Processing method, method for manufacturing a semiconductor device, processing apparatus, and program

Abstract

This technology provides an efficient method for etching the surface of a substrate. [Solution] The method comprises: (a) preparing a first processing container in which a layer containing substance X is formed inside; (b) transporting a substrate into the first processing container in which the layer containing substance X is formed; and (c) supplying a first processing agent to the substrate in the first processing container in which the layer containing substance X is formed, and reacting it with the substance X derived from the layer containing substance X to etch the surface of the substrate.

Description

[Technical Field]

[0001] This disclosure relates to processing methods, methods for manufacturing semiconductor devices, processing apparatuses, and programs. [Background technology]

[0002] As part of the manufacturing process for semiconductor devices, etching of the substrate surface is sometimes performed (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-137735 [Overview of the project] [Problems that the invention aims to solve]

[0004] This disclosure provides a technology that enables efficient etching of the surface of a substrate. [Means for solving the problem]

[0005] According to one aspect of this disclosure, (a) A step of preparing a first processing container in which a layer containing substance X is formed inside, (b) A step of transporting a substrate into the first processing container in which the substance X-containing layer is formed, (c) A step of supplying a first processing agent to the substrate in the first processing container on which the substance X-containing layer is formed, and reacting it with the substance X derived from the substance X-containing layer to etch the surface of the substrate, Technology to perform this will be provided. [Effects of the Invention]

[0006] According to this disclosure, it becomes possible to efficiently etch the surface of a substrate. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a schematic diagram of a vertical processing furnace of a processing apparatus preferably used in the first aspect of this disclosure, and shows the processing furnace 202 portion in a vertical cross-sectional view. [Figure 2] Figure 2 is a schematic diagram of a vertical processing furnace of a processing apparatus preferably used in the first aspect of this disclosure, and shows the processing furnace 202 portion as a cross-sectional view along line AA in Figure 1. [Figure 3] Figure 3 is a schematic configuration diagram of a controller 121 of a processing device preferably used in the first aspect of this disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4] Figure 4(a) is a schematic partial cross-sectional view of the apparatus in the first embodiment of the present disclosure, showing the state before a substrate with an oxide formed on its surface is loaded into a first processing container in which a layer containing substance X is formed internally. Figure 4(b) is a schematic partial cross-sectional view of the apparatus in the first embodiment of the present disclosure, showing the state after the substrate has been loaded into the first processing container. Figure 4(c) is a schematic partial cross-sectional view of the apparatus in the first embodiment of the present disclosure, showing the state after the first processing agent is supplied to the substrate in the first processing container and the surface of the substrate is etched. Figure 4(d) is a schematic partial cross-sectional view of the apparatus in the first embodiment of the present disclosure, showing the state after the etching of the surface of the substrate is completed. Figure 4(e) is a schematic partial cross-sectional view of the apparatus in the first embodiment of the present disclosure, showing the state after the second processing agent is supplied to the substrate in the first processing container and a film is formed on the etched surface of the substrate. [Figure 5]Figure 5(a) is a schematic partial cross-sectional view of the apparatus in a second aspect of the present disclosure, showing the state before a first boat supporting a substrate with an oxide formed on its surface is loaded into a first processing container having a layer containing substance X formed inside. Figure 5(b) is a schematic partial cross-sectional view of the apparatus in a second aspect of the present disclosure, showing the state after a first processing agent is supplied to a substrate on a first boat loaded into the first processing container, and the surface of the substrate is etched. Figure 5(c) is a schematic partial cross-sectional view of the apparatus in a second aspect of the present disclosure, showing the state after the first boat supporting the etched substrate is removed from the first processing container and before it is loaded into the second processing container, and before a second boat supporting a substrate with an oxide formed on its surface is loaded into the first processing container. Figure 5(d) is a schematic partial cross-sectional view of a processing apparatus in a second aspect of the present disclosure, showing that the following processes are carried out in parallel: supplying a second processing agent to a substrate on a first boat that has been brought into a second processing container to form a film on the substrate whose surface has been etched, and supplying a first processing agent to a substrate on a second boat that has been brought into a first processing container to etch the surface of the substrate. [Figure 6] This is a flowchart of a second aspect of the present disclosure, showing how steps A to D are performed multiple times, with the nth step D being performed in parallel with at least one of the (n+1)th steps A to C. [Figure 7] Figure 7(a) is a schematic partial cross-sectional view of a processing apparatus in a third aspect of the present disclosure, showing an example in which the content, concentration, density, and thickness of substance X in the substance X-containing layer differ between the upper part of the first processing vessel and other parts (middle and lower parts). Figure 7(b) is a schematic partial cross-sectional view of a processing apparatus in a third aspect of the present disclosure, showing another example in which the content, concentration, density, and thickness of substance X in the substance X-containing layer differ between the middle part of the first processing vessel and other parts (upper and lower parts). Figure 7(c) is a schematic partial cross-sectional view of a processing apparatus in a third aspect of the present disclosure, showing another example in which the content, concentration, density, and thickness of substance X in the substance X-containing layer differ between the lower part of the first processing vessel and other parts (upper and middle parts). [Figure 8] Figure 8(a) is a schematic partial cross-sectional view showing one example of the configuration of a processing furnace in the processing apparatus of the third aspect of this disclosure. Figure 8(b) is a schematic partial cross-sectional view showing another example of the configuration of a processing furnace in the processing apparatus of the third aspect of this disclosure. [Modes for carrying out the invention]

[0008] <First aspect of this disclosure> The first aspect of this disclosure will be described below, mainly with reference to Figures 1 to 3 and Figures 4(a) to 4(e). Note that the drawings used in the following description are all schematic, and the dimensional relationships and ratios of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements do not necessarily correspond between multiple drawings.

[0009] (1) Configuration of the processing unit As shown in Figure 1, the processing furnace 202 of the apparatus has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas with heat.

[0010] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with the upper and lower ends open. The upper end portion of the manifold 209 engages with the lower end portion of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a as a seal member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically like the heater 207. Mainly, the reaction tube 203 and the manifold 209 constitute a first processing container (first reaction container). A processing chamber 201 is formed in the cylindrical hollow portion of the first processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed in this processing chamber 201.

[0011] In the processing chamber 201, nozzles 249a to 249c as the first to third supply parts are respectively provided so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also respectively referred to as the first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0012] Gas supply pipes 232a to 232c are equipped with mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, respectively, in order from the upstream side of the gas flow. Downstream of valve 243a in gas supply pipe 232a, gas supply pipes 232d and 232f are connected, respectively. Downstream of valve 243b in gas supply pipe 232b, gas supply pipes 232e and 232g are connected, respectively. Downstream of valve 243c in gas supply pipe 232c, gas supply pipe 232h is connected. Gas supply pipes 232d to 232h are equipped with MFCs 241d to 241h and valves 243d to 243h, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232a to 232h are made of a metal material such as SUS.

[0013] As shown in FIG. 2, the nozzles 249a to 249c are each provided in an annular space between the inner wall of the reaction tube 203 and the wafer 200, along the upper part from the lower part of the inner wall of the reaction tube 203, rising upward in the arrangement direction of the wafer 200 in a plan view. That is, the nozzles 249a to 249c are each provided in a region on the side of the wafer arrangement region where the wafers 200 are arranged, surrounding the wafer arrangement region horizontally, along the wafer arrangement region. In a plan view, the nozzle 249b is arranged to face the exhaust port 231a (to be described later) in a straight line across the center of the wafer 200 in the processing chamber 201. The nozzles 249a and 249c are arranged so as to sandwich the straight line L passing through the centers of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer peripheral portion 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. That is, it can also be said that the nozzle 249c is provided on the opposite side of the nozzle 249a across the straight line L. The nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250c 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 open so as to face (opposite) the exhaust port 231a in a plan view, and it is possible to supply 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.

[0014] From the gas supply pipe 232a, a fluorine (F)-containing substance is supplied into the processing chamber 201 through the MFC241a, the valve 243a, and the nozzle 249a. The F-containing substance is used as one of the etching agents as the first treatment agent.

[0015] From the gas supply pipe 232b, a raw material is supplied into the processing chamber 201 through the MFC241b, the valve 243b, and the nozzle 249b. The raw material is used as one of the film-forming agents as the second treatment agent. The raw material is also used as one of the precoat agents.

[0016] From the gas supply pipe 232c, the catalyst is supplied into the processing chamber 201 via the MFC 241c, valve 243c, and nozzle 249c. The catalyst is used as one of the precoat agents.

[0017] From the gas supply pipe 232d, substance X is supplied into the processing chamber 201 via the MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a. Substance X is used as one of the precoat agents.

[0018] From the gas supply pipe 232e, the reducing agent is supplied into the processing chamber 201 via the MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0019] Inert gas is supplied from gas supply pipes 232f to 232h into the processing chamber 201 via MFCs 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0020] The F-containing substance supply system is mainly composed of gas supply pipe 232a, MFC 241a, and valve 243a. The raw material supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b. The catalyst supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. The substance X supply system is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d. The reducing agent supply system is mainly composed of gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system is mainly composed of gas supply pipes 232f to 232h, MFC 241f to 241h, and valves 243f to 243h. The F-containing substance supply system is also called the first treatment agent supply system (etching agent supply system). The raw material supply system is also called the second treatment agent supply system (film-forming agent supply system). The raw material supply system, catalyst supply system, and substance X supply system, in part or in whole, are also called the precoat agent supply system. The inert gas supply system is also called the purge gas supply system.

[0021] Of the various supply systems described above, one or all of them may be configured as an integrated supply system 248, which is comprised of valves 243a to 243h and MFCs 241a to 241h. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232h, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232h, i.e., the opening and closing operation of valves 243a to 243h and the flow rate adjustment operation of MFCs 241a to 241h, is controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or segmented integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232h, etc., in units of the integrated unit, and is configured so that maintenance, replacement, and expansion of the integrated supply system 248 can be performed in units of the integrated unit.

[0022] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, the exhaust port 231a is located in a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between, in a plan view. The exhaust port 231a may also be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation in the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure in the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed outside the reaction tube 203 as a lifting mechanism. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0024] Below the manifold 209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as lifting and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0025] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0026] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121. The processing unit may be configured to have one control unit or multiple control units. That is, the control for performing the processing sequence described later may be performed using one control unit or using multiple control units. Furthermore, the multiple control units may be configured as a control system connected to each other by a wired or wireless communication network, and the control for performing the processing sequence described later may be performed by the entire control system. In this specification, the term "control unit" may refer to a single control unit, a plurality of control units, or a control system composed of a plurality of control units.

[0028] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the processing device, and process recipes that describe the procedures and conditions for the substrate processing described later. The process recipe functions as a program, combining the procedures in the substrate processing described later so that the controller 121 causes the processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs" (program products). Similarly, process recipes will be simply referred to as "recipes." In this specification, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0029] I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotary mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0030] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241h, the opening and closing operation of valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0031] The controller 121 can be configured by installing the above-mentioned program, which is recorded and stored in the external storage device 123, onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, and semiconductor memory such as USB memory and SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Processing steps Using the above-described processing apparatus, an example of a processing sequence in which a substrate is processed as one step in the manufacturing process (manufacturing method) of a semiconductor device, namely, a process of etching the surface of a wafer 200 as a substrate and a process of growing a film on the wafer 200 after etching, will be explained mainly using Figures 4(a) to 4(e). In the following explanation, the operation of each part constituting the processing apparatus is controlled by the controller 121. The processing apparatus will also be referred to as a substrate processing apparatus, etching processing apparatus, etching apparatus, film deposition processing apparatus, or film deposition apparatus, depending on the processing content. Similarly, the processing method will also be referred to as a substrate processing method, etching processing method, etching method, film deposition processing method, or film deposition method, depending on the processing content.

[0033] In the processing sequence of this embodiment, (a) Step A, which involves preparing a first processing container in which a layer containing substance X is formed inside, (b) Step B, in which a wafer 200 as a substrate is brought into a first processing container on which a layer containing substance X has been formed, (c) Step C, in which a first processing agent is supplied to a wafer 200 in a first processing container on which a layer containing substance X is formed, and reacts with substance X derived from the layer containing substance X to etch the surface of the wafer 200, To do so.

[0034] In the following example, we will describe the case in which a substance X-containing layer is formed on the inner wall of the first processing container in step A. In addition, in the following example, we will describe the case in which a substance X-containing layer is formed inside the first processing container in step A without loading the wafer 200 into the first processing container.

[0035] Also, in the following example, after performing step C, (d) The case in which step D is further performed by supplying a second processing agent to the wafer 200 whose surface has been etched will be described.

[0036] Furthermore, the following example describes a case in which, in step D, a film-forming agent is supplied as a second treatment agent to the surface-etched wafer 200 to form a film on the surface-etched wafer 200.

[0037] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and layers or films formed on its surface. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or to the surface of a film or other film formed on the wafer. In this specification, when it is stated that "a film is formed on the surface of the wafer," it may mean that a film is formed directly on the surface of the wafer itself or that a film is formed on a film or other film already formed on the wafer. In this specification, the term "substrate" has the same meaning as when it is used with the term "wafer."

[0038] In this specification, the terms "agent" and "substance" include at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, each of the etching agent (F-containing substance), film-forming agent (raw material, dopant agent), reducing agent, and precoat agent (raw material, catalyst, substance X) may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0039] (Step A) First, with no boat 217, i.e., wafer 200, loaded into the processing chamber 201, the shutter 219s is moved by the shutter opening / closing mechanism 115s, closing the lower end opening of the manifold 209. In this state, the shutter 219s seals the lower end of the manifold 209 via the O-ring 220c (shutter closed).

[0040] Subsequently, the processing chamber 201 is evacuated (reduced pressure exhausted) by the vacuum pump 246 to achieve the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The processing chamber 201 is also heated by the heater 207 to achieve the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 to ensure a desired temperature distribution inside the processing chamber 201. Furthermore, both the exhaust and heating of the processing chamber 201 are continued at least until the processing inside the processing chamber 201 is completed.

[0041] Next, perform the following steps A1 and A2.

[0042] [Step A1] In step A1, raw materials and catalysts are supplied as precoating agents into processing room 201, which has not yet received the wafer 200.

[0043] Specifically, valves 243b and 243c are opened, and the raw materials and catalyst are supplied into the gas supply pipes 232b and 232c, respectively. The flow rates of the raw materials and catalyst are adjusted by MFCs 241b and 241c, respectively, and supplied into the processing chamber 201 via nozzles 249b and 249c. They are mixed in the processing chamber 201 and exhausted from the exhaust port 231a. At this time, the surface of the inner wall of the processing chamber 201, i.e., the first processing container, is exposed to the raw materials and catalyst (raw material + catalyst supply, exposure). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0044] After supplying the raw materials and catalyst into the processing chamber 201 for a predetermined time, valves 243b and 243c are closed to stop the supply of raw materials and catalyst into the processing chamber 201, respectively. Then, the processing chamber 201 is evacuated to remove any remaining gaseous substances. At this time, valves 243f to 243h are opened, and inert gas is supplied into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201.

[0045] [Step A2] In step A2, substance X and catalyst are supplied as a precoat agent to processing room 201, which has not yet received the wafer 200.

[0046] Specifically, valves 243d and 243c are opened, and substance X and catalyst are introduced into gas supply pipes 232d and 232c, respectively. The flow rates of substance X and catalyst are adjusted by MFCs 241d and 241c, respectively, and supplied into the processing chamber 201 via nozzles 249a and 249c. They are mixed in the processing chamber 201 and exhausted from exhaust port 231a. At this time, the inside of the processing chamber 201, i.e., the surface of the inner wall of the first processing container, is exposed to substance X and catalyst (supply of substance X + catalyst, exposure). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0047] After supplying substance X and catalyst into the processing chamber 201 for a predetermined time, valves 243d and 243c are closed to stop the supply of substance X and catalyst into the processing chamber 201, respectively. Then, using the same processing procedure and conditions as in step A1, any remaining gaseous substances, etc., in the processing chamber 201 are removed (purged).

[0048] [Perform the prescribed number of times] Then, the cycle including steps A1 and A2 is performed a predetermined number of times (m times, where m is 1 or an integer of 2 or more). As a result, as shown in Figure 4(a), a material X-containing layer (precoat layer) of the desired thickness is formed inside the processing chamber 201, that is, on the inner wall of the first processing vessel. When materials described later are used as the raw material, material X, and catalyst, a layer containing elements (Si) contained in the raw material and material X (H2O) is formed as the material X-containing layer, that is, a silicon oxide layer (SiO layer) containing water (H2O) as material X.

[0049] Furthermore, the substance X contained in the substance X-containing layer formed on the inner wall of the first processing container is released into the processing chamber 201 in step C, which will be described later. As will be described later, the substance X released into the processing chamber 201 reacts with the first processing agent (etching agent) supplied into the processing chamber 201 in step C, producing predetermined reaction products (etching species), thereby promoting the etching reaction on the surface of the substrate. In other words, the substance X released from the substance X-containing layer functions as a reaction accelerator that promotes the progress of the etching reaction carried out in step C.

[0050] The processing conditions when supplying the raw materials and catalyst in step A1 are as follows: Processing temperature: Room temperature (25°C) to 200°C, preferably room temperature to 150°C Processing pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa Processing time: 1 to 180 seconds, preferably 10 to 120 seconds Raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Catalyst supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0-10 slm, preferably 0.1-5 slm Examples are given.

[0051] In this specification, numerical ranges such as "25~200°C" mean that the lower and upper limits are included within that range. For example, "25~200°C" means "25°C or more and 200°C or less." The same applies to other numerical ranges. In this specification, processing temperature means the surface temperature of the object to be processed (in step A, the inside of the processing chamber 201, i.e., the surface temperature of the inner wall of the first processing container; in steps C and D, the surface temperature of the wafer 200 brought into the processing chamber 201). In this specification, processing pressure means the pressure inside the processing chamber 201. Processing time means the time during which the processing is continued. When 0 slm is included in the supply flow rate, 0 slm means the case in which the substance (gas) is not supplied. These also apply in the following explanations.

[0052] The processing conditions when supplying substance X and catalyst in step A2 are as follows: Processing temperature: Room temperature (25°C) to 200°C, preferably room temperature to 150°C Processing pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa Processing time: 1 to 180 seconds, preferably 10 to 120 seconds Supply flow rate of substance X: 0.01 to 20 slm, preferably 0.01 to 10 slm Catalyst supply flow rate: 0.01 to 20 slm, preferably 0.01 to 10 slm Inert gas supply flow rate (per gas supply pipe): 0-10 slm, preferably 0.1-5 slm Examples are given.

[0053] The amount of substance X included in the substance X-containing layer, that is, the content, concentration, density, and thickness of substance X in the substance X-containing layer (hereinafter collectively referred to simply as the content, etc., of substance X), can be controlled by adjusting the processing conditions described above. It is preferable that the content, etc., of substance X in the substance X-containing layer be such that almost all of it is consumed (released into the processing chamber 201) by carrying out step C, which is performed afterward. This suppresses the release of substance X from the substance X-containing layer in step D, which is performed after step C, and makes it possible to avoid the influence of substance X on the processing of the substrate carried out in step D. If substance X is still released from the substance X-containing layer after step C is completed, for example, after carrying out step C and before carrying out step D, a process to remove and deplete substance X from the substance X-containing layer (if substance X is water, this process is also called a water depletion process) may be carried out by raising the temperature in the processing chamber 201. The processing temperature in this step is preferably higher than the processing temperature in steps A and C, and more preferably at or above the processing temperature in step D.

[0054] As raw materials, for example, silicon (Si)-containing substances can be used. As raw materials, for example, chlorosilanes such as monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), and hexachlorodisilane (Si2Cl6) can be used. In addition, as raw materials, for example, monosilane (SiH4), disilane (Si2H6), trisilane (Si3H8), and tetrasilane (Si4H 10 Silicon hydride such as ) can be used. One or more of these can be used as raw materials.

[0055] For example, substance X can be a hydrogen (H) and oxygen (O)-containing substance such as water (H2O) or hydrogen peroxide (H2O2).

[0056] As catalysts, for example, substances containing carbon (C), nitrogen (N), and hydrogen can be used. As catalysts, for example, chain-like amines such as triethylamine ((C2H5)3N), diethylamine ((C2H5)2NH), monoethylamine ((C2H5)NH2), trimethylamine ((CH3)3N), dimethylamine ((CH3)2NH), and monomethylamine ((CH3)NH2) can be used. In addition, as catalysts, for example, aminopyridine (C5H6N2), pyridine (C5H5N), picoline (C6H7N), lutidine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), and piperazine (C4H 10 N2), piperidine (C5H 11 Cyclic amines such as N, aniline (C6H7N), etc. can be used. One or more of these can be used as catalysts.

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

[0058] After the formation of the substance X-containing layer inside the processing chamber 201, that is, on the inner wall of the first processing vessel, and after the preparation of the first processing vessel with the substance X-containing layer formed inside is complete, inert gas as a purge gas is supplied into the processing chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purge). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0059] (Step B) Subsequently, or in parallel with the execution of step A described above, multiple wafers 200 are loaded (wafer charged) into the boat 217. It is preferable that at least a portion of the wafer charging is performed in parallel with the execution of step A and completed before step A is finished.

[0060] Oxides may be formed on the surface of wafer 200. These oxides are silicon oxide films (SiO2) with a non-stoichiometric composition. x The film may contain at least one of the following: a film (where x is a real number less than 2) and a silicon oxide film (SiO2 film) of stoichiometric composition. Furthermore, the oxide may contain at least one of the following: a native oxide film and a chemical oxide film. x The film and SiO2 film will collectively be referred to as SiO film below.

[0061] After wafer charging is complete, the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the manifold 209 (shutter open). Then, as shown in Figure 1, the boat 217 supporting the wafer 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loaded). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0062] Upon completion of the boatloading, as shown in Figure 4(b), the wafer 200, which serves as the substrate, is loaded (placed) into the first processing container on which the substance X-containing layer has been formed. The substance X-containing layer is positioned at a location away from the wafer 200, but adjacent to the wafer 200.

[0063] (Pressure adjustment and temperature adjustment) After the boat loading is complete, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by the vacuum pump 246 to the desired pressure (vacuum level). The wafer 200 in the processing chamber 201 is also heated by the heater 207 to the desired processing temperature. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0064] (Step C) Subsequently, an etching agent is supplied to the wafer 200 in the processing chamber 201 as the first processing agent.

[0065] Specifically, valve 243a is opened and the etching agent is flowed into the gas supply pipe 232a. The etching agent's flow rate is adjusted by MFC 241a and supplied into the processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, as shown in Figure 4(c), the etching agent is supplied to the wafer 200 as a substrate from the side of the wafer 200, and the wafer 200 is exposed to the etching agent as the first processing agent (etching agent supply, exposure). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0066] By supplying an etching agent to the wafer 200 under the processing conditions described later, the etching agent reacts with substance X derived from the substance X-containing layer, thereby etching the surface of the wafer 200 as shown in Figure 4(d).

[0067] For example, when the oxide on the surface of the wafer 200 contains silicon oxide (SiO2), the substance X-containing layer pre-formed inside the processing chamber 201 contains water (H2O) as the substance X, and the etching agent as the first processing agent supplied into the processing chamber 201 contains hydrogen fluoride (HF) as the F-containing substance, under the conditions described below, the reaction shown in the following formula can proceed. That is, using the etching species (HF2 - etc.) obtained by the reaction of the substance X (H2O) and the etching agent (HF), it becomes possible to etch and remove the oxide (SiO2) formed on the surface of the wafer 200.

[0068] 2HF + H2O → HF2 - + H3O + SiO2 + 2HF2 - + 2H3O + → SiF4 + 4H2O

[0069] As described above, according to the present disclosure, the etching of the oxide (SiO2) on the surface of the wafer 200 can be initiated by triggering the reaction between the etching agent (HF) as the first processing agent supplied into the processing chamber 201 and the trace amount of the substance X (H2O) derived from the substance X-containing layer pre-formed inside the processing chamber 201. When the etching of the oxide is initiated, the trace amount of the substance X (H2O) previously contained in the substance X-containing layer formed inside the processing chamber 201 is consumed. FIG. 4(d) schematically shows a state in which the surface of the wafer 200 as a substrate is etched and most of the substance X contained in the substance X-containing layer is consumed (released) by performing step C.

[0070] However, in the reaction system in step C, water (H2O) is generated by the etching of the oxide. Therefore, in step C, it is possible to etch the oxide on the surface of the wafer 200 by repeatedly carrying out the above reaction in a chain reaction without supplying additional substance X into the processing chamber 201. Note that if additional substance X is supplied into the processing chamber 201 in step C, the amount of substance X in this reaction system will become excessive, which may actually hinder the progress of the etching reaction.

[0071] Furthermore, substance X is released in a substantially uniform amount across the entire arrangement direction of the substrates within the processing chamber 201. Therefore, the etching reaction-promoting effect of substance X is obtained uniformly among multiple substrates within the processing chamber 201, thereby improving the uniformity of the etching amount across the substrates on the substrate surface.

[0072] After etching the surface of the wafer 200, valve 243a is closed to stop the supply of etching agent into the processing chamber 201. Then, using the same processing procedure and conditions as in step A1, any remaining gaseous substances in the processing chamber 201 are removed (purged).

[0073] The processing conditions when supplying the etching agent in step C are as follows: Processing temperature: Room temperature (25°C) to 170°C, preferably 25 to 150°C Processing pressure: 10-4000, preferably 500-2000 Pa Processing time: 1 to 120 minutes, preferably 10 to 100 minutes Etching agent supply flow rate: 0.5 to 3 slm, preferably 1 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0-10 slm, preferably 1-5 slm Examples are given.

[0074] Here, if the processing temperature when supplying the etching agent in step C is set below room temperature (25°C), the etching rate can be increased. However, if other processing such as film deposition is performed at least before or after the etching process, the time required to change the processing temperature between the etching process and the other processing (heating-up time and / or cooling-down time) may become too long, which can reduce productivity.

[0075] By setting the processing temperature to room temperature (25°C) or higher, it is possible to maintain a high etching rate while shortening the time required to change processing temperatures between processes, thereby suppressing a decrease in productivity.

[0076] Furthermore, while setting the processing temperature above 170°C can significantly reduce the time required to change processing temperatures between different processes, it can also lead to an excessively low etching rate, resulting in reduced productivity.

[0077] By setting the processing temperature to 170°C or lower, it is possible to suppress the decrease in etching rate while maintaining a significant reduction in the time required to change processing temperatures between processes, thereby suppressing the decrease in productivity. By setting the processing temperature to 150°C or lower, it is possible to further suppress the decrease in etching rate while maintaining a significant reduction in the time required to change processing temperatures between processes, thereby suppressing the decrease in productivity. By setting the processing temperature to 130°C or lower, it is possible to significantly suppress the decrease in etching rate while maintaining a significant reduction in the time required to change processing temperatures between processes, thereby suppressing the decrease in productivity.

[0078] Based on the above, it is desirable that the processing temperature described above be between room temperature (25°C) and 170°C, preferably between 25°C and 150°C, and more preferably between 25°C and 130°C.

[0079] As described above, an F-containing substance can be used as the first treatment agent (etching agent), for example, an F and H-containing substance such as HF can be used. Alternatively, for example, as the first treatment agent, an F-containing substance such as fluorine (F2), nitrogen trifluoride (NF3), chlorine trifluoride (ClF3), chlorine fluoride (ClF), an F and N-containing substance, or an F and Cl-containing substance can be used. One or more of these can be used as the first treatment agent.

[0080] (Step D) Subsequently, a raw material, which is a film-forming agent, is supplied to the wafer 200 whose surface has been etched. At this time, a reducing agent is also supplied along with the raw material.

[0081] Specifically, valves 243b and 243e are opened, and the raw material and reducing agent are flowed into the gas supply pipes 232b and 232e, respectively. The flow rates of the raw material and reducing agent are adjusted by MFCs 241b and 241e, respectively, and supplied into the processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, as shown in Figure 4(e), the raw material as a second processing agent and the reducing agent are supplied to the wafer 200 from the side of the wafer 200, which serves as the substrate, and the wafer 200 is exposed to the raw material and reducing agent (raw material + reducing agent supply, exposure). At this time, valves 243f to 243h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0082] Under the processing conditions described later, by supplying raw materials and a reducing agent to the wafer 200, a film of a desired thickness can be formed on the surface of the etched wafer 200. For example, if the surface of the wafer 200 exposed by the etching process is composed of single-crystal Si, and the raw materials and reducing agents are the substances described later, it becomes possible to grow and form an epitaxial Si film as a film on the surface of the wafer 200. At this time, the action of the reducing agent keeps the surface of the wafer 200 and the inside of the processing chamber 201 clean, allowing for proper epitaxial growth and the formation of a high-purity epitaxial Si film.

[0083] After forming a film of the desired thickness on the surface of the wafer 200, valves 243b and 243e are closed to stop the supply of raw materials and reducing agent into the processing chamber 201. Then, the processing chamber 201 is purged using the same processing procedure and conditions as in step A1.

[0084] The processing conditions when supplying the raw materials and reducing agent in step D are as follows: Processing temperature: 500-650°C, preferably 550-600°C Processing pressure: 4-200 Pa, preferably 1-120 Pa Processing time: 10-120 minutes, preferably 20-60 minutes Raw material supply flow rate: 0.1 to 5 slm, preferably 0.2 to 3 slm Reducing agent supply flow rate: 1 to 20 slm, preferably 1 to 10 slm Inert gas supply flow rate (per gas supply pipe): 0-10 slm, preferably 0.1-5 slm Examples are given.

[0085] Examples of the second treatment agent (raw material) include SiH4, Si2H6, Si3H8, and Si4H 10 Silicon hydride such as the above can be used. Furthermore, chlorosilanes such as SiH3Cl, SiH2Cl2, SiHCl3, SiCl4, and Si2Cl6 can be used as raw materials. One or more of these can be used as raw materials.

[0086] As reducing agents, for example, hydrogen-containing substances such as hydrogen (H2) and deuterium (D2), or deuterium-containing substances can be used. One or more of these can be used as reducing agents.

[0087] (After-purge and return to atmospheric pressure) After step D is completed, inert gas is supplied as a purge gas into the processing chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purge). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0088] (Boat unloading) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutters 219s are moved, and the lower end opening of the manifold 209 is sealed by the shutters 219s via the O-ring 220c (shutter close). After boat unloading, the processed wafer 200 is removed from the boat 217 (wafer discharge).

[0089] The processing step in one aspect of this disclosure is thus completed.

[0090] Furthermore, as in this embodiment, steps C and D can be performed in the same processing container (in situ). Performing the series of processes in situ ensures that the wafer 200 is not exposed to the atmosphere during the process, and allows for consistent and stable processing while the wafer 200 remains under vacuum.

[0091] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0092] (a) Step A is to prepare a first processing container in which a layer containing substance X is formed inside; Step B is to bring a substrate into the first processing container in which the layer containing substance X is formed; and Step C is to supply a first processing agent to the substrate in the first processing container in which the layer containing substance X is formed, and etch the surface of the substrate by reacting it with substance X derived from the layer containing substance X. That is, in Step C, when etching the surface of the substrate, the first processing agent supplied in Step C is reacted with substance X derived from the layer containing substance X that was formed in the first processing container before Step B. This makes it possible to react the first processing agent with a small amount of substance X in Step C, thereby promoting the etching reaction. As a result, it becomes possible to etch the surface of the substrate efficiently.

[0093] Furthermore, step B allows the material X-containing layer to be positioned at a location away from the substrate but adjacent to it. By performing step C in this state, material X is released in a substantially uniform amount across the entire arrangement direction of the substrates in the first processing container, thereby improving the uniformity of the etching process, particularly the uniformity between substrates.

[0094] Furthermore, the etching temperature in step C can be increased, and if other processes such as film deposition are performed at least before or after the etching process, the etching temperature can be brought closer to the temperature of the other process. This reduces the time required to change the processing temperature between the etching process and other processes, i.e., at least one of the heating time and cooling time, thereby increasing productivity.

[0095] (b) In step A, a layer containing substance X is formed on the inner wall of the first processing vessel. This makes it possible to effectively position the layer containing substance X in step B at a position that is evenly separated from each substrate and evenly adjacent to each substrate. As a result, it is possible to further improve the uniformity of the etching process performed in step C, in particular the uniformity of the etching process between substrates.

[0096] (c) In step A, a substance X-containing layer is formed inside the first processing container before the substrate is loaded into the first processing container. This makes it possible to form the substance X-containing layer in step A at a specific location inside the first processing container, for example, on the inner wall of the first processing container, without forming it on the substrate. In other words, in step A, it is possible to avoid forming the substance X-containing layer on the entire surface of the substrate (front, back, and sides) or on any of the components present in the space inside the first processing container.

[0097] This allows for an effective reaction between the first treatment agent and a trace amount of substance X in step C, thereby effectively promoting the etching reaction. As a result, etching of the substrate surface becomes more efficient.

[0098] Furthermore, the amount of substance X remaining in the first processing container after etching (hereinafter referred to as residual substance X) can be minimized, and the impact of residual substance X on the substrate after etching can be suppressed.

[0099] (d) In step A, raw materials, substance X, and a catalyst are supplied into the first processing vessel, and a layer containing the elements contained in the raw materials and substance X is formed as a substance X-containing layer. This makes it possible to efficiently prepare the first processing vessel in which the substance X-containing layer is formed inside.

[0100] (e) Substance X contains H and O-containing substances such as H2O. This makes it possible to effectively obtain the effects described above.

[0101] (f) The first treatment agent contains F-containing substances such as F and H-containing substances. This makes it possible to effectively obtain the effects described above.

[0102] (g) In step C, oxides including at least one of the native oxide film and the chemical oxide film formed on the surface of the substrate are removed. This makes it possible to effectively obtain the effects described above.

[0103] (h) In step D, the substrate is treated by supplying a second treatment agent to the substrate whose surface has been etched and cleaned. This makes it possible to treat the substrate efficiently.

[0104] (i) In step D, a raw material that is a film-forming agent is supplied as a second treatment agent to the substrate whose surface has been etched, and a film is formed on the substrate whose surface has been etched. This makes it possible to reduce the concentration of impurities (oxygen concentration, etc.) at the interface between the substrate and the film.

[0105] (j) The effects described above can also be obtained when a predetermined substance is arbitrarily selected from the various precoating agents (raw materials, substance X, catalyst), various first treatment agents (etching agents), various second treatment agents (raw materials), various reducing agents, and various inert gases described above.

[0106] <Second aspect of this disclosure> Next, a second aspect of this disclosure will be described mainly with reference to Figures 5(a) to 5(d) and Figure 6. This aspect differs from the first aspect described above in that steps C and D are performed in different processing vessels (ex-situ). In this aspect, step C is performed in the first processing vessel, and step D is performed in the second processing vessel. Except for this point, the processing procedures and conditions in steps A to D of this aspect are the same as those in steps A to D of the first aspect. In this aspect, the second processing vessel can be supplied with a film-forming agent, a reducing agent, and an inert gas from a film-forming agent supply system, a reducing agent supply system, and an inert gas supply system, respectively. The configuration of the second processing vessel other than the supply systems is the same as that of the first processing vessel.

[0107] First, as shown in Figure 5(a), step A is performed to prepare a first processing vessel in which a layer containing substance X, that is, a layer capable of releasing substance X as a reaction accelerator, is formed inside. In this embodiment, the first processing vessel and the second processing vessel are each in communication with a load lock chamber. The load lock chamber is configured as an airtight container capable of creating a vacuum atmosphere or a non-atmospheric atmosphere inside. A transport mechanism (boat changer, boat elevator, etc.) is provided inside the load lock chamber. The transport mechanism is configured to transport the first and second boats, which serve as substrate supports, into the first and second processing vessels under a vacuum atmosphere or a non-atmospheric atmosphere.

[0108] Subsequently, as shown in Figure 5(b), step B is performed, and a substrate supported by a first boat and with oxide formed on its surface is brought into a first processing container where a layer containing substance X has been formed. Then, step C is performed, and a first processing agent is supplied to the substrate in the first processing container where the layer containing substance X has been formed, reacting with substance X derived from the substance X-containing layer to etch the surface of the substrate and remove the oxide formed on the surface of the substrate.

[0109] Subsequently, as shown in Figure 5(c), the first boat supporting the etched substrate is moved from the first processing container into the load lock chamber.

[0110] Subsequently, a boat changer is used to change the positions of the first boat supporting the substrate with the etched surface and the second boat supporting the substrate with oxide formed on its surface. As shown in Figure 5(d), the first boat supporting the substrate with the etched surface is transported into the second processing container under a vacuum or airless atmosphere. Then, with the substrate with the etched surface inside the second processing container, step D is performed, and a film-forming agent is supplied to the substrate with the etched surface as the second processing agent, forming a film on the substrate with the etched surface. In parallel, steps A to C described above are performed again. That is, a first processing container with a layer containing substance X formed inside is prepared. Then, the substrate supported by the second boat and with oxide formed on its surface is transported into the first processing container with the layer containing substance X. Then, the first processing agent is supplied to the substrate inside the first processing container with the layer containing substance X, reacting with substance X derived from the substance X-containing layer to etch the surface of the substrate and remove the oxide formed on the surface of the substrate.

[0111] In this embodiment, the same effects as those described above can be obtained.

[0112] Furthermore, according to this embodiment, step D is performed with the substrate whose surface has been etched already placed in the second processing container. By performing steps C and D ex-situ in this way, it is possible to prevent the introduction of substance X and the first processing agent into the second processing container, and also to prevent the introduction of the second processing agent into the first processing container. In other words, cross-contamination within each processing container can be prevented, and the quality of the processing performed in each processing container can be improved.

[0113] Furthermore, according to this embodiment, the substrate with the etched surface is transported from the first processing container to the second processing container under a vacuum atmosphere or a non-air atmosphere. This makes it possible to avoid exposure of the substrate to the air after step C, and to keep the surface of the etched and cleaned substrate clean until step D is performed, and to avoid oxidation of the surface.

[0114] In this embodiment, when steps A to D are performed multiple times, it is preferable to provide a period during which the nth step D is performed in parallel with at least one of the (n+1)th steps A to C. Figures 5(a) to 5(d) and 6 show a case where the implementation period of the nth step D using the second processing container and the total implementation period of the (n+1)th steps A to C using the first processing container partially overlap.

[0115] Such parallel processing can be achieved, for example, by preparing multiple boats (first and second boats) in the load lock chamber and transporting them using a boat exchange device (boat changer). As described above, when steps A to C are performed for the nth time, as shown in Figure 5(c), the first boat supporting the substrate with the etched surface is unloaded from the first processing container into the load lock chamber. Until or after the unloading of the first boat is complete, a new substrate (for example, a substrate with oxide on its surface) to be processed for the (n+1th) time is loaded into the second boat. After these processes are completed, the positions of the first and second boats are swapped using the boat changer, and the first boat is loaded into the second processing container. Then, as shown in Figure 5(d), the nth step D using the second processing container and at least one of the (n+1th) steps A to C using the first processing container are performed in parallel.

[0116] Based on the above, when steps A to D are performed multiple times, the total processing time can be reduced, thereby improving productivity.

[0117] <Third aspect of this disclosure> Next, a third aspect of this disclosure will be explained, mainly using Figures 7(a) to 7(c), 8(a), and 8(b).

[0118] When performing step C, a portion of the first processing container may be deficient in substance X. In this case, the substance X-containing layer corresponding to the deficient portion of substance X in the first processing container may be made thicker than the other portions. Alternatively, the content, concentration, and density of substance X in the substance X-containing layer corresponding to the deficient portion of substance X in the first processing container may be made greater (higher) than in the other portions. In other words, in step A, at least one of the following may be made different between a portion of the first processing container and another portion: the content of substance X in the substance X-containing layer, the concentration of substance X, the density of substance X, and the thickness.

[0119] For example, when performing step C, if there is a shortage of substance X in the upper part of the first processing container, the substance X-containing layer formed in the upper part of the first processing container may be made thicker than the substance X-containing layers formed in other parts (middle and lower parts), as shown in Figure 7(a). Alternatively, the content, concentration, and density of substance X in the substance X-containing layer formed in the upper part of the first processing container may be made greater (higher) than the content, concentration, and density of substance X in the substance X-containing layers formed in other parts.

[0120] For example, if there is a shortage of substance X in the middle of the first processing container when performing step C, the substance X-containing layer formed in the middle of the first processing container may be made thicker than the substance X-containing layers formed in other parts (upper and lower), as shown in Figure 7(b). Furthermore, the content, concentration, and density of substance X in the substance X-containing layer formed in the middle of the first processing container may be made greater (higher) than those in the substance X-containing layers formed in other parts.

[0121] Furthermore, for example, if there is a shortage of substance X in the lower part of the first processing container when performing step C, the substance X-containing layer formed in the lower part of the first processing container may be made thicker than the substance X-containing layers formed in other parts (upper and middle), as shown in Figure 7(c). Also, the content, concentration, and density of substance X in the substance X-containing layer formed in the lower part of the first processing container may be made greater (higher) than the content, concentration, and density of substance X in the substance X-containing layers formed in other parts.

[0122] In any case, the content of substance X, the concentration of substance X, the density of substance X, and the thickness of the substance X-containing layer may be varied in one or more locations within the first processing container. In any case, the content of substance X, the concentration of substance X, the density of substance X, and the thickness of the substance X-containing layer may be varied in stages (multi-stages) depending on the location within the first processing container. In any case, the thickness of the substance X-containing layer may be varied depending on the location within the first processing container, or it may be varied while the content of substance X, the concentration of substance X, and the density of substance X in the substance X-containing layer are varied depending on the location within the first processing container.

[0123] Furthermore, by using, for example, the processing furnace shown in Figure 8(a) or the processing furnace shown in Figure 8(b), the content of substance X in the substance X-containing layer can be made different in a part of the first processing vessel and in another part.

[0124] The processing furnace shown in Figure 8(a) is equipped with multiple nozzles (upper nozzle, middle nozzle, and lower nozzle) that correspond to the upper, middle, and lower parts of the first processing vessel, respectively. In step A, by individually controlling the flow rate, concentration, and type of precoat agent supplied from the upper nozzle, middle nozzle, and lower nozzle so that they differ from each other, it is possible to make at least one of the following different in the substance X-containing layer: the content of substance X, the concentration of substance X, the density of substance X, and the thickness of substance X, between a part of the first processing vessel and another part.

[0125] Furthermore, the processing furnace shown in Figure 8(b) is equipped with a multi-zone heater including an upper heater, a middle heater, and a lower heater, which are provided to correspond to the upper, middle, and lower parts of the first processing vessel, respectively. In step A, by individually controlling the heating conditions of the upper heater, middle heater, and lower heater to be different from each other, it is possible to make at least one of the following different in the substance X-containing layer: the content of substance X, the concentration of substance X, the density of substance X, and the thickness. Note that the multi-zone heater is not limited to including three zones, but may include four, five, or more zones.

[0126] In this embodiment, the same effects as those described above can be obtained.

[0127] Furthermore, according to this embodiment, in step C, the amount of etching on the substrate surface can be adjusted according to the position within the first processing container. This makes it possible to suppress variations in the amount of etching on the substrate surface depending on the position within the first processing container, i.e., between substrates.

[0128] <Other aspects of this disclosure> The aspects of this disclosure have been specifically described above. However, this disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0129] The substance X-containing layer can be any layer capable of releasing substance X, which acts as a reaction accelerator to promote the etching reaction, into the first processing vessel (supplying substance X into the processing vessel), and it is possible to use a layer other than the SiO layer containing water as substance X. For example, in step A, raw materials containing Si and carbon (C), such as bis(trimethylsilyl)methane, and a catalyst, along with H2O as substance X and a catalyst, may be supplied alternately into the first processing vessel. In this case, it is possible to form a layer containing elements (Si, C) contained in the raw materials and H2O as substance X, i.e., a silicon carbide layer (SiOC layer) containing water as substance X, as the substance X-containing layer in the first processing vessel. The same effects as in the above-described embodiment can be obtained in this embodiment as well.

[0130] For example, in step A, the raw material, substance X, and catalyst may be supplied alternately into the first processing container. Alternatively, in step A, the raw material, catalyst, and substance X may be supplied alternately into the first processing container. That is, in step A, the catalyst may be supplied into the first processing container together with at least one of the raw material and substance X. In this embodiment as well, it is possible to form a substance X-containing layer in the first processing container, which contains elements contained in the raw material and substance X, and the same effects as in the above embodiment can be obtained.

[0131] Alternatively, for example, in step A, the raw materials and substance X may be supplied into the first processing vessel without supplying a catalyst as a precoat agent. In this embodiment as well, it is possible to form a layer containing substance X as a substance X-containing layer in the first processing vessel, which contains elements contained in the raw materials and substance X, and the same effects as in the above embodiment can be obtained.

[0132] For example, in step A, substance X may be supplied into the first processing container as a precoat agent without supplying raw materials or catalysts. In this case, an adsorption layer of substance X can be formed in the first processing container as a substance X-containing layer. If substance X is H2O, the substance X-containing layer can also be a liquid film. Substance X may be H2O2, or a substance other than H2O or H2O2, and any H and O-containing substance can be used. After forming the adsorption layer of substance X, the thickness of the adsorption layer of substance X and the content of substance X in the adsorption layer can be adjusted by purging the inside of the first processing container. These adjustments can also be made by adjusting the processing conditions, including the exposure amount of substance X when forming the adsorption layer of substance X, and the processing conditions, including the exposure amount of purge gas when purging the inside of the first processing container. Furthermore, by changing the exposure amount of substance X and the exposure amount of purge gas according to the position within the first processing container, the thickness of the adsorption layer of substance X and the content of substance X in the adsorption layer of substance X can be varied and adjusted according to the position within the first processing container. These adjustments can be achieved, for example, by using the processing furnace shown in Figure 8(a). In this embodiment, the same effects as in the above-described embodiment can be obtained.

[0133] Alternatively, in step A, a layer capable of absorbing or adsorbing substance X may be formed in the first processing container, and then substance X may be supplied to the first processing container to form a layer containing substance X, which has absorbed or adsorbed substance X. For example, in step A, a hydrophilic layer having hygroscopic or water-absorbing properties may be formed in the first processing container, and then H2O may be supplied to the first processing container as substance X to form a layer in which moisture has been absorbed and / or adsorbed onto the hydrophilic layer. As the hydrophilic layer, an SiO layer or a layer formed by the above method, i.e., a moisture-containing SiO layer or SiOC layer, etc., can be used. When an SiO layer is used as the hydrophilic layer, by supplying H2O, a layer in which moisture has been newly absorbed and / or adsorbed onto the SiO layer can be formed as a substance X-containing layer. Furthermore, since the layer formed by the above method (a moisture-containing SiO layer or SiOC layer) contains moisture immediately after formation, when these layers are used as the hydrophilic layer, the layer can be modified in a way that increases the moisture content by supplying H2O. Furthermore, by changing the amount of H2O exposure, i.e., the amount and flow rate of H2O supply, according to the position within the first processing container, the content of substance X in the substance X-containing layer can be varied and adjusted according to the position within the first processing container. In this embodiment, the same effects as in the embodiment described above can be obtained.

[0134] Alternatively, for example, step A may be performed with an empty substrate holder, without a substrate loaded, placed into the first processing container. In this case, a layer containing substance X of the desired thickness is formed on the inner wall of the first processing container, the surface of the substrate holder, etc. The same effects as in the above-described embodiment can be obtained in this embodiment as well.

[0135] Furthermore, in step D, for example, a dopant agent may be supplied to the substrate as a film-forming agent in addition to the raw materials and reducing agent. The dopant agent can be supplied from the film-forming agent supply system described above. As the dopant agent, a substance containing any of the Group 15 elements such as phosphorus (P) and arsenic (As), and any of the Group 13 elements such as boron (B), can be used. Examples of dopant agents include phosphine (PH3), arsine (AsH3), diborane (B2H6), and trichloroborane (BCl3). One or more of these can be used as the dopant agent. In this embodiment, the same effects as in the above embodiment can be obtained. In addition, according to this embodiment, it is possible to form a dopant-doped film (P, As, B, etc.) on the substrate.

[0136] Furthermore, in step D, for example, a material containing semiconductor elements other than Si may be used to form a semiconductor element-containing film on the substrate. For example, a material containing germanium (Ge), such as monogermane (GeH4), may be used as a raw material to form a Ge-containing film on the substrate. Alternatively, for example, a Si-containing material and a Ge-containing material may be used as raw materials to form Si and Ge-containing films on the substrate. Alternatively, for example, a material containing metallic elements such as tungsten (W), molybdenum (Mo), aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), and tantalum (Ta) may be used as a raw material to form a metallic element-containing film on the substrate. In these cases as well, the same effects as those described above can be obtained.

[0137] Furthermore, in step D, for example, an amorphous film, a polycrystalline film, or a mixed crystalline film thereof may be formed on the substrate in addition to the epitaxial film. In these cases as well, the same effects as those described above can be obtained.

[0138] Furthermore, in step D, for example, instead of performing a process to form a film on the substrate, a process to modify the surface of the substrate to a predetermined surface may be performed, or a process to etch the surface of the substrate may be performed. In these cases as well, the same effects as in the embodiments described above can be obtained.

[0139] It is preferable that the recipes used for each process be prepared individually according to the content of the process, recorded and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes recorded and stored in the storage device 121c according to the content of the process. This allows the processing device to perform various processes with high reproducibility. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0140] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed on the processing unit. When modifying a recipe, the modified recipe may be installed on the processing unit via a telecommunications line or a recording medium on which the recipe is stored. Alternatively, existing recipes already installed on the processing unit may be directly modified by operating the input / output device 122 provided on the existing processing unit.

[0141] The above-described embodiments illustrate an example of processing using a batch-type processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above-described embodiments and can also be applied to processing using a single-wafer processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of processing using a processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can also be applied to processing using a processing apparatus having a cold-wall type processing furnace.

[0142] Even when using these processing devices, each process can be carried out using the same processing procedures and conditions as described above for the embodiments and modifications, and the same effects as described above for the embodiments and modifications can be obtained.

[0143] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications. [Explanation of symbols]

[0144] 200 wafers (substrates)

Claims

1. (a) A step of preparing a first processing container in which a layer containing substance X is formed inside, (b) A step of transporting a substrate into the first processing container on which the substance X-containing layer is formed, (c) A step of supplying a first processing agent to the substrate in the first processing container on which the substance X-containing layer is formed, and reacting it with the substance X derived from the substance X-containing layer to etch the surface of the substrate, A processing method having the following characteristics.

2. (a) The processing method according to claim 1, wherein the substance X-containing layer is formed on the inner wall of the first processing container.

3. (a) The processing method according to claim 1, wherein the substrate is not loaded into the first processing container, and the substance X-containing layer is formed in the first processing container.

4. (a) The processing method according to claim 1, wherein the substance X is supplied into the first processing container.

5. (a) The processing method according to claim 4, wherein an adsorption layer of substance X is formed as the substance X-containing layer.

6. (a) The processing method according to claim 1, wherein a raw material and substance X are supplied into the first processing container, or a raw material, substance X and catalyst are supplied into the first processing container.

7. (a) The processing method according to claim 6, wherein a layer containing the elements contained in the raw material and the substance X is formed as the substance X-containing layer.

8. (a) The processing method according to claim 1, wherein a layer capable of absorbing or adsorbing the substance X is formed in the first processing container, and then the substance X is supplied to the first processing container.

9. (a) The processing method according to claim 8, wherein a layer is formed in which the substance X has been absorbed or adsorbed as the substance X-containing layer.

10. (a) The processing method according to claim 1, wherein at least one of the content of substance X in the substance X-containing layer, the concentration of substance X, the density of substance X, and the thickness of substance X is different in a part of the first processing container and in another part.

11. The processing method according to claim 1, wherein the substance X comprises a hydrogen and oxygen-containing substance.

12. The treatment method according to claim 1, wherein the first treatment agent comprises a fluorine-containing substance.

13. The treatment method according to claim 1, wherein the first treatment agent comprises a fluorine and hydrogen-containing substance.

14. (c) The processing method according to claim 1, wherein an oxide formed on the surface of the substrate is removed.

15. The treatment method according to claim 14, wherein the oxide comprises at least one of a native oxide film and a chemical oxide film.

16. (d) The processing method according to any one of claims 1 to 15, further comprising the step of supplying a second processing agent to the substrate whose surface has been etched to process the substrate.

17. (d) The processing method according to claim 16, wherein a film-forming agent is supplied as the second processing agent to the substrate whose surface has been etched, and a film is formed on the substrate whose surface has been etched.

18. The processing method according to claim 16, wherein (d) is performed with the substrate whose surface has been etched being brought into the second processing container.

19. The processing method according to claim 18, further comprising the step of transporting the substrate whose surface has been etched from the first processing container to the second processing container in a non-air atmosphere.

20. The processing method according to claim 16, wherein steps (a) to (d) are performed multiple times, and there is a period during which the nth step (d) and at least one of the (n+1) steps (a), (b), and (c) are performed in parallel.

21. (a) A step of preparing a first processing container in which a layer containing substance X is formed inside, (b) A step of transporting a substrate into the first processing container on which the substance X-containing layer is formed, (c) A step of supplying a first processing agent to the substrate in the first processing container on which the substance X-containing layer is formed, and reacting it with the substance X derived from the substance X-containing layer to etch the surface of the substrate, A method for manufacturing a semiconductor device having [a certain feature].

22. The first processing container into which the substrates are brought, A first treatment agent supply system that supplies a first treatment agent to the substrate, A transport device for transporting the substrate into the first processing container, (a) A process of preparing the first processing container in which a layer containing substance X is formed inside, (b) A process of transporting a substrate into the first processing container on which the substance X-containing layer is formed, (c) A control unit configured to control the process of supplying a first processing agent to the substrate in the first processing container on which the substance X-containing layer is formed, and reacting it with the substance X derived from the substance X-containing layer to etch the surface of the substrate, A processing device.

23. (a) A procedure for preparing a first processing container in which a layer containing substance X is formed inside, (b) A procedure for transporting a substrate into the first processing container on which the substance X-containing layer is formed, (c) A procedure to supply a first processing agent to the substrate in the first processing container on which the substance X-containing layer is formed, and to react with the substance X derived from the substance X-containing layer to etch the surface of the substrate, A program that causes a computer to execute a command on a processing unit.

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