SUBSTRATE PROCESSING METHOD, SEMICONDUCTOR DEVICE MANUFACTURING APPARATUS, PROGRAM, AND SUBSTRATE PROCESSING APPARATUS

Abstract

To provide a technology that enables good hydrophobization of a substrate surface regardless of the composition of an underlying film.SOLUTION: A method comprises the steps of: (a) forming an oxide layer containing a predetermined element on a first film formed on a substrate by supplying a raw material gas containing the predetermined element to the substrate, wherein a hydroxyl group termination is formed on the surface and the density of the hydroxyl group termination is higher than that of the hydroxyl group termination formed on the surface of the first film; and (b) hydrophobizing the surface of the oxide layer by supplying a modified gas containing hydrocarbon groups to a substrate on which the oxide layer is formed.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a substrate surface may be subjected to a hydrophobic treatment (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-152517 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, depending on the composition of the undercoat film formed on the substrate surface, it may be difficult to satisfactorily hydrophobize the substrate surface.

[0005] The present disclosure provides a technique that can satisfactorily hydrophobize a substrate surface regardless of the composition of an undercoat film formed on the substrate surface. [Means for solving the problem]

[0006] According to one aspect of the present disclosure, (a) supplying a source gas containing a predetermined element to a substrate, thereby forming an oxide layer containing the predetermined element on a first film formed on the substrate, the oxide layer having a hydroxyl group termination on a surface thereof and a higher density of the hydroxyl group termination than that of the hydroxyl group termination formed on the surface of the first film; (b) supplying a modifying gas containing a hydrocarbon group to the substrate on which the oxide layer is formed, thereby hydrophobizing a surface of the oxide layer; The present invention provides a technique having the following features: Effect of the Invention

[0007] According to the present disclosure, the substrate surface can be satisfactorily hydrophobized regardless of the composition of the undercoat film formed on the substrate surface. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 4 is a diagram showing a processing sequence according to an embodiment of the present disclosure. [Diagram 5] Fig. 5(a) is a schematic cross-sectional view showing a surface portion of a wafer on which a first film is formed. Fig. 5(b) is a schematic cross-sectional view showing a surface portion of a wafer after an oxide layer is formed on the surface of the first film by supplying a source gas to the wafer in the state of Fig. 5(a). Fig. 5(c) is a schematic cross-sectional view showing a surface portion of a wafer after the surface of the oxide layer is hydrophobized by supplying a modifying gas to the wafer in the state of Fig. 5(b). [Figure 6] Fig. 6(a) is a schematic cross-sectional view showing a surface portion of a wafer having a first film and a second film. Fig. 6(b) is a schematic cross-sectional view showing a surface portion of a wafer after an oxide layer is formed on the surfaces of the first film and the second film by supplying a source gas to the wafer in the state of Fig. 6(a). Fig. 6(c) is a schematic cross-sectional view showing a surface portion of a wafer after the surface of the oxide layer is hydrophobized by supplying a modifying gas to the wafer in the state of Fig. 6(b). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <First Aspect of the Present Disclosure> The first embodiment of the present disclosure will be described below mainly with reference to Figures 1 to 4 and 5(a) to 5(c). Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match the actual ones. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0010] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0011] A reaction tube 203 is disposed inside the heater 207 concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO 2 The reaction tube 203 is made of a heat-resistant material such as SUS or silicon carbide (SiC) and is formed in a cylindrical shape with the upper end closed and the lower end open. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with the upper and lower ends open. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided as a seal member between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow part of the processing vessel. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

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

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

[0014] As shown in FIG. 2, the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged, so as to extend along the wafer arrangement region. In a plan view, the nozzle 249b is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249a and 249c are disposed so as to sandwich a straight line L passing through the nozzle 249b and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200. In other words, the nozzle 249c is provided on the opposite side of the nozzle 249a across the line L. The nozzles 249a and 249c are arranged symmetrically with respect to the line L. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are each opened to face (face) the exhaust port 231a in a plan view, and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0015] A source gas containing a predetermined element is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0016] A modifying gas containing a hydrocarbon group is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0017] An oxidizing agent is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0018] A cleaning agent is supplied from the gas supply pipe 232d into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232d, and the nozzle 249a.

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

[0020] From the gas supply pipes 232f to 232h, an inert gas is supplied via the MFCs 241f to 241h, the valves 243f to 243h, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0021] A raw material gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A modified gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. An oxidizing agent supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. A cleaning agent supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. A catalyst supply system is mainly composed of the gas supply pipe 232e, the MFC 241e, and the valve 243e. An inert gas supply system is mainly composed of the gas supply pipes 232f to 232h, the MFCs 241f to 241h, and the valves 243f to 243h.

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

[0023] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further configured to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

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

[0025] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that comes into contact with the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0026] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0027] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0028] As shown in Fig. 3, 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 121e. An input / output device 122 configured as, for example, a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121.

[0029] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are recorded and stored in a readable manner. The process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.

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

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

[0032] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line without using the external storage device 123.

[0033] (2) Substrate processing A method of processing a substrate as one step in the manufacturing process of a semiconductor device using the above-mentioned substrate processing apparatus, i.e., an example of a processing sequence for hydrophobizing the surface of a wafer 200 as a substrate via an oxide layer, will be described mainly with reference to Figure 4 and Figures 5(a) to 5(c). In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0034] A first film is formed as a base on the wafer 200. For convenience, the following will describe a typical example in which the first film is a silicon film (Si film) that does not contain oxygen (O).

[0035] In the processing sequence of this embodiment, (a) a step of forming an oxide layer containing a predetermined element on a first film formed on the wafer 200 by supplying a source gas containing a predetermined element to the wafer 200, the oxide layer having a density of hydroxyl (OH) terminations formed on the surface of the first film and a higher density of the OH terminations than the density of the OH terminations formed on the surface of the first film (oxide layer forming step); (b) supplying a modifying gas containing a hydrocarbon group to the wafer 200 on which the oxide layer is formed to hydrophobize the surface of the oxide layer (hydrophobization step); Do the following.

[0036] In the following example, as shown in Fig. 4, a cycle including a step of supplying a raw material gas to the wafer 200 and a step of supplying an oxidizing agent to the wafer 200 is performed a predetermined number of times in the oxide layer forming step, and a catalyst is supplied to the wafer 200 in at least one of the steps of supplying the raw material gas and the step of supplying the oxidizing agent. Note that Fig. 4 shows a typical example in which a catalyst is supplied in both the step of supplying the raw material gas and the step of supplying the oxidizing agent.

[0037] That is, the processing sequence shown in FIG. 4 is performed in a non-plasma atmosphere. (a) a step of forming an oxide layer containing a predetermined element on the first film (oxide layer formation step) by performing a cycle including a step of supplying a source gas containing a predetermined element and a catalyst to the wafer 200 on which the first film has been formed, and a step of supplying an oxidizing agent and a catalyst to the wafer 200 a predetermined number of times (n times, n is an integer of 1 or more); (b) supplying a modifying gas containing a hydrocarbon group to the wafer 200 on which the oxide layer is formed to hydrophobize the surface of the oxide layer (hydrophobization step); This shows an example of how to do this.

[0038] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples and other aspects.

[0039] (raw gas + catalyst → oxidant + catalyst) × n → reformed gas

[0040] As in the process sequence shown below, a catalyst may be supplied to the wafer 200 in at least one of the steps of supplying a source gas and supplying an oxidizing agent.

[0041] (raw gas + catalyst → oxidant) × n → reformed gas (raw gas → oxidant + catalyst) × n → reformed gas (raw gas + catalyst → oxidant + catalyst) × n → reformed gas

[0042] Furthermore, as shown in FIG. 4 and the process sequence shown below, before performing the oxide layer formation step, a cleaning agent may be supplied to the wafer 200, so that, for example, a step of removing a native oxide film formed on the surface of the first film (cleaning step) may be further performed.

[0043] Cleaning agent → (raw gas + catalyst → oxidant) × n → reformed gas Cleaning agent → (raw gas → oxidant + catalyst) × n → reformed gas Cleaning agent → (raw gas + catalyst → oxidant + catalyst) × n → reformed gas

[0044] The term "wafer" used in this specification may mean the wafer itself or 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 mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on a wafer", it may mean that a predetermined layer is formed directly on the surface of the wafer itself or that a predetermined layer is formed on a layer or the like formed on the wafer. When the term "substrate" is used in this specification, it is synonymous with the term "wafer".

[0045] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist-like substance. That is, the cleaning agent and the oxidizing agent may each include a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0046] As used herein, the term "layer" includes continuous and / or discontinuous layers.

[0047] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this manner, the wafers 200 are prepared in the processing chamber 201.

[0048] As shown in FIG. 5(a), a first film is formed as a base on the surface of the wafer 200 loaded into the boat 217. As described above, the case where the first film is a Si film will be described as an example. Also, the case where a step of cleaning the surface of the first film (cleaning step) is performed before the oxide layer forming step will be described as an example.

[0049] (Pressure and temperature regulation) After the boat loading is completed, the inside of the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafers 200 in the processing chamber 201 are heated by the heater 207 so that the temperature is a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0050] (Washing step) Thereafter, a cleaning agent is supplied to the wafer 200 .

[0051] Specifically, the valve 243d is opened to allow the cleaning agent to flow into the gas supply pipe 232d. The cleaning agent is adjusted in flow rate by the MFC 241d, and is supplied into the processing chamber 201 via the gas supply pipe 232d and the nozzle 249a, and is exhausted from the exhaust port 231a. At this time, the cleaning agent is supplied to the wafer 200 from the side of the wafer 200 (cleaning agent supply). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c.

[0052] By supplying a cleaning agent to the wafer 200 under processing conditions described below, for example, the native oxide film formed on the surface of the first film can be removed (etched) to expose the surface of the first film. At this time, the surface of the first film is in a state in which OH terminations are not formed in many regions, that is, in which OH terminations are formed in some regions, and the surface has a non-uniform distribution of OH terminations, as shown in FIG. 5(a).

[0053] The processing conditions for supplying the cleaning agent in the cleaning step are as follows: Treatment temperature: 50 to 200°C, preferably 70 to 150°C Treatment pressure: 10 to 2000 Pa, preferably 100 to 1500 Pa Processing time: 10 to 60 minutes, preferably 30 to 60 minutes Cleaning agent supply flow rate: 0.05 to 1 slm, preferably 0.1 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm, preferably 2 to 10 slm Examples are given below.

[0054] In this specification, the expression of a numerical range such as "50 to 200°C" means that the lower limit and the upper limit are included in the range. Therefore, for example, "50 to 200°C" means "50°C or more and 200°C or less". The same applies to other numerical ranges. In this specification, the processing temperature means the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure means the pressure in the processing chamber 201. In addition, the processing time means the time for which the processing continues. In addition, when the supply flow rate includes 0 slm, 0 slm means a case where the substance (gas) is not supplied. These are the same in the following explanations.

[0055] After the surface of the first film is cleaned, the valve 243d is closed to stop the supply of the cleaning agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243f to 243h are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, and the processing chamber 201 is purged (purged).

[0056] The processing conditions for purging in the cleaning step are as follows: Processing pressure: 1~30Pa Treatment time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm In addition, the processing temperature when purging is performed in this step is preferably the same as the processing temperature when the cleaning agent is supplied.

[0057] As the cleaning agent, for example, a fluorine (F)-containing gas can be used. As the F-containing gas, for example, chlorine trifluoride (ClF 3 ) gas, chlorine fluoride (ClF) gas, nitrogen fluoride (NF 3 ) gas, hydrogen fluoride (HF) gas, fluorine (F 2 ) gas, etc., can be used as the cleaning agent. 3 COOH) gas, formic acid (HCOOH) gas, hexafluoroacetylacetone (C 5 H 2 F 6 O 2 ) gas, hydrogen (H 2) gas, etc. can be used. Various cleaning solutions can also be used as the cleaning agent. For example, an acetic acid solution, a formic acid solution, etc. can also be used as the cleaning agent. For example, a HF solution can be used as the cleaning agent to perform DHF cleaning. For example, a cleaning solution containing ammonia water, hydrogen peroxide water, and pure water can be used as the cleaning agent to perform SC-1 cleaning (APM cleaning). For example, a cleaning solution containing hydrochloric acid, hydrogen peroxide water, and pure water can be used as the cleaning agent to perform SC-2 cleaning (HPM cleaning). For example, a cleaning solution containing sulfuric acid and hydrogen peroxide water can be used as the cleaning agent to perform SPM cleaning. That is, the cleaning agent may be a gaseous substance or a liquid substance. The cleaning agent may be a liquid substance such as a mist substance. One or more of these can be used as the cleaning agent.

[0058] As an inert gas, nitrogen (N 2 ) gas, or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0059] In addition, in the case of using a wafer 200 in which the surface of the first film has been cleaned in advance, for example, with any native oxide film formed on the surface of the first film removed, the cleaning step can be omitted.

[0060] (Oxide layer formation step) After the cleaning step, a source gas and an oxidizing agent are supplied to the wafer 200 to form an oxide layer on the first film formed on the wafer 200 as a base. More specifically, a source gas supply step and an oxidizing agent supply step are executed in sequence. In the source gas supply step and the oxidizing agent supply step, the output of the heater 207 is adjusted to maintain the temperature of the wafer 200 at or below the temperature of the wafer 200 in the cleaning step, preferably at a temperature lower than the temperature of the wafer 200 in the cleaning step, as shown in FIG.

[0061] [Source gas supply step] In this step, a source gas containing a predetermined element and a catalyst (catalytic gas) are supplied to the wafer 200 after the cleaning step.

[0062] Specifically, the valves 243a and 243e are opened to allow the source gas and catalyst to flow into the gas supply pipes 232a and 232e, respectively. The source gas and catalyst are adjusted in flow rate by the MFCs 241a and 241e, respectively, and are supplied into the processing chamber 201 via the nozzles 249a and 249b, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the source gas and catalyst are supplied to the wafer 200 from the side of the wafer 200 (source gas + catalyst supply). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0063] For example, a source gas containing silicon (Si) as a predetermined element is supplied to the wafer 200 under processing conditions to be described later, and a Si-containing layer is formed as a first layer on the surface of the first film.

[0064] By forming the first layer under temperature conditions described later, it is possible to prevent the source gas from thermally decomposing (vapor phase decomposition), i.e., from self-decomposing, in the processing chamber 201. This makes it possible to prevent Si contained in the source gas from being multiply deposited on the first film, and to allow Si to be adsorbed onto the first film.

[0065] The processing conditions for supplying the raw material gas and the catalyst are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C, more preferably room temperature to 100°C Processing pressure: 133~1333Pa Raw gas supply flow rate: 0.001 to 2 slm Catalyst supply flow rate: 0.001~2slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Examples are given below.

[0066] After the first layer is formed on the surface of the first film, the valves 243a and 243e are closed to stop the supply of the source gas and catalyst into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in the cleaning step. Note that the processing temperature for purging in this step is preferably the same as the processing temperature for supplying the source gas and catalyst.

[0067] As the source gas, for example, a gas containing Si and a halogen (a material containing Si and a halogen) can be used. The halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like. The gas containing Si and a halogen preferably includes a halogen in the form of a chemical bond between Si and a halogen. As the gas containing Si and a halogen, for example, a silane-based gas having a Si-Cl bond, i.e., a chlorosilane-based gas, can be used. The gas containing Si and a halogen may further include C, and in that case, it is preferable to include C in the form of a Si-C bond. As the gas containing Si and a halogen, for example, a silane-based gas having a Si-C bond, i.e., an alkylenechlorosilane-based gas, can be used. The alkylene group includes a methylene group, an ethylene group, a propylene group, a butylene group, and the like. As the gas containing Si and a halogen, for example, a silane-based gas having a Si-C bond, i.e., an alkylchlorosilane-based gas, can be used. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, and the like. The Si- and halogen-containing gas may further include O, and in this case, it is preferable that O is included in the form of a Si-O bond, for example, in the form of a siloxane bond (Si-O-Si bond). For example, a silane-based gas having Si, Cl, and a siloxane bond, that is, a chlorosiloxane-based gas, can be used as the Si- and halogen-containing gas. It is preferable that each of these gases contains Cl in the form of a Si-Cl bond. In addition to these, an amino group-containing gas (amino group-containing substance) such as an aminosilane-based gas can also be used as the raw material gas.

[0068] The source gas is, for example, bis(trichlorosilyl)methane (SiCl 3 ) 2 CH 2 ) gas, 1,2-bis(trichlorosilyl)ethane ((SiCl 3 ) 2 C 2 H 4 ) gas, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH 3 )2 S 2 Cl 4 ) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH 3 ) 4 S 2 Cl 2 ) gas, 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C 2 H 4 Cl 4 S 2 ) gas, etc. Also, as the source gas, for example, tetrachlorosilane (SiCl 4 ) gas, hexachlorodisilane (Si 2 Cl 6 ) gas, octachlorotrisilane (Si 3 Cl 8 ) gas, etc., can be used. In addition, as the raw material gas, for example, hexachlorodisiloxane (Cl 3 Si-O-SiCl 3 ) gas, octachlorotrisiloxane (Cl 3 Si-O-SiCl 2 -O-SiCl 3 ) gas, etc. As the source gas, one or more of these can be used.

[0069] The source gas is, for example, tetrakis(dimethylamino)silane (Si[N(CH 3 ) 2 ] 4 ) gas, tris(dimethylamino)silane (Si[N(CH 3 ) 2 ] 3 H) gas, bis(diethylamino)silane (Si[N(C 2 H 5 ) 2 ] 2 H 2 ) gas, bis(tertiary butyl amino)silane (SiH 2 [NH(C 4 H 9 )] 2 ) gas, (diisopropylamino)silane (SiH 3 [N(C 3 H7 ) 2 ]) gases, etc. One or more of these can be used as the source gas.

[0070] As the catalyst, for example, an amine-based gas (amine-based substance) containing carbon (C), nitrogen (N), and hydrogen (H) can be used. As the amine-based gas (amine-based substance), a cyclic amine-based gas (cyclic amine-based substance) or a chain amine-based gas (chain amine-based substance) can be used. As the catalyst, for example, pyridine (C 5 H 5 N), aminopyridine (C 5 H 6 N 2 ), Picoline (C 6 H 7 N), lutidine (C 7 H 9 N), pyrimidine (C 4 H 4 N 2 ), quinoline (C 9 H 7 N), piperazine (C 4 H 10 N 2 ), piperidine (C 5 H 11 N), aniline (C 6 H 7 Cyclic amines such as triethylamine (C 2 H 5 ) 3 N), diethylamine ((C 2 H 5 ) 2 NH), monoethylamine ((C 2 H 5 )NH 2 ), trimethylamine ((CH 3 ) 3 N), dimethylamine ((CH 3 ) 2 NH), monomethylamine ((CH 3 )NH 2As the catalyst, one or more of these can be used. This also applies to the oxidizing agent supplying step described below.

[0071] [Oxidant supply step] After the source gas supply step is completed, an oxidizing agent (reactive gas) and a catalyst are supplied to the wafer 200, that is, the wafer 200 after the first layer has been formed on the surface of the first film.

[0072] Specifically, the valves 243c and 243e are opened to allow the oxidant and catalyst to flow into the gas supply pipes 232c and 232e, respectively. The oxidant and catalyst are adjusted in flow rate by the MFCs 241c and 241e, respectively, and are supplied into the processing chamber 201 via the nozzles 249c and 249b, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the oxidant and catalyst are supplied to the wafer 200 from the side of the wafer 200 (oxidant+catalyst supply). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0073] By supplying an oxidizing agent to the wafer 200 under processing conditions described below, at least a part of the first layer formed on the surface of the first film in the source gas supply step is oxidized. As a result, the first layer is oxidized on the surface of the first film as a base, and a second layer having OH termination formed on the surface is formed.

[0074] By forming the second layer under temperature conditions described below, it is possible to form the second layer while suppressing disappearance (detachment) of OH terminations from the surface.

[0075] The treatment conditions for supplying the oxidant and catalyst are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C, more preferably room temperature to 100°C Processing pressure: 133~1333Pa Oxidizer supply flow rate: 0.001~2slm Catalyst supply flow rate: 0.001~2slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Examples are given below.

[0076] After the first layer formed on the surface of the first film is oxidized and changed (converted) into the second layer, the valves 243c and 243e are closed to stop the supply of the oxidant and catalyst into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those for purging in the cleaning step. Note that the processing temperature for purging in this step is preferably the same as the processing temperature for supplying the oxidant and catalyst.

[0077] As the oxidizing agent, for example, a gas containing oxygen (O) and hydrogen (H) (O and H containing substance) can be used. As the O and H containing gas, for example, water vapor (H 2 O gas), hydrogen peroxide (H 2 O 2 ) gas, hydrogen (H 2 ) gas + oxygen (O 2 ) Gas, H 2 Gas + Ozone (O 3 In other words, as the O and H-containing gas, an O-containing gas + H-containing gas can be used. In this case, the H-containing gas can be H 2 Instead of gas, deuterium (D 2 ) gas can also be used. As the oxidizing agent, one or more of these can be used.

[0078] In this specification, "H 2 Gas + O 2 In the case of a listing of two gases, such as "H 2 Gas and O 2When supplying a mixed gas, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be separately supplied into the processing chamber 201 through different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0079] As the oxidizing agent, in addition to O and H containing gas, O containing gas (O containing substance) can be used. As the O containing gas, for example, O 2 Gas, O 3 Gas, Nitrous Oxide (N 2 O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO 2 ) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, etc. can be used. In addition to these, the various aqueous solutions and various cleaning solutions described above can also be used as the oxidizing agent. In this case, by exposing the wafer 200 to the cleaning solution, the object to be oxidized on the surface of the wafer 200 can be oxidized. One or more of these can be used as the oxidizing agent.

[0080] As the catalyst, for example, the same catalysts as those exemplified in the above-mentioned raw material gas supplying step can be used.

[0081] [Perform the specified number of times] By performing a cycle of alternately performing the above-mentioned source gas supply step and oxidant supply step asynchronously, i.e., without synchronization, a predetermined number of times (n times, n is an integer of 1 or more), an oxide layer with an OH-terminated surface can be formed on the first film formed on the wafer 200. For example, when the above-mentioned source gas and oxidant are used, a silicon oxycarbide layer (SiOC layer) or a silicon oxide layer (SiO layer) can be formed on the first film as an oxide layer containing Si as a predetermined element. It is preferable to repeat the above-mentioned cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired film thickness, and to repeat the above-mentioned cycle multiple times until the thickness of the oxide layer formed by stacking the second layer reaches a desired thickness, for example, 1.5 to 5 nm. By supplying the source gas and the oxidant to the wafer 200 under the above-mentioned processing conditions, a uniform and sufficiently thin oxide layer can be formed.

[0082] By performing the oxide layer forming step under the above-mentioned processing conditions, the density of OH terminations formed on the surface of the oxide layer can be made higher than the density of OH terminations formed on the surface of the first film. Also, the distribution of the density of OH terminations formed on the surface of the oxide layer can be made closer to a uniform state than the distribution of the density of OH terminations formed on the surface of the first film (see FIG. 5(a) and FIG. 5(b)).

[0083] In the oxide layer forming step, a catalyst is supplied together with the raw material gas and the oxidizing agent, so that the above-mentioned reaction can proceed in a non-plasma atmosphere and under the above-mentioned low temperature conditions. By performing the oxide layer forming step under temperature conditions equal to or lower than the processing temperature for forming the first film, for example, it is possible to suppress the influence of thermal history on the structure on the wafer 200 having the first film.

[0084] (Hydrophobization step) After the oxide layer forming step is performed, a modifying gas is supplied to the wafer 200 to hydrophobize the surface of the oxide layer formed on the first film. In the hydrophobization step, the output of the heater 207 is adjusted to maintain the temperature of the wafer 200 at or below the temperature of the wafer 200 in the source gas supply step and the oxidizing agent supply step, preferably at a temperature lower than the temperature of the wafer 200 in the source gas supply step and the oxidizing agent supply step as shown in FIG.

[0085] Specifically, the valve 243b is opened to allow the modifying gas to flow into the gas supply pipe 232b. The modifying gas has a flow rate adjusted by the MFC 241b, is supplied into the processing chamber 201 through the nozzle 249b, and is exhausted from the exhaust port 231a. At this time, the modifying gas is supplied to the wafer 200 from the side of the wafer 200 (modifying gas supply). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249c.

[0086] By supplying a modifying gas containing a hydrocarbon group, which is a hydrophobic substituent, to the wafer 200 under processing conditions described below, the modifying gas reacts with OH, which terminates the surface of the oxide layer, to make the surface of the oxide layer hydrophobic. Specifically, by supplying the modifying gas to the wafer 200, the hydrocarbon group contained in the modifying gas is chemically adsorbed to OH, which is an adsorption site on the surface of the oxide layer, and the surface of the oxide layer is terminated with the hydrocarbon group, which is a hydrophobic substituent. The surface of the oxide layer terminated with the hydrocarbon group becomes hydrophobic. In other words, a modified layer composed of a hydrophobic substituent is formed on the surface of the oxide layer. For example, when the hydrocarbon group contained in the modifying gas is a methyl group, the surface of the oxide layer is terminated with the methyl group, as shown in FIG. 5(c). In this way, the surface of the wafer 200 is hydrophobized via the oxide layer.

[0087] By supplying the modifying gas under temperature conditions described below, it is possible to suppress the desorption of OH terminations formed on the oxide layer.

[0088] The processing conditions for supplying the reformed gas in the hydrophobization step are as follows: Treatment temperature: room temperature (25°C) to 250°C, preferably room temperature to 150°C, more preferably room temperature to 100°C Treatment pressure: 5 to 2000 Pa, preferably 10 to 1000 Pa Processing time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Reformed gas supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0089] It is preferable to carry out this step at the same temperature as the temperature condition in the oxide layer forming step, or at a temperature lower than the temperature condition in the oxide layer forming step. Here, "the same temperature" includes not only the case where the temperature is exactly the same, but also the case where there is a temperature difference within a range of, for example, ±5°C.

[0090] As the modifying gas, for example, a compound represented by the following formula 1 is preferably used.

[0091] [R 11 ]n 1 -(X 1 )-[R 12 ]m 1 : formula 1 In the above formula 1, R 11 represents a first substituent bonded directly to X, R 12 represents a second substituent bonded directly to X, 1 represents a tetravalent atom selected from the group consisting of a carbon (C) atom, a Si atom, a germanium (Ge) atom, and a tetravalent metal atom; n 1 represents an integer from 1 to 3, m 1 represents an integer from 1 to 3, and n 1 +m 1 =4.

[0092] In formula 1, the first substituent R 11 The number of 1 is an integer of 1 to 3, and more preferably 2 or 3.1 When is 2 or 3, the first substituent R 11 may be the same or different.

[0093] R 11 As the first substituent represented by the formula (I), a hydrocarbon group, a hydrogen group (-H), an alkoxy group, a fluoro group, and a fluoroalkyl group are preferable. 11 The first substituent represented by the formula (1) is preferably a hydrogen group or a hydrocarbon group, and more preferably a hydrocarbon group. Here, the hydrocarbon group may be an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, or an alkynyl group, or may be an aromatic hydrocarbon group.

[0094] The alkyl group of the partial structure in the hydrocarbon group and alkoxy group as the first substituent is preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Specific examples of the alkoxy group as the first substituent include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0095] In formula 1, the second substituent R 12 The number of, i.e., m 1 is an integer of 1 to 3, and more preferably 1 or 2. 1 When R is 2 or 3, the second substituent R 12 may be the same or different.

[0096] R 12 The second substituent represented by the formula: is preferably a substituent that enables chemical adsorption of the reforming gas to an adsorption site (eg, OH termination) on the surface of the oxide layer.

[0097] R 12Examples of the second substituent represented by the formula (I) include an amino group, a chloro group, a bromo group, an iodo group, and a hydroxy group. 12 The second substituent represented by R is preferably an amino group, and more preferably a substituted amino group. In particular, from the viewpoint of the adsorption of the reformed gas to the oxide layer, 12 It is preferable that all of the second substituents represented by the following formula (I) are substituted amino groups.

[0098] The substituent of the substituted amino group is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group of the substituted amino group may be linear or branched. Specific examples of the alkyl group of the substituted amino group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0099] The number of substituents that the substituted amino group has is 1 or 2, and is preferably 2. When the number of substituents that the substituted amino group has is 2, the two substituents may be the same or different.

[0100] In formula 1, X 1 The atom to which the first and second substituents represented by the formula (I) are directly bonded is a tetravalent atom selected from the group consisting of a C atom, a Si atom, a Ge atom, and a tetravalent metal atom. Here, examples of the tetravalent metal atom include a titanium (Ti) atom, a zirconium (Zr) atom, a hafnium (Hf) atom, a molybdenum (Mo) atom, and a tungsten (W) atom.

[0101] Among these, X 1 The atom to which the first and second substituents represented by the following formula (I) are directly bonded is preferably a C atom, a Si atom, or a Ge atom. 1When X is any one of C atom, Si atom, and Ge atom, at least one of the following characteristics can be obtained: high adsorption of the reformed gas to the surface of the oxide layer, and high chemical stability of the reformed gas after adsorption to the surface of the oxide layer, i.e., residues derived from the reformed gas. Among these, Si atom is more preferable as X. This is because when X is a Si atom, it is possible to obtain a good balance between the two characteristics: high adsorption of the reformed gas to the surface of the oxide layer, and high chemical stability of the reformed gas after adsorption to the surface of the oxide layer, i.e., residues derived from the reformed gas.

[0102] Although the compound represented by formula 1 has been described above, the modified gas is not limited to the compound represented by formula 1. For example, the modified gas is preferably composed of a molecule including the above-mentioned first substituent, the above-mentioned second substituent, and an atom to which the first and second substituents are directly bonded, but the atom to which the first and second substituents are directly bonded may be a metal atom capable of bonding with five or more ligands. When the atom to which the first and second substituents are directly bonded is a metal atom capable of bonding with five or more ligands, the number of the first and second substituents in the molecule of the modified gas can be increased compared to the compound represented by formula 1. The modified gas may also be composed of a molecule including the above-mentioned first substituent, the above-mentioned second substituent, and two or more atoms to which the first and second substituents are directly bonded.

[0103] A specific example of the modified gas is (dimethylamino)trimethylsilane: (CH 3 ) 2 NSi(CH 3 ) 3 , (ethylamino)trimethylsilane: (C 2 H 5 )HNSi(CH 3 ) 3 , (propylamino)trimethylsilane: (C 3 H 7 ) 2 HNSi(CH 3 ) 3 , (butylamino)trimethylsilane: (C 4 H 9 )2 HNSi(CH 3 ) 3 , (diethylamino)trimethylsilane: (C 2 H 5 ) 2 NSi(CH 3 ) 3 , (dipropylamino)trimethylsilane: (C 3 H 7 ) 2 NSi(CH 3 ) 3 , (dibutylamino)trimethylsilane: (C 3 H 7 ) 2 NSi(CH 3 ) 3 , (dimethylamino)dimethylsilane: (CH 3 ) 2 NSiH(CH 3 ) 2 , (ethylamino)dimethylsilane: (C 2 H 5 )HNSiH(CH 3 ) 2 , (propylamino)dimethylsilane: (C 3 H 7 ) 2 HNSiH(CH 3 ) 2 , (butylamino)dimethylsilane: (C 4 H 9 ) 2 HNSiH(CH 3 ) 2 , (diethylamino)dimethylsilane: (C 2 H 5 ) 2 NSiH(CH 3 ) 2 , (dipropylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dibutylamino)dimethylsilane: (C 3 H 7 ) 2 NSiH(CH 3 ) 2 , (dimethylamino)methylsilane: (CH3 ) 2 NSiH 2 (CH 3 ), (ethylamino)methylsilane: (C 2 H 5 )HNSiH 2 (CH 3 ), (propylamino)methylsilane: (C 3 H 7 ) 2 HNSiH 2 (CH 3 ), (butylamino)methylsilane: (C 4 H 9 ) 2 HNSiH 2 (CH 3 ), (diethylamino)methylsilane: (C 2 H 5 ) 2 NSiH 2 (CH 3 ), (dipropylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dibutylamino)methylsilane: (C 3 H 7 ) 2 NSiH 2 (CH 3 ), (dimethylamino)diethylsilane: (CH 3 ) 2 NSiH(C 2 H 5 ) 2 , (ethylamino)diethylsilane: (C 2 H 5 )HNSiH(C 2 H 5 ) 2 , (propylamino)diethylsilane: (C 3 H 7 ) 2 HNSiH(C 2 H 5 ) 2 , (butylamino)diethylsilane: (C 4 H 9 ) 2 HNSiH(C 2 H5 ) 2 , (diethylamino)diethylsilane: (C 2 H 5 ) 2 NSiH(C 2 H 5 ) 2 , (dipropylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dibutylamino)diethylsilane: (C 3 H 7 ) 2 NSiH(C 2 H 5 ) 2 , (dimethylamino)ethylsilane: (CH 3 ) 2 NSiH 2 (C 2 H 5 ), (ethylamino)ethylsilane: (C 2 H 5 )HNSiH 2 (C 2 H 5 ), (propylamino)ethylsilane: (C 3 H 7 ) 2 HNSiH 2 (C 2 H 5 ), (butylamino)ethylsilane: (C 4 H 9 ) 2 HNSiH 2 (C 2 H 5 ), (diethylamino)ethylsilane: (C 2 H 5 ) 2 NSiH 2 (C 2 H 5 ), (dipropylamino)ethylsilane: (C 3 H 7 ) 2 NSiH 2 (C 2 H 5 ), (dibutylamino)ethylsilane: (C 3 H7 ) 2 NSiH 2 (C 2 H 5 ), (dipropylamino)silane: [(C 3 H 7 ) 2 N]SiH 3 , (dibutylamino)silane: [(C 4 H 9 ) 2 N]SiH 3 , (dipentylamino)silane: [(C 5 H 11 ) 2 N]SiH 3 , bis(dimethylamino)dimethylsilane: [(CH 3 ) 2 N] 2 Si(CH 3 ) 2 , bis(ethylamino)dimethylsilane: [(C 2 H 5 )HN] 2 Si(CH 3 ) 2 , bis(propylamino)dimethylsilane: [(C 3 H 7 ) 2 HN] 2 Si(CH 3 ) 2 , bis(butylamino)dimethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(CH 3 ) 2 , bis(diethylamino)dimethylsilane: [(C 2 H 5 ) 2 N] 2 Si(CH 3 ) 2 , bis(dipropylamino)dimethylsilane: [(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 , bis(dibutylamino)dimethylsilane: [(C 3 H 7 )2 N] 2 Si(CH 3 ) 2 , bis(dimethylamino)methylsilane: [(CH 3 ) 2 N] 2 SiH(CH 3 ), bis(ethylamino)methylsilane: [(C 2 H 5 )HN] 2 SiH(CH 3 ), bis(propylamino)methylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(CH 3 ), bis(butylamino)methylsilane: [(C 4 H 9 ) 2 HN] 2 SiH(CH 3 ), bis(diethylamino)methylsilane: [(C 2 H 5 ) 2 N] 2 SiH(CH 3 ), bis(dipropylamino)methylsilane: [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dibutylamino)methylsilane: [(C 3 H 7 ) 2 N] 2 SiH(CH 3 ), bis(dimethylamino)diethylsilane: [(CH 3 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(ethylamino)diethylsilane: [(C 2 H 5 )HN] 2 Si(C 2 H 5 ) 2 , bis(propylamino)diethylsilane: [(C 3 H 7 )2 HN] 2 Si(C 2 H 5 ) 2 , bis(butylamino)diethylsilane: [(C 4 H 9 ) 2 HN] 2 Si(C 2 H 5 ) 2 , bis(diethylamino)diethylsilane: [(C 2 H 5 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dipropylamino)diethylsilane: [(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dibutylamino)diethylsilane: [(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 , bis(dimethylamino)ethylsilane: [(CH 3 ) 2 N] 2 SiH(C 2 H 5 ), bis(ethylamino)ethylsilane: [(C 2 H 5 )HN] 2 SiH(C 2 H 5 ), bis(propylamino)ethylsilane: [(C 3 H 7 ) 2 HN] 2 SiH(C 2 H 5 ), bis(butylamino)ethylsilane: [(C 4 H 9 ) 2 HN] 2 SiH(C 2 H 5), bis(diethylamino)ethylsilane: [(C 2 H 5 ) 2 N] 2 SiH(C 2 H 5 ), bis(dipropylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(dibutylamino)ethylsilane: [(C 3 H 7 ) 2 N] 2 SiH(C 2 H 5 ), bis(diethylamino)silane: [(C 2 H 5 ) 2 N] 2 SiH 2 , bis(dipropylamino)silane [(C 3 H 7 ) 2 N] 2 SiH 2 , bis(dibutylamino)silane: [(C 4 H 9 ) 2 N] 2 SiH 2 , bis(dipentylamino)silane: [(C 5 H 11 ) 2 N] 2 SiH 2 , (dimethylamino)trimethoxysilane: (CH 3 ) 2 NSi(OCH 3 ) 3、 (Dimethylamino)triethoxysilane: (CH 3 ) 2 NSi(OC 2 H 5 ) 3、 (Dimethylamino)triprotoxysilane: (CH 3 ) 2 NSi(OC 3 H 7 ) 3、 (Dimethylamino)tributoxoxysilane: (CH3 ) 2 NSi(OC 4 H 9 ) 3 As the modifying gas, one or more of these can be used.

[0104] In the hydrophobization step, the first substituents, such as a hydrocarbon group, a hydrogen group, an alkoxy group, a fluoro group, and a fluoroalkyl group, are adsorbed on the surface of the oxide layer to form at least a part of the hydrophobic termination. However, the hydrophobic termination formed on the surface of the oxide layer may include only a part of the first substituent, or may further include other atoms. In addition, in the hydrophobization step, when a reformed gas having a fluoro group, a fluoroalkyl group, a hydrogen group, or the like as a first substituent cannot exist stably as a single compound, a reformed gas having another first substituent and capable of existing stably as a single compound may be adsorbed on the oxide layer, and then a specific treatment may be applied to convert the other first substituents to a hydrogen group, a fluoro group, or a fluoroalkyl group. An example of a method for converting the first substituent is shown below.

[0105] In the first example, a modifying gas having a hydrogen group as a first substituent is adsorbed on the oxide layer, and then the wafer 200 is treated with fluorine (F 2 The hydrogen groups can be converted to fluoro groups by exposure to hydrogen fluoride (HF) gas or hydrogen fluoride (HF) gas. As a second example, a modifying gas having an alkyl group as the first substituent is adsorbed on the oxide layer, and then the wafer 200 is exposed to F 2 In a third example, a modifying gas having a chloro group as the first substituent is adsorbed on the oxide layer, and then the wafer 200 is exposed to H 2 Exposure to plasma can convert the chloro groups to hydrogen groups.

[0106] After the oxide layer formed on the first film is modified, the valve 243b is closed to stop the supply of the modifying gas into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in the cleaning step. Note that the processing temperature for purging in this step is preferably the same as the processing temperature for supplying the modifying gas.

[0107] (After purging and atmospheric pressure recovery) After the heat treatment step is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0108] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0109] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0110] In the oxidation layer forming step, an oxidation layer having OH terminations formed at a higher density than the OH terminations formed on the surface of the first film is formed on the first film, so that in the hydrophobization step, the surface of the wafer 200 can be sufficiently and uniformly hydrophobized through the oxidation layer regardless of the composition of the first film. For example, even if the first film is an O-free film having a low density of OH terminations, the surface of the wafer 200 can be sufficiently and uniformly hydrophobized through the oxidation layer.

[0111] In the oxide layer forming step (particularly the raw material gas supply step and oxidant supply step for forming the first layer), by setting the processing temperature to 150°C or less, it is possible to form an oxide layer while suppressing OH termination from being detached from the surface. This allows the formation of an oxide layer with a high density of OH termination. By setting the processing temperature to 100°C or less, it is possible to more reliably obtain an oxide layer with a sufficiently high density of OH termination. If the processing temperature in this step exceeds 150°C, it may be difficult to form an oxide layer with a sufficiently high density of OH termination. If the processing temperature in this step exceeds 100°C, it may be impossible to form an oxide layer with a sufficiently high density of OH termination.

[0112] In the hydrophobization step, the treatment temperature is set to 250°C or less, so that the OH termination formed on the surface of the oxide layer can be prevented from being detached from the surface. This allows the density of the OH termination on the oxide layer to be maintained. The treatment temperature is set to 150°C or less, so that the density of the OH termination can be reliably maintained at a sufficiently high level. If the treatment temperature of this step exceeds 250°C, it may be difficult to maintain the density of the OH termination on the oxide layer. If the treatment temperature of this step exceeds 150°C, it may be impossible to maintain the density of the OH termination on the oxide layer at a sufficiently high level.

[0113] By carrying out the hydrophobization step at the same temperature as or lower than the temperature conditions in the oxide layer formation step, it is possible to carry out hydrophobization while maintaining the OH termination on the surface of the oxide layer without causing detachment of the OH termination due to temperature changes from the oxide layer formation step.

[0114] By making the thickness of the oxide layer 1.5 nm or more, it is possible to form and maintain a termination with a uniform and sufficient density on the surface of the oxide layer. If the thickness of the oxide layer is less than 1.5 nm, it may be difficult to form and maintain a termination with a uniform and sufficient density on the surface of the oxide layer. Furthermore, by making the thickness of the oxide layer 5 nm or less, it becomes easy to remove the oxide layer in a subsequent process, and even if the oxide layer is left as it is, it is possible to reduce the influence of the oxide layer on the characteristics of the device. If the thickness of the oxide layer exceeds 5 nm, it may be difficult to remove the oxide layer, or the influence of the oxide layer on the characteristics of the device may be large.

[0115] The above-mentioned effects can be obtained in the same way even when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the various cleaning agents, various raw material gases, various oxidizing agents, various modifying gases, various catalysts, and various inert gases described above.

[0116] <Second Aspect of the Present Disclosure> Hereinafter, as one step of the manufacturing process of the semiconductor device in the second embodiment of the present disclosure, a method of processing the wafer 200, i.e., an example of a processing sequence for hydrophobizing the surface of the wafer 200 via an oxide layer, will be described mainly with reference to Figures 6(a) to 6(c). In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0117] A first film as a base and a second film having a composition different from that of the first film are formed on the wafer 200. For convenience, a typical example will be described below in which the first film is a Si film as a non-O-containing film, and the second film is a silicon oxide film (SiO film) as an O-containing film.

[0118] In the processing sequence of this embodiment, (a) a step of forming an oxide layer containing a predetermined element on a first film and a second film formed on the wafer 200 by supplying a source gas containing a predetermined element to the wafer 200, the oxide layer having an OH termination formed on the surface and a higher density of the OH termination than the density of the OH termination formed on the surface of the first film (oxide layer forming step); (b) supplying a modifying gas containing a hydrocarbon group to the wafer 200 on which the oxide layer is formed to hydrophobize the surface of the oxide layer (hydrophobization step); Do the following.

[0119] In this embodiment, the cleaning step, the oxide layer forming step, and the hydrophobizing step are carried out in the same manner as in the first embodiment described above.

[0120] The cleaning step, the oxide layer forming step, and the hydrophobization step in this embodiment may be the same as the processing procedures and processing conditions in the cleaning step, the oxide layer forming step, and the hydrophobization step in the above-mentioned embodiment 1. The cleaning step, the oxide layer forming step, and the hydrophobization step in this embodiment will be described below.

[0121] (Washing step)

[0122] In this step, by supplying a cleaning agent to the wafer 200, for example, the natural oxide film formed on the surface of the first film or the second film can be etched to expose the surfaces of the first film and the second film. At this time, the surface of the first film is in a state where OH termination is not formed in many areas, that is, OH termination is formed in some areas, as shown in FIG. 6(a). The surface of the second film is in a state where OH termination is formed at a higher density than the surface of the first film, as shown in FIG. 6(a). In this way, the density of OH termination on the surfaces of the first film and the second film is different. In addition, the OH termination formed on the surfaces of the first film and the second film both have a non-uniform distribution.

[0123] The cleaning agent and inert gas used in this embodiment may be the same as those used in the first embodiment.

[0124] In addition, in the case of using a wafer 200 in which the surfaces of the first film and the second film have been cleaned in advance, for example, by removing any native oxide film formed on the surfaces of the first film and the second film, the cleaning step can be omitted.

[0125] (Oxide layer formation step) In the oxide layer forming step in this embodiment, a raw material gas supplying step and an oxidizing agent supplying step are sequentially performed in the same manner as in the oxide layer forming step in the above-mentioned first embodiment. The raw material gas supplying step and the oxidizing agent supplying step in this embodiment can be performed under the same processing procedures and processing conditions as in the above-mentioned first embodiment.

[0126] [Source gas supply step]

[0127] In this step, for example, a source gas containing Si as a predetermined element is supplied to the wafer 200, so that a Si-containing layer is formed as a third layer on the surfaces of the first film and the second film. The third layer is formed by adsorbing Si contained in the source gas onto the surfaces of the first film and the second film.

[0128] [Oxidant supply step] In this step, at least a part of the third layer formed on the surfaces of the first film and the second film in the source gas supply step is oxidized by supplying an oxidizing agent to the wafer 200. As a result, the third layer is oxidized on the surfaces of the first film and the second film as the base, and a fourth layer having OH termination formed on the surface is formed.

[0129] The raw material gas, oxidizing agent, and catalyst used in this embodiment may be the same as those in the first embodiment.

[0130] [Perform the specified number of times] By performing the above-mentioned raw material gas supply step and oxidizing agent supply step alternately a predetermined number of times (m times, m is an integer of 1 or more) without simultaneous operation, a uniform oxide layer with OH-terminated surfaces can be formed on the first film and the second film formed on the wafer 200. For example, when the above-mentioned raw material gas and oxidizing agent are used, a SiOC layer or a SiO layer can be formed on the first film and the second film as an oxide layer containing Si as a predetermined element. It is preferable to repeat the above-mentioned cycle multiple times. That is, it is preferable to repeat the above-mentioned cycle multiple times until the thickness of the second layer formed per cycle is thinner than the desired film thickness and the thickness of the oxide layer formed by stacking the fourth layer becomes the desired thickness, for example, 1.5 to 5 nm.

[0131] By performing the oxide layer forming step under the above-mentioned processing conditions, the density of OH terminations formed on the surface of the oxide layer can be made higher than the density of OH terminations formed on the surface of either the first film or the second film. In addition, the distribution of the density of OH terminations formed on the surface of the oxide layer can be made closer to a uniform state than the distribution of the density of OH terminations formed on the surface of either the first film or the second film. In addition, regardless of the difference in composition between the first film and the second film, which are the undercoat films, the density of OH terminations formed on the surface of the oxide layer on the first film and the density of OH terminations formed on the surface of the oxide layer formed on the surface of the second film can be made uniform (see FIG. 6(a) and FIG. 6(b)).

[0132] (Hydrophobization step) In this step, a modifying gas containing a hydrocarbon group is supplied to the wafer 200, and the modifying gas reacts with OH terminating the surface of the oxide layer, thereby making the surface of the oxide layer hydrophobic. Specifically, by supplying the modifying gas to the wafer 200, the hydrocarbon group contained in the modifying gas is chemically adsorbed to OH, which is an adsorption site on the surface of the oxide layer, and the surface of the oxide layer is terminated with a hydrocarbon group. The surface of the oxide layer terminated with a hydrocarbon group becomes hydrophobic. For example, when the hydrocarbon group is a methyl group, the surface of the oxide layer is terminated with a methyl group as shown in FIG. 6(c). In this way, the surface of the wafer 200 is hydrophobicized via the oxide layer.

[0133] According to this aspect, in addition to the effects obtained in the first aspect described above, one or more of the following effects can be obtained.

[0134] In the oxidation layer forming step, an oxidation layer having OH terminations formed at a higher density than the OH terminations formed on the surface of the first film is formed on the first film and the second film, so that in the hydrophobization step, even if the compositions of the first film and the second film are different from each other, the surface of the wafer 200 can be uniformly and sufficiently hydrophobized through the oxidation layer. For example, even if the densities of the OH terminations formed on the surfaces of the first film and the second film are different, the surface of the wafer 200 can be uniformly and sufficiently hydrophobized through the oxidation layer.

[0135] In the oxidation layer formation step, an oxidation layer is formed on the surface in which the density of OH terminations is higher than the density of OH terminations formed on the surface of the second film, and therefore, in the hydrophobization step, the surface of the wafer 200 can be uniformly and more sufficiently hydrophobized via the oxidation layer.

[0136] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0137] (Hydrophobicity control) In the above-mentioned aspects (first and second aspects) of the present disclosure, an example was described in which the surface of the wafer 200 is made hydrophobic via an oxide layer. In the technology of the present disclosure, the degree of hydrophobicity of the surface of the wafer 200 can be further controlled by a method described in the following example. The process procedure and process conditions in this aspect can be the same as those in each step in the above-mentioned aspects, except as specifically mentioned below.

[0138] (Variation 1: Control by temperature adjustment in the oxide layer formation step) In the oxide layer forming step, as the processing temperature increases, the density of OH terminations formed on the surface of the oxide layer tends to decrease. Here, the density of OH terminations reacting with the modifying gas decreases, and thus the density of hydrophobic terminations such as hydrocarbon group terminations formed on the surface of the oxide layer in the hydrophobization step (i.e., the density of the modified layer) decreases, resulting in a decrease in the hydrophobicity of the wafer surface. In this example, the processing temperature in the oxide layer forming step is adjusted to control the density of OH terminations formed on the surface of the oxide layer to a desired density. That is, the processing temperature in the oxide layer forming step is adjusted to control the degree of hydrophobicity of the wafer surface to a desired degree (in other words, the density of hydrophobic terminations formed on the surface of the oxide layer to a desired degree).

[0139] Specifically, for example, the set temperature of the heater 207, etc. is adjusted so that the processing temperature in the oxide layer forming step is higher than a predetermined temperature, thereby decreasing the density of OH terminations formed on the surface of the oxide layer, and the hydrophobicity of the wafer surface is controlled to be decreased. Similarly, the set temperature of the heater 207, etc. is adjusted so that the processing temperature in the oxide layer forming step is lower than a predetermined temperature, thereby increasing the density of OH terminations formed on the surface of the oxide layer, and the hydrophobicity of the wafer surface is controlled to be increased. From another perspective, the processing temperature in the oxide layer forming step is controlled to a predetermined temperature corresponding to the desired hydrophobicity of the wafer surface, thereby controlling the wafer surface to have the desired hydrophobicity.

[0140] (Variation 2: Control by Heat Treatment After Oxide Layer Formation Step) In the above-mentioned variant 1, the density of OH terminations formed on the surface of the oxide layer is controlled by adjusting the processing temperature in the oxide layer formation step, whereas in this variant, a step of heating the wafer (hereinafter sometimes referred to as the annealing step) is further performed between the oxide layer formation step and the hydrophobization step, thereby desorbing the OH terminations formed on the surface of the oxide layer and controlling the density of the OH terminations.

[0141] Specifically, in the annealing step, the wafer on which the oxide layer is formed in the oxide layer formation step is heated to a predetermined processing temperature for a predetermined processing time in an inert gas atmosphere, thereby desorbing the OH terminations until the density of the OH terminations formed on the surface of the oxide layer reaches a desired level (i.e., until the density of the OH terminations reaches such a level that the hydrophobicity of the wafer surface reaches a desired level in the hydrophobization step).

[0142] The longer the processing time in the annealing step, and the higher the processing temperature, the greater the amount of OH terminations that are desorbed. Therefore, by adjusting at least one of the processing time and the processing temperature in the annealing step, the density of OH terminations formed on the surface of the oxide layer and the degree of hydrophobicity of the wafer surface are controlled to be the desired degree. From another perspective, by adjusting at least one of the processing time and the processing temperature in the annealing step to a predetermined processing time and processing temperature corresponding to the desired degree of hydrophobicity of the wafer surface, the wafer surface is controlled to have the desired degree of hydrophobicity.

[0143] The processing temperature in the annealing step is preferably the same as or higher than the processing temperature in the oxide layer forming step. The higher the processing temperature in the annealing step, the more the desorption of OH terminations formed on the surface of the oxide layer can be promoted. In addition, by making the processing temperature in the annealing step the same (or substantially the same) as the processing temperature in the oxide layer forming step, the density of OH terminations can be adjusted gradually, and the time required for heating and cooling the wafer can be shortened.

[0144] (Variation 3: Control by Selection of Reformed Gas) The hydrophobic termination formed on the surface of the oxide layer in the hydrophobization step has different hydrophobicity on the surface of the wafer depending on its composition. In this modification, the composition (type) of the hydrophobic termination is changed by selecting the modifying gas used in the hydrophobization step, and the hydrophobicity of the surface of the wafer is changed.

[0145] For example, among the hydrophobic terminations formed on the surface of the oxide layer, terminations composed of a hydrocarbon group, a hydrogen group, and an alkoxy group have a relationship of "hydrocarbon group>hydrogen group>alkoxy group" in terms of the magnitude of hydrophobicity. In this modification, for example, the modifying gas in the hydrophobization step is changed from a gas containing a hydrocarbon group (i.e., a gas that forms a hydrocarbon group termination on the surface of the oxide layer) to a gas containing a hydrogen group (i.e., a gas that forms a hydrogen group termination on the surface of the oxide layer), thereby adjusting the hydrophobicity of the wafer surface to be lower. Similarly, the hydrophobicity of the wafer surface is adjusted to be further lower by changing from a gas containing a hydrogen group to a gas containing an alkoxy group (i.e., a gas that forms an alkoxy group termination on the surface of the oxide layer).

[0146] (Variation 4: Control by supplying water vapor-containing gas after the oxide layer formation step) In this modified example, between the oxide layer formation step and the hydrophobization step, a step of supplying a gas containing water vapor to the wafer (hereinafter sometimes referred to as a water vapor-containing gas supply step) is further performed, whereby the water vapor is reacted with the surface of the oxide layer, thereby controlling the density of the OH terminations so as to increase the density of the OH terminations formed on the surface of the oxide layer.

[0147] Specifically, in the water vapor-containing gas supply step, a water vapor-containing gas is supplied for a predetermined time to the wafer on which an oxide layer is formed in the oxide layer formation step, thereby increasing the density of the OH terminations formed on the surface of the oxide layer until the density of the OH terminations reaches a desired level (i.e., until the density of the OH terminations reaches such a level that the hydrophobicity of the wafer surface becomes a desired level in the hydrophobization step).

[0148] By adjusting the processing time in the water vapor-containing gas supply step, the density of OH termination formed on the surface of the oxide layer and the hydrophobicity of the wafer surface are controlled to be the desired level. From another point of view, by adjusting the processing time in the water vapor-containing gas supply step to a predetermined processing time corresponding to the desired hydrophobicity of the wafer surface, the wafer surface is controlled to have the desired hydrophobicity.

[0149] The water vapor-containing gas used in the steam-containing gas supply step can be atmospheric air containing water vapor. When atmospheric air is used, this step can be performed by carrying the wafer out of the processing chamber, which is under atmospheric air, after the oxide layer formation step and exposing it to the atmosphere. After this step is performed by exposing it to the atmosphere, the hydrophobization step is performed. The oxide layer formation step, the water vapor-containing gas supply step, and the hydrophobization step can also be performed in the same processing chamber (in-situ).

[0150] In these modified examples 1 to 4, the same effects as those of the above embodiment can be obtained.

[0151] In the above-mentioned embodiment, the first film is an Si film as an O-free film, but the present disclosure is not limited thereto. The first film may be a film containing a semiconductor element such as a silicon nitride film (SiN film), a silicon carbonitride film (SiCN film), a silicon carbide film (SiC film), a silicon borocarbonitride film (SiBCN film), or a silicon boronitride film (SiBN film), or a film containing a metal element such as a titanium nitride film (TiN film), a tungsten film (W film), a tungsten nitride film (WN film), a hafnium nitride film (HfN film), a zirconium nitride film (ZrN film), a tantalum nitride film (TaN film), a molybdenum film (Mo film), a molybdenum nitride film (MoN), an aluminum film (Al film), an aluminum nitride film (AlN film), a ruthenium film (Ru film), a cobalt film (Co film), or a titanium film (Ti film). In these cases, the same effect as that of the above-mentioned embodiment can be obtained.

[0152] In the above embodiment, the first film is an O-free film, but the present disclosure is not limited to this. For example, the first film may be an O-containing film, for example, a film containing a semiconductor element such as a silicon oxide film (SiO film) or a silicon oxide carbide film (SiOC film), or a film containing a metal element such as a titanium oxide film (TiO film), a titanic oxide carbide film (TiOC film), a tungsten oxide film (WO film), a tungsten oxide carbide film (WOC film), a hafnium oxide film (HfO film), a hafnic oxide carbide film (HfOC film), a zirconium oxide film (ZrO film), a zirconic oxide carbide film (ZrOC film), a tantalum oxide film (TaO film), a tantalic oxide carbide film (TaOC film), a molybdenum oxide film (MoO film), a molybdenum oxide carbide film (MoOC film), an aluminum oxide film (AlO film), an aluminum oxide carbide film (AlOC film), a ruthenium oxide film (RuO film), a cobalt oxide film (CoO film), or a titanium oxide film (TiO film). In these cases, at least some of the effects of the above-mentioned aspects can be obtained. Specifically, even if the first film is an O-containing film, that is, a film in which OH terminations are formed in most of the surface area, the distribution of OH terminations may not be uniform. In such cases, the surface of the wafer 200 can be made uniformly hydrophobic by providing an oxide layer.

[0153] In the above-mentioned embodiment, the second film is an O-containing film, but the present disclosure is not limited thereto. For example, the second film may be the above-mentioned O-free film. In addition, in the above-mentioned embodiment, the first film is an O-free film, and the second film is an O-containing film, but the present disclosure is not limited thereto. For example, the first film and the second film may be the above-mentioned O-containing film, or the first film and the second film may be the above-mentioned O-free film. In these cases, at least some of the effects of the above-mentioned embodiment can be obtained. Specifically, even if the first film and the second film are a combination of O-free films or a combination of O-containing films, the density of OH terminations formed on the surfaces of these films may differ, and the distribution of OH terminations may not be uniform. Even in such a case, the surface of the wafer 200 can be uniformly hydrophobized by the oxide layer.

[0154] In the above-mentioned embodiment, the case where the density of OH termination formed on the surface is higher than the density of OH termination formed on the surface of both the first film and the second film in the oxide layer forming step is described as an example, but the present disclosure is not limited thereto. For example, the density of OH termination formed on the surface of the oxide layer may be lower than the density of OH termination formed on the surface of the second film. Even in this case, at least some of the effects of the above-mentioned embodiment can be obtained. Specifically, for example, even if the densities of OH termination formed on the surfaces of the first film and the second film are different, the surface of the wafer 200 can be uniformly hydrophobized through the oxide layer.

[0155] Although not specifically described in the above embodiment, the cleaning step, the oxide layer forming step, and the hydrophobization step are preferably performed in the same processing chamber (in-situ). As a result, after the surface of the wafer 200 is cleaned by the cleaning step (after the native oxide film is removed), the oxide layer forming step and the hydrophobization step can be performed without exposing the wafer 200 to the atmosphere, that is, while the surface of the wafer 200 is kept clean. In addition, when the cleaning step can be omitted as described above, it is preferable to perform the oxide layer forming step and the hydrophobization step in the same processing chamber. As a result, it becomes easy to perform the hydrophobization process in the hydrophobization step while maintaining the OH group termination on the surface of the oxide layer formed in the oxide layer forming step. In addition, by performing both the oxide layer forming step and the hydrophobization step under the above-mentioned low temperature conditions, it becomes easy to perform these steps as continuous processing in the same processing chamber. By performing these steps continuously, it becomes easy to perform the hydrophobization process in the hydrophobization step while maintaining the OH group termination on the surface of the oxide layer formed in the oxide layer forming step. The continuous process means that, for example, between the oxide layer forming step and the hydrophobizing step, no other process that substantially affects the density or distribution of OH group terminations on the oxide layer surface is performed. More specifically, the continuous process can include, for example, not supplying a modifying gas other than that used in the oxide layer forming step and the hydrophobizing step to the oxide layer surface, not annealing the wafer 200 (i.e., modifying process by heating), and the like.

[0156] Although not specifically described in the above embodiment, the method may further include a step of forming a resist film on the surface of the oxide layer whose surface has been hydrophobized (resist coating step) after the hydrophobization step. In this case, since the surface of the wafer 200 is sufficiently and uniformly hydrophobized via the oxide layer, it is possible to sufficiently and uniformly adhere the resist to the wafer 200.

[0157] In the above embodiment, the hydrophobization step is performed by supplying the above-mentioned modifying gas to the wafer 200 to hydrophobize the surface of the wafer 200 through the oxide layer, but the present disclosure is not limited to this. For example, the surface of the oxide layer may be terminated with methyl groups by applying hexamethyldisilazane (HMDS) in a vapor state to the wafer 200. In this case, the same effect as in the above embodiment can be obtained.

[0158] It is preferable that the recipes used for each process are prepared individually according to the process contents, and are recorded and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes recorded and stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing device. It is also possible to reduce the burden on the operator, and to quickly start each process while avoiding operational errors.

[0159] The above-mentioned recipes may not only be newly created, but may also be prepared by modifying an existing recipe that has already been 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 recipe has been recorded. Also, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0160] In the above-mentioned 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-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0161] When using these substrate processing apparatuses, each process can be performed according to the same process procedures and under the same process conditions as in the above-mentioned aspects and modifications, and the same effects as in the above-mentioned aspects and modifications can be obtained.

[0162] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in such a case may be the same as those of the above-mentioned aspects and modifications. [Explanation of symbols]

[0163] 200 wafers (substrates)

Claims

1. (a) forming an oxide layer containing a predetermined element on a first film formed on a substrate, the oxide layer having a surface terminated with hydroxyl groups and a density of the hydroxyl groups higher than a density of the hydroxyl groups formed on the surface of the first film; (b) supplying a modifying gas containing a hydrocarbon group to the substrate on which the oxide layer is formed, thereby hydrophobizing a surface of the oxide layer; having In (a), (a1) supplying a source gas containing the predetermined element to the substrate; (a2) supplying an oxidizing agent to the substrate; (a3) supplying a catalyst to the substrate; The method for processing a substrate includes performing a cycle including the steps of:

2. The first film is an oxygen-free film. The method of claim 1 .

3. In the step (a), the oxide layer is further formed on a second film having a composition different from that of the first film, the second film being formed on the substrate. The method of claim 1 .

4. the density of the hydroxyl group terminations formed on the surface of the first film is different from the density of the hydroxyl group terminations formed on the surface of the second film; The substrate processing method according to claim 3 .

5. the density of hydroxyl group terminations formed on the surface of the oxide layer is higher than the density of hydroxyl group terminations formed on the surface of the second film; The substrate processing method according to claim 4 .

6. The first film is an oxygen-free film, and the second film is an oxygen-containing film. The substrate processing method according to any one of claims 3 to 5.

7. In step (b), the modifying gas is supplied to the substrate to terminate the surface of the oxide layer with a hydrocarbon group. The method of claim 1 .

8. In (b), the modifying gas is reacted with hydroxyl groups terminating the surface of the oxide layer to hydrophobize the surface of the oxide layer. The method of claim 1 .

9. The modifying gas is a gas containing an alkyl group. The substrate processing method according to claim 7 or 8.

10. The modifying gas is an aminosilane gas. The substrate processing method according to claim 9 .

11. (a) is carried out at a temperature equal to or lower than a processing temperature for forming the first film; The method of claim 1 .

12. (a) is carried out at a temperature of 150° C. or less; The method of claim 11.

13. (b) is carried out at the same temperature as (a) or at a lower temperature than (a); The substrate processing method according to claim 11 or 12.

14. (a) and (b) are carried out in the same processing chamber; The method of claim 1 .

15. (b) is carried out consecutively following (a); The method of claim 1 .

16. The thickness of the oxide layer is 1.5 nm or more. The method of claim 1 .

17. The source gas is a gas containing a halogen element. The method of claim 1 .

18. (a) forming an oxide layer containing a predetermined element on a first film formed on a substrate, the oxide layer having a surface terminated with hydroxyl groups and a density of the hydroxyl groups higher than a density of the hydroxyl groups formed on the surface of the first film; (b) supplying a modifying gas containing a hydrocarbon group to the substrate on which the oxide layer is formed, thereby hydrophobizing a surface of the oxide layer; having In (a), (a1) supplying a source gas containing the predetermined element to the substrate; (a2) supplying an oxidizing agent to the substrate; (a3) supplying a catalyst to the substrate; The method for manufacturing a semiconductor device includes the steps of: forming the oxide layer by performing a cycle including the steps of:

19. (a) forming an oxide layer containing a predetermined element on a first film formed on a substrate, the oxide layer having a surface terminated with hydroxyl groups and a density of the hydroxyl groups higher than a density of the hydroxyl groups previously formed on the surface of the first film; (b) supplying a modifying gas containing a hydrocarbon group to the substrate on which the oxide layer is formed, thereby hydrophobizing a surface of the oxide layer; In (a), (a1) supplying a source gas containing the predetermined element to the substrate; (a2) supplying an oxidizing agent to the substrate; (a3) supplying a catalyst to the substrate; forming the oxide layer by performing a predetermined number of cycles including the steps of: A program for causing a computer to execute the above in a substrate processing apparatus.

20. a gas supply system configured to be able to supply a source gas containing a predetermined element, an oxidizing agent, a catalyst, and a modifying gas containing a hydrocarbon group to the substrate; a control unit configured to be capable of controlling the gas supply system to execute the following processes: (a) forming an oxide layer containing the predetermined element on a first film formed on the substrate, the oxide layer having a surface terminated with hydroxyl groups and a density of the hydroxyl groups that is higher than a density of the hydroxyl groups that were formed on the surface of the first film; and (b) supplying the modifying gas to the substrate on which the oxide layer is formed, thereby hydrophobizing the surface of the oxide layer. Has (a) is (a1) supplying the source gas to the substrate; (a2) supplying the oxidizing agent to the substrate; (a3) supplying the catalyst to the substrate; a step of forming the oxide layer by performing a cycle including the steps of:

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