD)Ru(CO)3, (BD)Ru(CO3), (CHD)Ru(CO)3, C 14 H 10 Gases obtained by vaporizing organometallic materials such as O4Ru2, (Ru(CO)3Cl2)2, etc. can be used. As the metal-containing gas, one or more of these can be used.

[0071] Specifically, for example, when a Ru-containing gas is supplied as a source gas to a wafer 200 having a W film and a SiO2 film on the surface of which Si(CH3)3 is adsorbed and a silylamine layer is formed, a Ru-containing layer is formed on the W film, and the Ru-containing gas is not easily adsorbed on the SiO2 film on which Si(CH3)3 is adsorbed and a silylamine layer is formed, making it difficult for a Ru-containing film to be formed. In other words, a Ru-containing film is selectively formed on the W film on the wafer 200. This is also referred to as a Ru-containing film being preferentially formed on the W film on the wafer 200.

[0072] After a predetermined time has elapsed since the start of the supply of the source gas, the valve 314 of the gas supply pipe 310 is closed to stop the supply of the source gas. That is, the time for supplying the source gas to the wafer 200 is, for example, 1 to 120 seconds. At this time, the APC valve 243 of the exhaust pipe 231 is left open, and the processing chamber 201 is evacuated by the pump 246 to remove the source gas remaining in the processing chamber 201, either unreacted or having contributed to the formation of the metal-containing layer 800. That is, the processing chamber 201 is purged. At this time, the valves 514, 524, 534, and 544 are left open, and the supply of the inert gas into the processing chamber 201 is maintained.

[0073] (Reaction gas supply, step S4) After removing the residual gas from the processing chamber 201, the valve 324 is opened to allow the reactive gas to flow into the gas supply pipe 320. The flow rate of the reactive gas is adjusted by the MFC 322, and the reactive gas is supplied into the processing chamber 201 through the gas supply holes 420a of the nozzle 420 and exhausted through the exhaust pipe 231. At this time, the reactive gas is supplied to the wafer 200. At the same time, the valve 524 is opened to allow the inert gas to flow into the gas supply pipe 520. The flow rate of the inert gas flowing through the gas supply pipe 520 is adjusted by the MFC 522. The inert gas is supplied into the processing chamber 201 together with the reactive gas and exhausted through the exhaust pipe 231. At this time, in order to prevent the reactive gas from entering the nozzles 410, 430, and 440, the valves 514, 534, and 544 are opened to allow the inert gas to flow into the gas supply pipes 510, 530, and 540. The inert gas is supplied into the processing chamber 201 through gas supply pipes 310 , 330 , and 340 and nozzles 410 , 430 , and 440 , and is exhausted from an exhaust pipe 231 .

[0074] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 within a range of, for example, 5 to 15,000 Pa. The supply flow rate of the reactive gas controlled by the MFC 322 is set within a range of, for example, 1 to 100 slm, preferably 15 to 50 slm. The supply flow rates of the inert gases controlled by the MFCs 512 to 542 are each set within a range of, for example, 0.1 to 50 slm.

[0075] The reactive gas reacts with the metal-containing layer 800 adsorbed on the first film 300 to form a metal-containing layer 900 having reduced O compared to the metal-containing layer 800. That is, by supplying the reactive gas to the wafer 200, the metal-containing layer 900 is formed on the first film 300 of the wafer 200. Because the modified layer 700 has been formed on the second film 400, the metal-containing layer 900 is not formed.

[0076] The reactive gas may be, for example, hydrogen (H)-containing gas such as H2 gas, deuterium (D2) gas, or gas containing activated hydrogen, etc. One or more of these may be used as the reactive gas.

[0077] Here, when H gas is used as the reactive gas, the H gas undergoes a substitution reaction with at least a portion of the metal-containing layer 800 formed on the wafer 200 in step S3. For example, when a gas containing a metal element and a carbonyl group is used as the source gas, O and the like in the metal-containing layer 800 react with H, are desorbed from the metal-containing layer 800, and are exhausted from the processing chamber 201 as reaction by-products such as water vapor (H O). Then, a metal-containing layer 900 containing a metal element and having reduced O is formed on the wafer 200.

[0078] After the metal-containing layer 900 is formed, the valve 324 is closed to stop the supply of the reaction gas. Then, by a process similar to that of step S3 described above, the reaction gas and reaction by-products remaining in the process chamber 201, which have not reacted or which have contributed to the formation of the metal-containing layer 900, are removed from the process chamber 201. In other words, the process chamber 201 is purged.

[0079] (Performed a specified number of times, S5) The cycle of sequentially performing the above-described steps S3 and S4 is repeated a predetermined number of times (N1 times, where N1 is an integer of 1 or 2 or more), thereby forming metal-containing layer 900 of a predetermined thickness.

[0080] (Performed a specified number of times, S6) Then, after the cycle of sequentially performing the above-described steps S3 and S4 is performed a predetermined number of times (N1 times, where N1 is an integer of 1 or 2 or greater), the process returns to the processing of step S2, and the cycle of sequentially performing steps S2 to S5 is performed a predetermined number of times (N2 times, where N2 is an integer of 1 or 2 or greater). That is, after the halogen-containing gas supply process of step S1, steps S2 to S5 are performed N2 times to form a metal-containing film 900 of a predetermined thickness on the first film 300, which is a region of the wafer 200 where the modified layer 700 is not formed. Steps S2 to S4 are preferably performed in this order. This allows the metal-containing film 900 to be formed on the first film 300 while suppressing desorption of halogen elements such as Cl contained in the modified layer 700 on the second film 400.

[0081] That is, as shown in FIG. 5(E), a metal-containing film 900 of a predetermined thickness can be selectively formed on the first film 300, which is an area of ​​the wafer 200 having the first film 300 and the second film 400 on its surface, where the modified layer 700 is not formed. The above-described cycle is preferably performed multiple times. This reduces the amount of metal oxide film 500 on the surface of the first film 300, allowing the metal-containing film 900 to be selectively formed on the first film 300. That is, the metal oxide film 500 on the first film 300 in the recessed portion on the wafer 200 is removed, allowing the metal-containing film 900 to be selectively formed on the first film 300.

[0082] Specifically, for example, a Ru-containing gas, which is an example of a source gas, and H gas, which is an example of a reactive gas, are supplied to a wafer 200 having a W film and a SiO film with a silylamine layer formed on the surface thereof, thereby selectively forming a Ru-containing film on the W film. That is, a Ru film can be grown on the W film.

[0083] (After purging and atmospheric pressure recovery) An inert gas is supplied into the processing chamber 201 from each of the gas supply pipes 510 to 540 and exhausted from the exhaust pipe 231. The inert gas acts as a purge gas, thereby purging the processing chamber 201 with the inert gas and removing residual gases and reaction by-products from the processing chamber 201. Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0084] (Wafer removal) Thereafter, the elevator 115 lowers the cap 219 to open the bottom end of the outer tube 203. Then, the processed wafers 200 supported by the boat 217 are carried out from the bottom end of the outer tube 203 to the outside of the outer tube 203. Thereafter, the processed wafers 200 are removed from the boat 217.

[0085] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained. (a) By supplying a halogen-containing gas, the metal oxide film 500 on the first film 300 can be removed (etched). Also, an adsorption promoting layer 600 that promotes the formation of a modified layer 700 can be formed on the second film 400. (b) By supplying an organic-containing gas, a modified layer 700 that inhibits film formation can be formed on the second film 400. (c) On a wafer 200 having a first film 300 and a second film 400 on its surface, a metal-containing film 900 can be selectively formed on the first film 300 where a modified layer 700 is not formed. (d) Furthermore, by supplying a halogen-containing gas before the film formation step, the contact resistance between first film 300 and metal-containing film 900 embedded in the recess can be reduced.

[0086] (4) Other aspects The above describes one embodiment of the present disclosure in detail. However, the present disclosure is not limited to the above embodiment and can be modified in various ways without departing from the spirit of the present disclosure. In the following modifications, only the differences from the above embodiment will be described in detail.

[0087] (Variation 1) In this modified example, as shown in FIG. 6, a raw material gas supply process in step S11 and a process of performing step S14 a predetermined number of times (M times, where M is an integer of 1 or 2 or more) are performed between the halogen-containing gas supply process in step S1 and the organic-containing gas supply process in step S2 in the substrate processing process described above.

[0088] That is, in this modification, after the halogen-containing gas supply process of step S1 described above, the source gas supply process of step S11 is performed a predetermined number of times (M times, where M is 1 or an integer equal to or greater than 2) in step S14, and then the above-described steps S2 to S6 are performed. That is, the substrate processing process of this modification can also be expressed as follows.

[0089] Halogen-containing gas → raw material gas × M → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 M, N1, and N2 are integers of 1 or greater

[0090] In this modification, the same effects as those of the above-described embodiment can be obtained. In this modification, the metal-containing film 900 can be formed on the first film 300 while further removing the metal oxide film 500 on the first film 300. In addition, the amount of halogen elements such as Cl adsorbed on the second film 400 can be reduced. Note that the source gas used in the source gas supply process of step S11 may be the same metal-containing gas as the source gas used in the source gas supply process of step S3 described above, or a different metal-containing gas may be used. In this modification, the same effects as those of the above-described embodiment can be obtained. The same applies below.

[0091] (Variation 2) In this modified example, between the halogen-containing gas supply process of step S1 and the organic-containing gas supply process of step S2 in the substrate processing process described above, a raw material gas supply process of step S11, a halogen-containing gas supply process of step S12 shown by the dotted line in FIG. 6, and a process of performing step S14 a predetermined number of times (M times, where M is an integer of 1 or 2 or more) are performed.

[0092] That is, in this modification, after the halogen-containing gas supply process of step S1 described above, the source gas supply process of step S11 similar to step S3 described above and the halogen-containing gas supply process of step S12 similar to step S1 described above are performed a predetermined number of times (M times, M is 1 or an integer of 2 or more) in step S14, and then the above-described steps S2 to S6 are performed. That is, the substrate processing process of this modification can also be expressed as follows.

[0093] Halogen-containing gas → (raw material gas → halogen-containing gas) × M → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 M, N1, and N2 are integers of 1 or greater

[0094] In this modification, the same effects as those of the above-described aspects and modifications can be obtained.

[0095] (Variation 3) In this modified example, between the halogen-containing gas supply process of step S1 and the organic-containing gas supply process of step S2 in the substrate processing process described above, a raw material gas supply process of step S11, a reactive gas supply process of step S13 shown by a dashed dotted line in FIG. 6, and a process of performing step S14 a predetermined number of times (M times, where M is an integer of 1 or 2 or more) are performed.

[0096] That is, in this modification, after the halogen-containing gas supply process of step S1 described above, the source gas supply process of step S11 similar to step S3 described above and the reactive gas supply process of step S13 similar to step S4 described above are performed a predetermined number of times (M times, M is 1 or an integer of 2 or more) in step S14, and then the above-described steps S2 to S6 are performed. That is, the substrate processing process of this modification can also be expressed as follows.

[0097] Halogen-containing gas → (raw material gas → reactive gas) × M → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 M, N1, and N2 are integers of 1 or greater

[0098] This modification also provides the same effects as those of the above-described aspects and modifications. Furthermore, it is preferable to perform the above-described steps S11 and S13 in this order. This prevents the halogen element on the second film 400 from being removed too much. That is, the halogen element adsorbed on the second film 400 can be left behind, and a metal-containing film can be selectively formed on the first film 300 where the halogen element is not adsorbed.

[0099] (Variation 4) In this modified example, as shown in FIG. 7, between the halogen-containing gas supply process of step S1 and the organic-containing gas supply process of step S2 in the substrate processing process described above, an organic-containing gas supply process of step S21 and a process of performing step S23 a predetermined number of times (M times, where M is an integer of 1 or 2 or more) are performed.

[0100] That is, in this modification, after the halogen-containing gas supply process of step S1 described above, the organic-containing gas supply process of step S21 is performed a predetermined number of times (M times, where M is 1 or an integer equal to or greater than 2) in step S23, and then the above-described steps S2 to S6 are performed. That is, the substrate processing process of this modification can also be expressed as follows.

[0101] Halogen-containing gas → organic-containing gas × M → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 M, N1, and N2 are integers of 1 or greater

[0102] This modification also provides the same effects as those of the above-described embodiments and modifications. Furthermore, in this modification, the organic-containing gas is further supplied M times, thereby forming the modified layer 700 on the second film 400 while removing reaction by-products. That is, the amount of halogen elements such as Cl adsorbed on the second film 400 can be reduced.

[0103] (Variation 5) In this modified example, between the halogen-containing gas supply process of step S1 and the organic-containing gas supply process of step S2 in the substrate processing process described above, an organic-containing gas supply process of step S21 and a reactive gas supply process of step S22 shown by the dotted line in FIG. 7 are performed a predetermined number of times (M times, where M is an integer of 1 or 2 or more) in step S23.

[0104] That is, in this modification, after the halogen-containing agent supplying step of step S1 described above, the organic-containing gas supplying step of step S21 similar to the above-described step S2 and the reactive gas supplying step of step S22 similar to the above-described step S4 are performed a predetermined number of times (M times, M is 1 or an integer of 2 or more) in step S23, and then the above-described steps S2 to S6 are performed. That is, the substrate processing step of this modification can also be expressed as follows.

[0105] Halogen-containing gas → (organic-containing gas → reactive gas) × M → [organic-containing gas → (raw material gas → reactive gas) × N1] × N2 M, N1, and N2 are integers of 1 or greater

[0106] In this modification, the same effects as those of the above-described aspects and modifications can be obtained.

[0107] In the substrate processing process described above, the case where the adsorption promoting layer 600 is formed on the second film 400 while removing the metal oxide film 500 formed on the first film 300 on the wafer 200 in the halogen-containing gas supply step of step S1 has been described as an example. However, the present disclosure is not limited to this. A step of removing the metal oxide film 500 may be provided before the halogen-containing gas supply step of step S1, separate from step S1. In this case, the gas used in the step of removing the metal oxide film 500 before the halogen-containing gas supply step of step S1 may be the same halogen-containing gas as in step S1, or may be a halogen-containing gas, such as a fluorine (F)-based gas, different from that used in step S1. In this modified example, the same effects as those of the above-described embodiment can be obtained.

[0108] Furthermore, in the above embodiment, an example in which a predetermined film is formed on the wafer 200 has been described, but the present disclosure is not particularly limited to the type of film.

[0109] 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.

[0110] In the above-described embodiment, the above-described processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiment, and for example, one step and another step of the above-described processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus.

[0111] 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.

[0112] It is preferable that recipes (programs describing processing procedures, processing conditions, etc.) used in substrate processing be individually prepared according to the processing contents (film type, composition ratio, film quality, film thickness, processing procedures, processing conditions, etc. of the film to be formed) and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting substrate processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the processing contents from among the multiple recipes stored in the storage device 121c. This makes it possible to reproducibly form films with various film types, composition ratios, film quality, and film thicknesses using a single substrate processing device. It also reduces the burden on the operator (such as the burden of inputting processing procedures, processing conditions, etc.), allowing for quick start of substrate processing while avoiding operational errors.

[0113] The above-mentioned process recipes may not only be newly created but also 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.

[0114] 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. [Explanation of symbols]

[0115] 200···Wafer (substrate), 600···Adsorption promoting layer, 700···Modified layer, 900···Metal-containing film

Claims

1. (a) forming an adsorption-promoting layer on a substrate by supplying a halogen-containing agent to the substrate, the adsorption-promoting layer promoting adsorption of an organic-containing agent; (b) forming a modified layer on the substrate by applying the organic containing agent to the substrate; (c) supplying a raw material containing a metal element to the substrate; (d) providing reactants to the substrate; (e) performing (b), (c), and (d) N times after (a), thereby forming a metal-containing film in an area of ​​the substrate where the modified layer is not formed; A substrate processing method comprising:

2. 2. The substrate processing method according to claim 1, wherein in (e), after (a), (c) is performed M times, and then (b), (c), and (d) are performed N times.

3. 2. The substrate processing method according to claim 1, wherein in (e), after (a), (c) and (a) are performed M times, and then (b), (c), and (d) are performed N times.

4. 2. The substrate processing method according to claim 1, wherein in (e), after (a), (c) and (d) are performed M times, and then (b), (c), and (d) are performed N times.

5. 2. The substrate processing method according to claim 1, wherein in (e), after (a), (b) is performed M times, and then (b), (c), and (d) are performed N times.

6. 2. The substrate processing method according to claim 1, wherein in (e), after (a), (b) and (d) are performed M times, and then (b), (c), and (d) are performed N times.

7. 5. The substrate processing method according to claim 4, wherein in (e), (c) and (d) are performed in this order.

8. 2. The substrate processing method according to claim 1, wherein in (e), (b), (c), and (d) are performed in this order.

9. 2. The substrate processing method according to claim 1, wherein N is an integer of 2 or more.

10. The substrate processing method according to claim 2 , wherein M is an integer of 2 or more.

11. the substrate has a metal oxide film and a non-metal oxide film; 2. The substrate processing method according to claim 1, wherein in step (a), the adsorption promoting layer is formed on the non-metal oxide film.

12. The substrate processing method according to claim 1 , wherein the halogen-containing agent contains any one of a Group 14 element, a Group 15 element, and a Group 16 element.

13. The substrate processing method of claim 1 , wherein the halogen-containing agent includes oxygen.

14. The substrate processing method of claim 1 , wherein the halogen-containing agent is an oxyhalide.

15. The substrate processing method of claim 1 , wherein the organic-containing agent includes an amino group.

16. The substrate processing method according to claim 1 , wherein the organic-containing agent contains one or more amino groups and two or more alkyl groups.

17. a metal oxide film is formed on the substrate; The substrate processing method according to claim 1 , further comprising the step of removing the metal oxide film before (a).

18. (a) forming an adsorption-promoting layer on a substrate by supplying a halogen-containing agent to the substrate, the adsorption-promoting layer promoting adsorption of an organic-containing agent; (b) forming a modified layer on the substrate by applying the organic containing agent to the substrate; (c) supplying a raw material containing a metal element to the substrate; (d) providing reactants to the substrate; (e) performing (b), (c), and (d) N times after (a), thereby forming a metal-containing film in an area of ​​the substrate where the modified layer is not formed; A method for manufacturing a semiconductor device having the above structure.

19. a first supply unit that supplies a raw material containing a metal element to the substrate; a second supply section for supplying a reactant to the substrate; a third supply unit that supplies an organic containing agent to the substrate; a fourth supply unit that supplies a halogen-containing agent to the substrate; (a) a process of forming an adsorption-promoting layer on the substrate by supplying the halogen-containing agent to the substrate, the adsorption-promoting layer promoting adsorption of the organic-containing agent; (b) forming a modified layer on the substrate by supplying the organic containing agent to the substrate; (c) supplying a raw material containing the metal element to the substrate; (d) providing the reactant to the substrate; (e) a process of forming a metal-containing film in an area of ​​the substrate where the modified layer is not formed by performing (b), (c), and (d) N times after (a); and a control unit configured to be able to control the first supply unit, the second supply unit, the third supply unit, and the fourth supply unit so as to perform the process. A substrate processing apparatus having:

20. (a) supplying a halogen-containing agent to a substrate to form an adsorption-promoting layer on the substrate that promotes adsorption of an organic-containing agent; (b) applying the organic containing agent to the substrate to form a modified layer on the substrate; (c) supplying a raw material containing a metal element to the substrate; (d) delivering reactants to the substrate; (e) performing (b), (c), and (d) N times after (a), thereby forming a metal-containing film in an area of ​​the substrate where the modified layer is not formed; A program that causes a computer to execute the above in a substrate processing apparatus.

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