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

Abstract

The present invention includes a step for etching a surface of a substrate by performing, a predetermined number of times, (a) a step for supplying a substance M that is filled in a first storage part in a gas state to the substrate that is under a reduced pressure a predetermined number of times so as to have the substance M adsorbed on the substrate, (b) a step for performing at least either supply of a purge gas to the substrate or exhaust of a space in which the substrate is present so as to desorb some of the substance M while leaving some of the substance M adsorbed on the substrate, (c) a step for supplying an etching agent to the substrate so as to have the substance M adsorbed and left on the substrate react with the etching agent, thereby generating an etching species, and (d) a step for performing at least either purge or exhaust of the space.

Description

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

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

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

[0003] Japanese Patent Publication No. 2023-137735

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

[0005] According to one aspect of the present disclosure, a technique is provided for etching the surface of a substrate by performing the following steps a predetermined number of times: (a) supplying a substance M, which has been filled in a first storage unit in a gaseous state, to a substrate under reduced pressure a predetermined number of times to adsorb the substance M onto the substrate; (b) desorbing a portion of the substance M adsorbed onto the substrate while leaving a portion of it on the substrate by supplying a purge gas to the substrate and exhausting the space in which the substrate is located; (c) supplying an etching agent to the substrate to react the substance M adsorbed onto and left on the substrate with the etching agent to generate etching species; and (d) purging the space and exhausting the space.

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

[0007] Figure 1 is a schematic diagram of a vertical processing furnace of a processing apparatus preferably used in one embodiment of the present disclosure, showing the processing furnace 202 portion in a vertical cross-sectional view. Figure 2 is a schematic diagram of a vertical processing furnace of a processing apparatus preferably used in one embodiment of the present disclosure, showing the processing furnace 202 portion in a cross-sectional view along line A-A in Figure 1. Figure 3 is a schematic diagram of a controller 121 of a processing apparatus preferably used in one embodiment of the present disclosure, showing the control system of the controller 121 in a block diagram. This figure shows a processing sequence in one embodiment of the present disclosure. This figure shows a modified example of the processing sequence in one embodiment of the present disclosure. This figure shows a modified example of the processing sequence in one embodiment of the present disclosure. Figure 7(a) shows an example in step A in which the amount of substance M exposed to the substrates differs between a portion of a plurality of substrates and another portion. Figure 7(b) shows another example in step A in which the amount of substance M exposed to the substrates differs between a portion of a plurality of substrates and another portion. Figure 7(c) is a diagram showing another example in step A where the amount of substance M exposed to the substrate differs between a portion of multiple substrates and another portion. Figure 8(a) is a diagram showing an example in step B where the amount of purge gas exposed to the substrate differs between a portion of multiple substrates and another portion. Figure 8(b) is a diagram showing another example in step B where the amount of purge gas exposed to the substrate differs between a portion of multiple substrates and another portion. Figure 8(c) is a diagram showing another example in step B where the amount of purge gas exposed to the substrate differs between a portion of multiple substrates and another portion. Figure 9 is a schematic configuration diagram of a processing apparatus preferably used in other embodiments of the present disclosure. Figure 10 is a schematic configuration diagram of a processing apparatus preferably used in other embodiments of the present disclosure.

[0008] <An Embodiment of the Disclosure> An embodiment of the disclosure will be described below, mainly with reference to Figures 1 to 4. Note that the drawings used in the following description are 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) As shown in the configuration diagram of the processing apparatus in FIG. 1, the processing furnace 202 of the processing apparatus has a heater 207 as a temperature regulator (heating unit). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) 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 (SiO ２ ), or silicon carbide (SiC), etc., 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), etc., 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 vertically installed in the same way as the heater 207. Mainly, the reaction tube 203 and the manifold 209 constitute a processing container (reaction container). A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing on 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 units 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, etc. 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 pipe 232a is equipped with, in order from the upstream side of the gas flow, a mass flow controller (MFC) 241a, which is a flow control unit (flow control section), a valve 243a, which is an on / off valve, a tank 260a, which is a gas reservoir, and a valve 247a. Gas supply pipes 232b and 232c are equipped with MFCs 241b and 241c and valves 243b and 243c, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232d and 232f are connected downstream of valve 247a on gas supply pipe 232a, respectively. Gas supply pipes 232e and 232g are connected downstream of valve 243b on gas supply pipe 232b, respectively. Gas supply pipe 232h is connected downstream of valve 243c on gas supply pipe 232c. Gas supply pipes 232d, 232f-232h are provided with MFCs 241d, 241f-241h, valves 243d, 243f-243h, tanks 260d, 260f-260h, and valves 247d, 247f-247h, respectively, in order from the upstream side of the gas flow. Gas supply pipe 232e is provided with MFC 241e and valve 243e, in order from the upstream side of the gas flow. Tank 260d is also referred to as the first storage section, tanks 260f-260h are also referred to as the second storage section, and tank 260a is also referred to as the third storage section. Gas supply pipes 232a-232h are made of a metal material such as SUS.

[0013] As shown in FIG. 2, the nozzles 249a to 249c are provided in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the upper part from the lower 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 respectively provided in a region on the side of the wafer arrangement region where the wafers 200 are arranged, in a region horizontally surrounding the wafer arrangement region, along the wafer arrangement region. In a plan view, the nozzle 249b is arranged so as to face the exhaust port 231a 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 the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are each opened 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. The nozzles 249a to 249c are also referred to as long nozzles and porous nozzles.

[0014] From the gas supply pipe 232a, a fluorine (F)-containing substance is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, the tank 260a, the valve 247a, and the nozzle 249a. The F-containing substance is used as one of the etching agents.

[0015] From the gas supply pipe 232b, a raw material is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b. The raw material is used as one of the film forming agents.

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

[0017] From the gas supply pipe 232d, substance M is supplied into the processing chamber 201 via the MFC 241d, valve 243d, tank 260d, valve 247d, gas supply pipe 232a, and nozzle 249a.

[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, tanks 260f to 260h, valves 247f to 247h, 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, valve 243a, and valve 247a. Tank 260a may also be included in the F-containing substance supply system. The raw material supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b. The dopant agent supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. The substance M supply system is mainly composed of gas supply pipe 232d, MFC 241d, valve 243d, tank 260d, and valve 247d. The reducing agent supply system is mainly composed of gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system mainly consists of gas supply pipes 232f to 232h, MFCs 241f to 241h, valves 243f to 243h, and valves 247f to 247h. Tanks 260f to 260h may also be included in the inert gas supply system. The F-containing substance supply system is also called the etching agent supply system. Parts or all of the raw material supply system and the dopant agent supply system are also called the film-forming agent supply system. The inert gas supply system is also called the purge gas supply system.

[0021] Of the various supply systems described above, any or all of them may be configured as an integrated supply system 248, which includes valves 243a to 243h, 247a, 247d, 247f to 247h, MFCs 241a to 241h, tanks 260a, 260d, 260f to 260h, etc. 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 and the tanks 260a, 260d, 260f to 260h, that is, the opening and closing operation of valves 243a to 243h, 247a, 247d, 247f to 247h and the flow rate adjustment operation by MFCs 241a to 241h, etc., 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 gas supply pipes 232a to 232h, etc., on an integrated unit basis. This configuration allows for maintenance, replacement, and expansion of the integrated supply system 248 to be performed on an integrated unit basis.

[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 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 exhaust 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 from 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 inside 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 hermetically 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, acting as a support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position, aligned vertically with their centers aligned, and arranged in multiple layers, that is, with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of 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 entire control system may perform the control necessary to carry out the processing sequence described later. 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] The I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, 247a, 247d, 247f to 247h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating 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, 247a, 247d, 247f to 247h, 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 rotation 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, into 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, when the term recording media is used, it 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 processing apparatus described above, an example of a processing sequence in which a substrate is processed as one step in the manufacturing process of a semiconductor device, that is, a processing sequence for etching the surface of the wafer 200 as a substrate and a processing sequence for growing a film on the wafer 200 after etching, are performed in succession, will be mainly explained with reference to Figure 4. 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, and the processing method will also be referred to as a substrate processing method.

[0033] In the processing sequence of this embodiment, (a) a substance M filled in a gaseous state in a tank 260d as a first storage unit is supplied to a wafer 200 under reduced pressure a predetermined number of times (m １ times, m １ Step A involves adsorbing substance M onto the wafer 200 by performing (b) a purge gas to the wafer 200 and / or exhausting the space in which the wafer 200 is located, thereby desorbing a portion of the substance M adsorbed onto the wafer 200 while leaving some of it behind, by performing (c) an etching agent to the wafer 200, causing the substance M adsorbed onto and left behind on the wafer 200 to react with the etching agent to generate etching species, and (d) a purging and / or exhausting the space in which the wafer 200 is located, by performing these steps a predetermined number of times (n times, where n is an integer of 1 or 2 or more).

[0034] As shown in Figure 4, the following example describes a case in which, in step A, the substance M, which has been filled in the tank 260d in a gaseous state, is supplied to the wafer 200 under reduced pressure only once.

[0035] Furthermore, as shown in Figure 4, the following example describes a case where steps A to D are performed multiple times to etch the surface of the wafer 200.

[0036] Furthermore, as shown in Figure 4, the following example describes a case in which, after performing steps A to D multiple times, step E is further performed, in which a film-forming agent is supplied to the wafer 200 whose surface has been etched, thereby forming a film on the wafer 200.

[0037] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film 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 predetermined film or the like formed on the wafer. In this specification, when it is stated that "a predetermined film is formed on the surface of the wafer," it may mean that the predetermined film is formed directly on the surface of the wafer itself or that the predetermined film is formed on a film or the like formed on the wafer. In this specification, the term "substrate" is used in the same sense as when the term "wafer" is used.

[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 substance M, etching agent, reducing agent, and film-forming agent (raw material, dopant agent, etc.) may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0039] (Wafer charging and boat loading) First, multiple wafers 200 are loaded (wafer charging) into the boat 217.

[0040] An oxide may be formed on the surface of the wafer 200 to be etched. The oxide is a non-stoichiometric silicon oxide film (SiO ｘ A film (where x is a real number less than 2) and a silicon oxide film (SiO) of stoichiometric composition. ２ It may contain at least one of the following (films). Furthermore, the oxide may contain at least one of the following: native oxide film and chemical oxide film. ｘ membranes and SiO ２The film will collectively be referred to as an SiO film below. Oxides may contain elements other than Si and O.

[0041] 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 load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0042] Upon completion of the boatloading, the substrate to be processed, i.e., the wafer 200 having oxide on its surface, is prepared (placed) in the processing chamber 201.

[0043] (Pressure and Temperature Adjustment) After 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 so that it reaches the desired pressure (vacuum level). As a result, the wafer 200 is under reduced pressure. At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by the heater 207 so that it reaches 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 so that the processing chamber 201 has the desired temperature distribution. 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. The space in which the wafer 200 is located, that is, the space within the processing chamber 201, is also referred to as the processing space.

[0044] (Charging of substance M) In parallel with these operations, substance M is filled in a gaseous state into the tank 260d, which serves as the first storage unit.

[0045] Specifically, with the valve 247d closed, the valve 243d is opened, and the substance M is flowed into the gas supply pipe 232d. The flow rate of the substance M is adjusted by the MFC 241d, supplied to the tank 260d, and stored in the tank 260d. After a predetermined pressure and a predetermined amount of the substance M are stored in the tank 260d, the valve 243d is closed to confine (seal) the substance M in the tank 260d in a gaseous state. By these series of operations, the filling of the substance M into the tank 260d is completed (charging of the substance M). In this step, an inert gas as a dilution gas may be supplied into the tank 260d together with the substance M to fill the tank 260d with a mixture of the substance M and the dilution gas.

[0046] As the substance M, a substance containing oxygen (O) and hydrogen (H), for example, water (H ２ 2 ２ O) can be used. As substances containing O and H, in addition, substances that generate H ２ 2 ２ O), such as hydrogen peroxide (H

[0047] 2 ２ O

[0048] (Step A) After the charging of the substance M into the tank 260d and the pressure adjustment and temperature adjustment in the processing chamber 201 are completed, the substance M (or a mixture of the substance M and the dilution gas) filled in the tank 260d in a gaseous state at high pressure is supplied to the wafer 200 under reduced pressure in one go in a short time. In the present disclosure, such a method of supplying a substance to the wafer 200 using a pressure difference is also referred to as flash supply (flash flow).

[0049] Specifically, with valve 243d closed, valve 247d is opened. This causes the high-pressure gaseous substance M (or a mixture of substance M and diluent gas) stored in tank 260d to be rapidly (pulsarily) supplied into the processing chamber 201 via the gas supply pipe 232a and nozzle 249a. At this time, substance M is rapidly supplied to the wafer 200, which is under reduced pressure, from the side of the wafer 200, and the wafer 200 is rapidly exposed to substance M (flash supply and exposure of substance M). At this time, valves 243f to 243h and 247f to 247h may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0050] Under the processing conditions described later, by flash-supplying substance M (or a mixture of substance M and diluent gas) filled in tank 260d in a gaseous state to wafer 200 under reduced pressure, it becomes possible to rapidly diffuse substance M throughout the entire processing chamber 201. This shortens the exposure time of substance M to wafer 200 and allows substance M to spread uniformly across the entire wafer 200 in a short time. It also makes it possible to synchronize the timing of the start of substance M adsorption onto wafer 200 across wafers 200. As a result, it becomes possible to adsorb substance M in a substantially uniform amount and density across the entire surface of multiple wafers 200, that is, across the entire surface of each of the multiple wafers 200, and across the entire area between the multiple wafers 200. In this step, by adjusting at least one of the number of times, supply time, supply flow rate, supply amount, processing pressure, and processing temperature when flash-supplying substance M to wafer 200, it is possible to adjust at least one of the amount and density of substance M adsorbed onto wafer 200.

[0051] In this step, after performing a flash supply of substance M (or a mixture of substance M and diluent gas), for example, after the flow rate or velocity of substance M supplied to the wafer 200 has decreased, valve 243d may be opened while valve 247d is open, and this state may be maintained for a predetermined time to continue the continuous supply of substance M (or a mixture of substance M and diluent gas) (continuous supply and exposure of substance M). In this case, the amount and density of substance M adsorbed on the wafer 200 can be finely adjusted by adjusting at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when continuously supplying substance M to the wafer 200.

[0052] After adsorbing substance M onto each of the multiple wafers 200, the valve 247d is closed to stop the supply of substance M (or a mixture of substance M and diluent gas) into the processing chamber 201.

[0053] Examples of processing conditions when supplying substance M in a flash in step A include: Processing temperature: room temperature (25°C) to 170°C, preferably 25 to 150°C Processing pressure: 10 to 3000 Pa, preferably 500 to 2000 Pa Amount of substance M flashed: 0.05 to 2 L, preferably 0.1 to 1 L Amount of diluent gas flashed: 0 to 2 L, preferably 0.1 to 1 L Amount of substance M (+ diluent gas) flashed: 1 to 20 seconds, preferably 1 to 10 seconds Number of times substance M (+ diluent gas) is flashed: 1 to 10 times Continuous supply flow rate of substance M: 0 to 2 slm, preferably 0 to 1 slm Continuous supply flow rate of diluent gas: 0 to 2 slm, preferably 0 to 1 slm Continuous supply time of substance M (+ diluent gas): 0 to 60 seconds, preferably 0 to 30 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm, preferably 0.5 to 5 slm

[0054] In this specification, numerical ranges such as "25 to 170°C" mean that the lower and upper limits are included within that range. For example, "25 to 170°C" means "25°C or more and 170°C or less." The same applies to other numerical ranges. In this specification, processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure refers to the pressure inside the processing chamber 201.

[0055] Furthermore, in this specification, "flash supply amount" means the supply amount per flash supply, and "flash supply time" means the supply time per flash supply. Furthermore, in this specification, "continuous supply flow rate" means the supply flow rate when continuous supply is performed after a flash supply, and "continuous supply time" means the supply time when continuous supply is performed after a flash supply. For example, "dilution gas flash supply amount: 0 L" means the case in which no dilution gas is supplied, that is, the case in which substance M is flash-supplied without dilution. Also, for example, "continuous supply flow rate of substance M: 0 slm" means the case in which substance M is not continuously supplied after a flash supply of substance M. Also, for example, "continuous supply flow rate of dilution gas: 0 slm" means the case in which dilution gas is not continuously supplied after a flash supply of dilution gas. Furthermore, "inert gas supply flow rate (per gas supply pipe)" means the flow rate of inert gas supplied from lines other than the line that flash-supplies substance M (+ dilution gas).

[0056] These points also apply to the following explanation.

[0057] (Step B) Subsequently, at least one of the following is performed: supplying an inert gas as a purge gas to the wafer 200 on which substance M has been adsorbed, or exhausting the space in which the wafer 200 is located.

[0058] Specifically, for example, when supplying purge gas to wafer 200, valves 243f to 243h and 247f to 247h are opened, and purge gas is allowed to flow into gas supply pipes 232f to 232h. The flow rate of the purge gas is adjusted by MFCs 241f to 241h, supplied to the processing chamber 201 via nozzles 249a to 249c, and exhausted from exhaust port 231a. At this time, purge gas is supplied to wafer 200 from the side, and wafer 200 is exposed to the purge gas (purge gas supply, exposure).

[0059] Under the processing conditions described later, by supplying a purge gas to the wafer 200 on which substance M is adsorbed and exhausting the space where the wafer 200 is located, it is possible to remove some of the substance M while leaving some of it adsorbed on the wafer 200. This makes it possible to create a state in which a small amount of substance M is adsorbed (remains) in a substantially uniform amount and density across the entire surface of multiple wafers 200, that is, across the entire in-plane area of ​​each of the multiple wafers 200, and across the entire area between the multiple wafers 200. In this step, the amount of substance M remaining can be adjusted so that only a predetermined small amount of substance M remains in the processing chamber 201 and on the surface of the wafer 200, that is, only the amount that will effectively contribute to the reaction with the etching agent in step C described later. In this step, by adjusting at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when supplying purge gas to the wafer 200, at least one of the amount and density of substance M adsorbed and remaining on the wafer 200 can be adjusted.

[0060] After creating a state in which a small amount of substance M is uniformly adsorbed across multiple wafers 200, if a purge gas was being supplied, valves 243f to 243h and 247f to 247h are closed to stop the supply of purge gas into the processing chamber 201.

[0061] Examples of processing conditions in step B include: processing temperature: 25 to 170°C, preferably 25 to 150°C; processing pressure: 10 to 2000 Pa, preferably 500 to 1000 Pa; purge gas supply flow rate (per gas supply pipe): 0 to 10 slm, preferably 0.5 to 5 slm; and purge gas supply time: 1 to 600 seconds, preferably 1 to 500 seconds.

[0062] Note that a purge gas supply flow rate of 0 slm means the case in which no purge gas is supplied, that is, the case in which only exhaust (vacuum evacuation) of the processing chamber 201 is performed. Even by exhausting the processing chamber 201 without supplying purge gas, it is possible to desorb some of the substance M adsorbed on the wafer 200 while leaving some of the substance M behind. In this case, by adjusting at least one of the processing pressure (vacuum level), processing time (evacuation time), or processing temperature, it is possible to adjust at least one of the amount and density of the substance M adsorbed and left behind on the wafer 200.

[0063] (Step C) Subsequently, a substance containing F as an etching agent is supplied to the wafer 200, which has a small amount of substance M adsorbed on it.

[0064] Specifically, valve 243a is opened and etching agent is flowed into gas supply pipe 232a. The etching agent's flow rate is adjusted by MFC 241a and supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, etching agent is supplied to the wafer 200 from the side of the wafer 200, and the wafer 200 is exposed to the etching agent (etching agent supply, exposure). At this time, valves 243f to 243h and 247f to 247h may be opened to supply inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0065] Under the conditions described later, by supplying an etching agent to the wafer 200, the substance M adsorbed on the wafer 200 reacts with the etching agent, generating reaction products that act as etching species. These etching species can then be used to etch the surface of the wafer 200, for example, oxides on the surface of the wafer 200.

[0066] For example, if the oxide on the surface of wafer 200 is silicon oxide (SiO ２ ) contains a trace amount of substance M adsorbed onto wafer 200, which is water (H ２ When the etching agent supplied into the processing chamber 201 contains (O) and contains hydrogen fluoride (HF), under the conditions described later, the reaction shown in the following formula can be carried out. That is, substance M (H) ２ Etching species (HF) obtained by reaction of O) and etching agent (HF) ２ － Using (etc.), the oxide (SiO) on the surface of the wafer 200 ２ This makes it possible to etch the material.

[0067] 2HF+H ２ O → HF ２ － +H ３ O ＋ SiO ２ +2HF ２ － +2H ３ O ＋ → SiF ４ +4H ２ O

[0068] In this step, the amount of etching on the surface of the wafer 200 can be adjusted by adjusting at least one of the following when supplying the etching agent to the wafer 200: the supply time, the supply flow rate, the supply amount, the processing pressure, and the processing temperature.

[0069] As described above, according to this disclosure, the oxide (SiO) on the surface of the wafer 200 ２ The etching of the wafer 200 is performed using an etching agent (HF) and a small amount of substance M (H) adsorbed onto the wafer 200. ２ The reaction between O) and can be used as a trigger to start the process. When the etching of the oxide starts, a small amount of substance M(H) that has been pre-adsorbed onto the wafer 200 is triggered. ２ O) is consumed. However, in the reaction system in step C, water (H) is consumed by etching the oxide. ２O) is generated. Therefore, in step C, the above reaction is repeated in a chain reaction without supplying additional substance M into the processing chamber 201, making it possible to etch the oxide on the surface of the wafer 200. Note that if additional substance M is supplied into the processing chamber 201 in step C, the amount of substance M in this reaction system becomes excessive, which may actually hinder the progress of the etching reaction.

[0070] After etching the surface of the wafer 200, the valve 243a is closed to stop the supply of etching agent into the processing chamber 201.

[0071] Examples of processing conditions when supplying the etching agent in step C include: Processing temperature: 25 to 170°C, preferably 25 to 150°C; Processing pressure: 10 to 4000, preferably 500 to 2000 Pa; Etching agent supply flow rate: 0.5 to 3 slm, preferably 1 to 2 slm; Etching agent supply time: 1 to 120 minutes, preferably 10 to 100 minutes; Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm, preferably 1 to 5 slm.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] As mentioned above, an F-containing substance can be used as an etching agent, for example, a substance containing hydrogen (H) and F, such as hydrogen fluoride (HF), can be used. Also, for example, as an etching agent, fluorine (F ２ ), nitrogen trifluoride (NF ３ ), chlorine trifluoride (ClF ３ ), chlorine fluoride (ClF), etc. can be used. One or more of these can be used as etching agents.

[0078] (Step D) Subsequently, at least one of purging and exhausting is performed in the space where the wafer 200 is located, i.e., in the processing chamber 201, using the same processing procedure as in Step B.

[0079] This allows for the removal of gaseous substances and other materials remaining in the processing chamber 201. For example, etching agents, etching species, etching residues, moisture, etc. remaining in the processing chamber 201 can be discharged from the processing chamber 201, thereby cleaning (resetting) the space where the wafer 200 is located. Furthermore, etching agents, etching species, etching residues, moisture, etc. remaining on the surface of the wafer 200 can be removed from the surface of the wafer 200, thereby cleaning (resetting) the surface of the wafer 200.

[0080] After purging and / or exhausting the processing chamber 201, if a purge gas was being supplied, the supply of purge gas to the processing chamber 201 is stopped.

[0081] Examples of processing conditions in step D include: processing temperature: 25 to 170°C, preferably 25 to 150°C; processing pressure: 1 to 100 Pa, preferably 1 to 50 Pa; purge gas supply flow rate (per gas supply pipe): 0 to 30 slm, preferably 1 to 10 slm; and purge gas supply time: 1 to 800 seconds, preferably 1 to 600 seconds.

[0082] Unlike step B, in step D, it is not necessary to leave some of the substance M adsorbed on the wafer 200, and the processing chamber 201 can be purged under conditions that provide a higher purging effect than in step B. For example, in step D, the processing pressure can be lower (the vacuum level can be higher), the amount of purge gas supplied can be increased, the flow rate of the purge gas can be increased, and the processing time (purge gas supply time, exhaust time) can be extended compared to step B. By making the processing conditions in step D different from those in step B in this way, the necessary processing in each step can be performed efficiently and effectively, and the control in step D can also be simplified.

[0083] (Performed a predetermined number of times) By performing the cycle including steps A to D described above a predetermined number of times (n times, where n is 1 or an integer of 2 or more), the surface of the wafer 200 is etched to a predetermined thickness, making it possible to remove oxide from the surface of the wafer 200 to a predetermined thickness.

[0084] It is preferable to repeat this cycle multiple times. That is, it is preferable to make the etching thickness (depth) per cycle thinner than the desired thickness (predetermined thickness, predetermined depth), and to repeat the above cycle multiple times until the etching thickness of the wafer 200 reaches the desired thickness (predetermined thickness, predetermined depth). By performing the above cycle a predetermined number of times, for example, all oxide can be removed from the surface of the wafer 200, exposing the underlying material.

[0085] Furthermore, when performing multiple cycles including steps A to D, it is preferable to perform the above-mentioned charging step of substance M in parallel with the execution of the cycle. That is, after performing step A for the nth time, it is preferable to start filling the tank 260d with substance M to be used in the (n+1)th cycle, and to complete the filling of the tank 260d with substance M before starting step A for the (n+1)th time. In this way, it is possible to perform cycles including steps A to D continuously without any waiting time in between.

[0086] (Pressure and Temperature Adjustment) After the etching process on the wafer 200 is completed, the processing chamber 201 is evacuated by the vacuum pump 246 so that the pressure inside reaches the predetermined processing pressure in step E described later. The output of the heater 207 is also adjusted so that the temperature of the wafer 200 reaches the predetermined processing temperature in step E.

[0087] (Step E) Subsequently, the wafer 200 whose surface has been etched is supplied with raw materials for the film-forming agent and a reducing agent.

[0088] 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, the raw material and reducing agent are supplied to the wafer 200 from the side of the wafer 200, 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 and 247f to 247h may be opened, and an inert gas may be supplied into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0089] Under the processing conditions described later, by supplying raw materials and a reducing agent to the wafer 200, it becomes possible to form a predetermined film on the surface of the etched wafer 200. For example, if the surface of the wafer 200 exposed by the etching process described above is composed of single-crystal Si, and the raw materials and reducing agent are 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.

[0090] After forming a predetermined film 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 D.

[0091] Examples of processing conditions when supplying raw materials and reducing agents in step E include: Processing temperature: 500 to 650°C, preferably 550 to 600°C; Processing pressure: 4 to 200 Pa, preferably 1 to 120 Pa; Processing time: 10 to 120 minutes, preferably 20 to 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 to 20 slm, preferably 0.1 to 10 slm.

[0092] As a raw material, for example, monosilane (SiH ４ ), disilane (Si ２ H ６ ), trisilane (Si ３ H ８ ), tetrasilane (Si ４ H １０ Silicon hydride such as ) can be used. One or more of these can be used as raw materials.

[0093] Examples of reducing agents include hydrogen (H ２ ), deuterium (D ２ H-containing substances such as ) and deuterium (D)-containing substances can be used. One or more of these can be used as reducing agents.

[0094] (After-purging and return to atmospheric pressure) After the film deposition process is completed, inert 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-purging). 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 normal pressure (return to atmospheric pressure).

[0095] (Boat Unloading) The seal cap 219 is then lowered by the boat elevator 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the boat 217, is then unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After 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 closing). After boat unloading, the wafer 200 is removed from the boat 217 (wafer discharge).

[0096] The processing step in one aspect of this disclosure is thus completed.

[0097] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0098] (a) In step A, substance M, which has been filled in the first storage unit in a gaseous state, is supplied to a substrate under reduced pressure. This shortens the exposure time of substance M to the substrate and allows the substance M to spread uniformly throughout the entire substrate in a short time. Furthermore, in step B, at least one of supplying a purge gas to the substrate or exhausting the space in which the substrate is located is performed. This allows some of the substance M adsorbed on the substrate to remain while desorbing other parts of the substance M. As a result, in steps A and B, the amount of substance M exposed to the substrate, the amount adsorbed, the amount remaining, etc. can be precisely controlled, and a state can be created in which a small amount of substance M is uniformly adsorbed throughout the entire substrate.

[0099] Subsequently, in step C, an etching agent is supplied to the substrate. This allows the etching agent to react with a small amount of substance M that is uniformly distributed throughout the substrate, thereby promoting the etching reaction uniformly across the entire substrate. Furthermore, by creating a state in which a small amount of substance M is uniformly adsorbed across the entire substrate at the start of step C, it is possible to suppress variations in the concentration of etching species generated in step C within and / or between substrates. As a result, it is possible to suppress variations in the amount of etching on the substrate surface within and / or between substrates.

[0100] As a result, it becomes possible to efficiently etch the surface of the substrate. Furthermore, it becomes possible to improve the uniformity of the etching amount on the substrate surface, that is, the uniformity of etching within the substrate surface and / or between substrates.

[0101] Furthermore, the etching process temperature can be increased, and if other processes such as film deposition are performed at least before or after the etching process, the etching process temperature can be brought closer to the processing 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.

[0102] (b) In step B, at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when supplying purge gas to the substrate is adjusted. This makes it possible to controlly remove some of the substance M adsorbed on the substrate while leaving some of it in place in step B. As a result, it becomes possible to create a state in which a small amount of substance M is uniformly adsorbed over the entire substrate with high precision and effectiveness.

[0103] (c) The etching agent contains F, and substance M contains O and H. This makes it possible to effectively obtain the above-mentioned effects. Furthermore, if the etching agent contains H and F, and substance M contains O and H, it becomes possible to obtain the above-mentioned effects more effectively.

[0104] (d) In the etching process, oxides on the surface of the substrate are etched. The oxides include silicon oxide films of stoichiometric or non-stoichiometric composition. The oxides also include at least one of native oxide films and chemical oxide films. The above-described effects can be effectively obtained in at least one of these cases.

[0105] (e) During the etching process of the substrate surface, material M is generated, and the amount and density (concentration) of material M may vary depending on the location. In such cases, steps A to D are performed multiple times as in this embodiment. This allows for purging and exhausting of the space where the substrate is located in step D during the etching process, thereby eliminating variations in the amount and density of material M depending on the location and resetting the atmosphere and surface condition of the substrate. Subsequently, by performing steps A and B again, the amount and density of material M can be made uniform or set to a desired amount and density. In other words, it is possible to suppress variations in the etching amount caused by variations in the amount and density of material M depending on the location.

[0106] (f) In step E, a film-forming agent is supplied to the substrate whose surface has been etched to form a film on the substrate. This makes it possible to reduce the concentration of impurities (such as O concentration) at the interface between the substrate and the film.

[0107] (g) In steps B and C, the second storage section (tanks 260f to 260h) and the third storage section (tank 260a) are not used, so they can be omitted. This simplifies the supply system and reduces the effort and cost of maintenance on the supply system.

[0108] (h) The effects described above can also be obtained when a predetermined substance is arbitrarily selected from the various purge gases, etching agents, film-forming agents, and reducing agents described above.

[0109] (4) Modifications The processing sequence in this embodiment can be modified as shown below. These modifications can be combined in any way. Unless otherwise specified, the processing procedures and processing conditions in each step of each modification can be the same as the processing procedures and processing conditions in each step of the processing sequence described above.

[0110] (Modification 1) In step A, the substance M, which has been filled in the first storage unit in a gaseous state, is supplied to the substrate under reduced pressure multiple times (m １ times, m１ (where is an integer of 2 or more) This can also be done in this way.

[0111] The same effects as those in the above-described embodiment can be obtained in this modified version as well. Furthermore, according to this modified version, in step A, the amount of substance M exposed to the substrate and the amount adsorbed can be controlled more precisely. This makes it possible to create a state in which a small amount of substance M is uniformly adsorbed across the entire substrate with higher precision and effectiveness.

[0112] (Modification 2) As described above, in step A, the substance M, which has been filled in the first storage unit in a gaseous state, is supplied to the substrate under reduced pressure for a predetermined number of times (m １ times, m １ After performing the procedure (where is an integer of 1 or 2 or more), or after performing it a predetermined number of times, the substance M may be continuously supplied to the substrate.

[0113] In this modified version, the same effects as those described above in the embodiments and modifications can be obtained. Furthermore, according to this modified version, in step A, the amount of substance M exposed to the substrate and the amount adsorbed can be controlled more precisely. This makes it possible to efficiently create a state in which a small amount of substance M is uniformly adsorbed across the entire substrate.

[0114] (Modification 3) As described above, in step A, a mixture of substance M filled in the first storage unit and diluent gas is supplied to the substrate under reduced pressure for a predetermined number of times (m １ times, m １ (where is an integer of 1 or 2 or more) may be used instead.

[0115] Furthermore, in step A, a mixture of substance M filled in the first storage unit and diluent gas is supplied to the substrate under reduced pressure for a predetermined number of times (m １ times, m １ The mixture may be continuously supplied to the substrate after the procedure (where is an integer of 1 or 2 or more), or after each predetermined number of procedures.

[0116] In this modified version, the same effects as in the above-described embodiment can be obtained. Furthermore, according to this modified version, the concentration of substance M in the first storage section can be reduced, and the amount of substance M exposed to the substrate in step A can be reduced. In addition, in step A, the amount of substance M exposed to and adsorbed on the substrate can be controlled more precisely. As a result, it becomes possible to efficiently create a state in which a small amount of substance M is uniformly adsorbed across the entire substrate.

[0117] (Modification 4) As shown in Figure 5, in step B, the purge gas filled in the second storage unit is supplied to the substrate, that is, the flash supply of purge gas is performed a predetermined number of times (m ２ times, m ２ (where is an integer of 1 or 2 or more) may be used instead.

[0118] In this case, step B involves the following steps in order: step B1, which involves filling the tanks 260f to 260h, which serve as the second storage section, with an inert gas as a purge gas; and step B2, which involves supplying the purge gas filled in the tanks 260f to 260h to the wafer 200.

[0119] Specifically, in step B1, with valves 247f to 247h closed, valves 243f to 243h are opened, and purge gas is flowed into the gas supply pipes 232f to 232h. The flow rate of the purge gas is adjusted by MFCs 241f to 241h and supplied to tanks 260f to 260h, where it is stored. After a predetermined pressure and amount of purge gas has been stored in each of the tanks 260f to 260h, valves 243f to 243h are closed, sealing (confining) the purge gas in tanks 260f to 260h. Through this series of operations, the filling of tanks 260f to 260h with purge gas is completed (purge gas charging).

[0120] Furthermore, in step B2, with valves 243f to 243h closed, valves 247f to 247h are opened. As a result, the high-pressure purge gas stored in tanks 260f to 260h is supplied all at once (in a pulsed manner) into the processing chamber 201 via gas supply pipes 232a to 232c and nozzles 249a to 249c. At this time, the purge gas is supplied all at once to the wafer 200 from the side, and the wafer 200 is exposed to the purge gas all at once (flash supply and exposure of purge gas).

[0121] Then, the cycle including steps B1 and B2 described above is repeated a predetermined number of times (m ２ times, m ２ This is performed (where is an integer of 1 or 2 or more). This allows a portion of the substance M adsorbed on the wafer 200 to remain while another portion of the substance M is removed. Figure 5 shows a case where the cycle including steps B1 and B2 is performed multiple times (3 times) in step B.

[0122] In step B, the amount of purge gas to be filled into the second storage unit, and the number of times the purge gas filled into the second storage unit is supplied to the wafer 200 (m ２ The amount and density of substance M adsorbed and remaining on the wafer 200 may be adjusted by adjusting at least one of the following:

[0123] In step B, after a predetermined number of flashes of purge gas have been performed, or after each predetermined number of flashes, the purge gas may be continuously supplied to the wafer 200. Continuous supply of purge gas to the wafer 200 can be performed by simultaneously opening valves 243f to 243h and 247f to 247h.

[0124] Examples of processing conditions when supplying purge gas in step B include: purge gas flush supply amount: 0.05 to 2 L, preferably 0.1 to 1 L; purge gas flush supply time: 1 to 20 seconds, preferably 1 to 10 seconds; number of purge gas flush supplies: 1 to 20 times; continuous purge gas supply flow rate: 0 to 5 slm, preferably 0 to 2 slm; continuous purge gas supply time: 0 to 180 seconds, preferably 0 to 120 seconds. Other processing conditions can be the same as the processing conditions in step B in the above-described embodiment.

[0125] In this modified example, the same effects as those in the above-described embodiment can be obtained. Furthermore, with this modified example, the timing of the start of supplying purge gas to the substrate, i.e., the timing of the start of desorption of substance M from the substrate, can be synchronized between substrates. In addition, by adjusting at least one of the number of supply cycles, supply time, supply flow rate, supply amount, processing pressure, and processing temperature when flashing purge gas to the substrate, at least one of the amount and density of substance M adsorbed and remaining on the substrate can be adjusted. Furthermore, by adjusting at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when continuously supplying purge gas to the substrate, at least one of the amount and density of substance M adsorbed and remaining on the substrate can be finely adjusted. As a result, in step B, it is possible to control the desorption of a portion of substance M while leaving a portion of the substance M adsorbed on the substrate. This makes it possible to create a state in which a small amount of substance M is uniformly adsorbed across the entire substrate with high precision and effectiveness.

[0126] Furthermore, the flush supply, multiple flush supplies, and continuous supply after the flush supply of purge gas in step B described above can also be applied to the supply of purge gas in step D. In this case as well, the same effects as in this modified example can be obtained.

[0127] (Modification 5) As shown in Figure 6, in step C, the etching agent filled in the third storage unit is supplied to the substrate, that is, the flash supply of the etching agent is performed a predetermined number of times (m ３ times, m３ (where is an integer of 1 or 2 or more) may be used instead.

[0128] In this case, step C is performed in the following order: step C1, which involves filling the tank 260a, which serves as the third storage unit, with etching agent; and step C2, which involves supplying the etching agent filled in the tank 260a to the wafer 200.

[0129] Specifically, in step C1, with valve 247a closed, valve 243a is opened to allow the etching agent to flow into the gas supply pipe 232a. The etching agent's flow rate is adjusted by MFC 241a and supplied to tank 260a, where it is stored. After a predetermined pressure and amount of etching agent has been stored in tank 260a, valve 243a is closed to seal (confine) the etching agent in tank 260a. Through this series of operations, the filling of tank 260a with etching agent is completed (etching agent charging).

[0130] Furthermore, in step C2, with valve 243a closed, valve 247a is opened. This causes the high-pressure etching agent stored in tank 260a to be supplied all at once (in a pulsed manner) into the processing chamber 201 via the gas supply pipe 232a and nozzle 249a. At this time, the etching agent is supplied all at once to the wafer 200 from the side of the wafer 200, and the wafer 200 is exposed to the etching agent all at once (flash supply and exposure of the etching agent).

[0131] Then, the cycle including steps C1 and C2 described above is repeated a predetermined number of times (m ３ times, m ３ This is performed (where is an integer of 1 or 2 or more). This allows the substance M adsorbed and remaining on the wafer 200 to react with the etching agent, and the etching species obtained from this reaction can be used to etch the surface of the wafer 200. Figure 6 shows a case where the cycle including steps C1 and C2 is performed multiple times (5 times) in step C.

[0132] In step C, after performing a predetermined number of flashes of the etching agent, or after each predetermined number of flashes, the etching agent may be continuously supplied to the wafer 200. Continuous supply of the etching agent to the wafer 200 can be performed by opening valves 243a and 247a simultaneously.

[0133] Examples of processing conditions when supplying the etching agent in step C include: Etching agent flash supply amount: 0.05 to 2 L, preferably 0.1 to 1 L Dilution gas flash supply amount: 0 to 2 L, preferably 0.1 to 1 L Etching agent (+ dilution gas) flash supply time: 1 to 20 seconds, preferably 1 to 10 seconds Number of times etching agent (+ dilution gas) flash supplies: 1 to 200 times Continuous etching agent supply flow rate: 0 to 2 slm, preferably 0 to 1 slm Continuous dilution gas supply flow rate: 0 to 2 slm, preferably 0 to 1 slm Continuous etching agent (+ dilution gas) supply time: 0 to 60 seconds, preferably 0 to 30 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm, preferably 1 to 5 slm.

[0134] In this modified example, the same effects as those in the above-described embodiment can be obtained. Furthermore, according to this modified example, the timing of the start of supplying the etching agent to the substrate, that is, the timing of the start of the reaction between the substance M adsorbed and remaining on the substrate and the etching agent, can be synchronized between substrates. In this case, the initial flash supply of the etching agent to the substrate triggers the start of the reaction between substance M and the etching agent. In addition, the amount of etching species generated by the reaction between substance M and the etching agent can be adjusted by adjusting at least one of the number of supply cycles, supply time, supply flow rate, supply amount, processing pressure, and processing temperature when flashing the etching agent to the substrate. Furthermore, the amount of etching species generated by the reaction between substance M and the etching agent can be finely adjusted by adjusting at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when continuously supplying the etching agent to the substrate. As a result, it becomes possible to etch the surface of the substrate with good controllability and efficiency. In addition, it becomes possible to improve the uniformity of the etching amount within the substrate surface and / or between substrates.

[0135] (Modification 6) When the above etching process is performed on multiple substrates, the amount of etching on the surface of the substrates may vary between substrates, that is, between a portion of the multiple substrates and other portions.

[0136] In this case, multiple substrates may be placed in the processing space, and in step A, the amount of substance M exposed to the substrates may be different for some of the multiple substrates and for others. Alternatively, in step B, the amount of purge gas exposed to the substrates may be different for some of the multiple substrates and for others. Alternatively, both the exposure control described above in step A and the exposure control described above in step B may be performed.

[0137] For example, when the above etching process is performed on multiple substrates arranged in a processing space, the amount of etching on the surface of the upper substrate may be less than that of the middle substrate, while the amount of etching on the surface of the lower substrate may be greater than that of the middle substrate. In such cases, for example, as shown in Figure 7(a), in step A, the amount of substance M exposed to the upper substrate may be greater than that exposed to the middle substrate, and the amount of substance M exposed to the lower substrate may be less than that exposed to the middle substrate. Alternatively, as shown in Figure 8(a), in step B, the amount of purge gas exposed to the upper substrate may be less than that exposed to the middle substrate, and the amount of purge gas exposed to the lower substrate may be greater than that exposed to the middle substrate. Alternatively, both the above-described exposure control in step A and the above-described exposure control in step B may be performed.

[0138] Furthermore, for example, when the above etching process is performed on multiple substrates arranged in a processing space, the amount of surface etching on the upper substrate may be greater than that on the middle substrate, and the amount of surface etching on the lower substrate may be less than that on the middle substrate. In such cases, for example, as shown in Figure 7(b), in step A, the amount of substance M exposed to the upper substrate may be made less than that exposed to the middle substrate, and the amount of substance M exposed to the lower substrate may be made greater than that exposed to the middle substrate. Alternatively, as shown in Figure 8(b), in step B, the amount of purge gas exposed to the upper substrate may be made greater than that exposed to the middle substrate, and the amount of purge gas exposed to the lower substrate may be made less than that exposed to the middle substrate. Alternatively, both the exposure control described above in step A and the exposure control described above in step B may be performed.

[0139] Furthermore, for example, when the above etching process is performed on multiple substrates arranged in a processing space, the amount of etching on the surface of the upper and lower substrates may be greater than that of the middle substrate. In such cases, for example, as shown in Figure 7(c), in step A, the amount of substance M exposed to the upper and lower substrates may be made smaller than the amount of substance M exposed to the middle substrate. Alternatively, as shown in Figure 8(c), in step B, the amount of purge gas exposed to the upper and lower substrates may be made larger than the amount of purge gas exposed to the middle substrate. Alternatively, both the exposure control described above in step A and the exposure control described above in step B may be performed.

[0140] In Figures 7(a) to 7(c) and 8(a) to 8(c), the length of each arrow ejected from each nozzle (upper nozzle, middle nozzle, lower nozzle) indicates the relative amounts or flow rates of the substance (substance M, purge gas). That is, the longer the length of the arrow ejected from the nozzle, the greater the amount or flow rate of the substance. Furthermore, the thickness of the layer containing substance M on each substrate indicates the amount of substance M adsorbed (or remaining). That is, the thicker the layer containing substance M on each substrate, the greater the amount of substance M adsorbed (or remaining), and / or the higher the density of substance M adsorbed (or remaining) on ​​the substrate. The control shown in these figures can be achieved, for example, by using multiple nozzles of different heights (lengths), so-called multi-nozzles, which are provided to correspond to the upper, middle, and lower parts of the space where the substrate is placed, and individually controlling the amount or flow rate of the substance supplied from each nozzle. Furthermore, the control shown in these figures can also be performed by individually adjusting the diameter of the gas supply holes provided in long nozzles such as nozzles 249a to 249c, i.e., the opening area, to correspond to the upper, middle, and lower parts of the space where the substrate is placed.

[0141] In this modified example, the same effects as those described above can be obtained. Furthermore, according to this modified example, in step B, at least one of the amount and density of substance M adsorbed and left on the substrate can be made different between a portion of the multiple substrates and another portion. As a result, the etching amount can be individually adjusted for each of the upper, middle, and lower parts of the space where the substrates are placed, and variations in the etching amount between substrates can be suppressed.

[0142] <Other Aspects of the Disclosure> The aspects of the Disclosure have been described in detail above. However, the Disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0143] For example, without providing tanks 260a, 260d, 260f-260h, the gas supply pipes 232a, 232d, 232f-232h between valves 243a, 243d, 243f-243h and valves 247a, 247d, 247f-247h may be used as the first to third storage sections. That is, in at least one of steps A to C, a substance (substance M, purge gas, etching agent) temporarily filled inside the gas supply pipe sandwiched between two valves may be flash-supplied to the substrate.

[0144] Furthermore, for example, in step E of the above embodiment, 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 dopant 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. As the dopant agent, for example, phosphine (PH) ３ ), Arsine (Ash ３ ), diborane (B ２ H ６ ), trichloroborane (BCl ３) and the like can be used. One or more of these can be used as the dopant agent. The same effects as in the above-described embodiment can be obtained in this embodiment as well. Furthermore, according to this embodiment, it is possible to form a dopant-doped film (P, As, B, etc.) on a substrate.

[0145] Furthermore, for example, in step E of the above embodiment, a material containing semiconductor elements other than Si may be used to form a semiconductor element-containing film other than the Si-containing film on the substrate. For example, monogermanine (GeH) may be used as a raw material. ４ A germanium (Ge)-containing substance such as ) may be used to form a Ge-containing film such as a Ge film on the substrate. Alternatively, for example, a Si-containing substance and a Ge-containing substance may be used as raw materials to form a Si and Ge-containing film such as a SiGe film on the substrate. Alternatively, for example, an oxidizing agent or a nitriding agent may be used in addition to a Si-containing substance to form a Si-based insulating film such as a silicon oxide film (SiO film), a silicon nitride film (SiN film), or a silicon oxynitride film (SiON film) on the substrate. Alternatively, for example, a substance containing metal elements such as tungsten (W), molybdenum (Mo), aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), or tantalum (Ta) may be used as raw materials to form a metal element-containing film on the substrate. Alternatively, for example, a metal element-containing substance and a Si-containing substance may be used as raw materials to form a metal element and Si-containing film such as a metal silicide film on the substrate. Furthermore, for example, an oxidizing agent may be used in addition to a metal element-containing material and a Si-containing material to form a metal silicate film or other metal element, Si, and oxygen-containing film on the substrate. In these cases as well, the same effects as those described above can be obtained.

[0146] Furthermore, in step E of the above-described embodiment, in addition to the epitaxial film, an amorphous film, a polycrystalline film, or a mixed crystal film thereof may be formed on the substrate. For example, in addition to the epitaxial Si film, an amorphous Si film, a poly Si film, or a mixed crystal Si film of amorphous and poly may be formed on the substrate. In these cases as well, the same effects as in the above-described embodiment can be obtained.

[0147] It is preferable that the recipes used for each process be prepared individually according to the processing content, 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 processing content. 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.

[0148] 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.

[0149] 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.

[0150] Furthermore, the above-described embodiments have explained an example in which the above-described processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiments, and for example, any step of the above-described processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or in different processing chambers of the same processing apparatus.

[0151] For example, as shown in Figure 9, this disclosure can also be applied when a processing system including multiple standalone processing units (first to third processing units) is used, and each step is performed ex-situ in different processing chambers of different processing units. In this case, for example, steps A and B can be performed in the first processing unit, steps C and D in the second processing unit, and step E in the third processing unit. Alternatively, for example, step A can be performed in the first processing unit, steps B, C, and D in the second processing unit, and step E in the third processing unit. Alternatively, for example, steps A, B, C, and D can be performed in the first processing unit, and step E can be performed in the second processing unit. In these cases, the first to third processing units are also referred to as the first to third processing units, respectively. The processing system is also referred to as the processing unit.

[0152] Furthermore, this disclosure can also be applied to cases where each step is performed in different processing rooms of the same processing unit, using a processing system that includes a cluster-type processing unit in which multiple processing rooms (first to third processing rooms) are arranged around a transport room, as shown in Figure 10. In this case, for example, steps A and B can be performed in the first processing room, steps C and D in the second processing room, and step E in the third processing room. Alternatively, for example, step A may be performed in the first processing room, steps B, C, and D in the second processing room, and step E in the third processing room. Alternatively, for example, steps A, B, C, and D may be performed in the first processing room, and step E in the second processing room. In these cases, the first to third processing rooms are also referred to as the first to third processing units, respectively. Note that the above embodiments and modifications can also be considered examples in which the first to third processing units are the same processing unit. Note that the processing system is also referred to as the processing unit.

[0153] Even when using these processing devices (processing systems), each process can be performed using the same processing procedures and conditions as described above, and the same effects as described above can be obtained. Furthermore, when steps A, B, C, D and step E of the above-described processing sequence are performed in ex-situ, it is possible to prevent the introduction of the film-forming agent into the processing chamber where etching is performed, and also to prevent the introduction of substance M and the etching agent into the processing chamber where film deposition is performed. As a result, cross-contamination within each processing chamber can be prevented, and the quality of the etching process and film deposition process can be improved.

[0154] 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.

[0155] 200 wafers (substrates)

Claims

1. A processing method comprising the steps of: (a) supplying a substance M, which has been filled in a first storage unit in a gaseous state, to a substrate under reduced pressure a predetermined number of times to adsorb the substance M onto the substrate; (b) desorbing a portion of the substance M adsorbed onto the substrate while leaving a portion of it on the substrate by supplying a purge gas to the substrate and exhausting the space in which the substrate is located; (c) supplying an etching agent to the substrate to react the substance M adsorbed onto and left on the substrate with the etching agent to generate etching species; and (d) etching the surface of the substrate by performing at least one of purging the space and exhausting the space a predetermined number of times.

2. The processing method according to claim 1, wherein after supplying the substance M, which has been filled in the first storage unit in a gaseous state, to the substrate under reduced pressure a predetermined number of times, or after supplying the substance M to the substrate continuously each time the predetermined number of times is performed.

3. The processing method according to claim 1, wherein (a) a mixture of the substance M filled in the first storage unit and the diluent gas is supplied to the substrate under reduced pressure a predetermined number of times.

4. The processing method according to claim 1, wherein, after supplying a mixture of the substance M filled in the first storage unit and the diluent gas to the substrate under reduced pressure a predetermined number of times, or after supplying the mixture to the substrate continuously each time the predetermined number of times is performed.

5. The processing method according to claim 1, wherein (b) the purge gas filled in the second storage section is supplied to the substrate a predetermined number of times.

6. The processing method according to claim 1, wherein after supplying the purge gas filled in the second storage section to the substrate a predetermined number of times, or after supplying the purge gas to the substrate each predetermined number of times.

7. The processing method according to claim 1, wherein (c) the etching agent filled in the third storage section is supplied to the substrate a predetermined number of times.

8. The processing method according to claim 1, wherein, after supplying the etching agent filled in the third storage section to the substrate a predetermined number of times, or after supplying the etching agent to the substrate continuously each time the predetermined number of times is performed.

9. The processing method according to claim 1, wherein, in (b), the amount and density of the substance M adsorbed and remaining on the substrate are adjusted by adjusting at least one of the supply time, supply flow rate, supply amount, processing pressure, and processing temperature when supplying the purge gas to the substrate.

10. The processing method according to claim 5, wherein in (b), the amount of purge gas to be filled into the second storage unit and the number of times the purge gas filled into the second storage unit is supplied to the substrate are adjusted to adjust at least one of the amount and density of the substance M to be adsorbed and left on the substrate.

11. The processing method according to claim 1, wherein a plurality of substrates are arranged in the space, and in (a), the amount of exposure of the substrates to a portion of the plurality of substrates and to other portions of the substrates is different.

12. The processing method according to claim 1, wherein a plurality of substrates are arranged in the space, and in (b), the amount of exposure of the substrates to a portion of the plurality of substrates and to other portions of the substrates is different.

13. The processing method according to claim 1, wherein a plurality of substrates are arranged in the space, and in (b), at least one of the amount and density of the substance M adsorbed and remaining on the substrates is different between a portion of the plurality of substrates and another portion.

14. The treatment method according to any one of claims 1 to 13, wherein the etching agent contains fluorine, and the substance M contains oxygen and hydrogen.

15. The treatment method according to claim 14, wherein the etching agent comprises hydrogen and fluorine.

16. The processing method according to any one of claims 1 to 13, wherein the step of etching the surface of the substrate is to etch the oxide on the surface of the substrate.

17. The treatment method according to claim 16, wherein the oxide comprises a silicon oxide film having a stoichiometric or non-stoichiometric composition.

18. The treatment method according to claim 16, wherein the oxide comprises at least one of a native oxide film and a chemical oxide film.

19. The processing method according to any one of claims 1 to 13, wherein the step of etching the surface of the substrate is to perform (a), (b), (c), and (d) multiple times.

20. (e) The processing method according to any one of claims 1 to 13, further comprising the step of supplying a film-forming agent to the substrate whose surface has been etched to form a film on the substrate.

21. A method for manufacturing a semiconductor device, comprising the steps of: (a) supplying a substance M, which has been filled in a first storage unit in a gaseous state, to a substrate under reduced pressure a predetermined number of times to adsorb the substance M onto the substrate; (b) desorbing a portion of the substance M adsorbed onto the substrate while leaving a portion of it on the substrate by supplying a purge gas to the substrate and exhausting the space in which the substrate is located; (c) supplying an etching agent to the substrate to react the substance M adsorbed onto and left on the substrate with the etching agent to generate etching species; and (d) etching the surface of the substrate by performing at least one of purging the space and exhausting the space a predetermined number of times.

22. A pressure adjustment unit for adjusting the pressure in the space where the substrate is located; a substance M supply system for supplying substance M, which is filled in a gaseous state in the first storage unit, to the substrate; a purge gas supply system for supplying purge gas to the substrate; an etching agent supply system for supplying etching agent to the substrate; and an exhaust system for exhausting the space where the substrate is located. A processing apparatus having: (a) a process of adsorbing the substance M onto a substrate by supplying the substance M, which has been filled in the first storage unit in a gaseous state, to a substrate under reduced pressure a predetermined number of times; (b) a process of desorbing the other part of the substance M while leaving a portion of the substance M adsorbed onto the substrate by supplying the purge gas to the substrate and exhausting the space; (c) a process of generating etching species by supplying the etching agent to the substrate to react the substance M adsorbed onto and left on the substrate with the etching agent, and (d) a process of etching the surface of the substrate by performing the process a predetermined number of times, which includes: (a) a process of adsorbing the substance M onto a substrate by supplying the substance M, which has been filled in the first storage unit in a gaseous state, to a substrate under reduced pressure; (b) a process of desorbing the other part of the substance M while leaving a portion of the substance M adsorbed onto the substrate by supplying the purge gas to the substrate and exhausting the space; (d) a process of etching the surface of the substrate by performing the process a predetermined number of times, which includes: (a) a process of adsorbing the substance M onto a substrate by supplying the substance M, which has been filled in the first storage unit in a gaseous state, to a substrate by which the substance M has been adsorbed onto the substrate by which the purge gas to the substrate and exhausting the space; (b) a process of desorbing the other part of the substance M while leaving a portion of the substance M adsorbed onto the substrate by supplying the purge gas to the substrate and exhausting the space; (c) a process of generating etching species by supplying the etching agent to the substrate by which the substance M adsorbed onto and left on the substrate and the etching agent; and (d) a process of etching the surface of the substrate by performing the process a predetermined number of times, which includes purging the space and exhausting the space.

23. A program that causes a processing device to perform the following steps by computer: (a) a procedure to adsorb substance M onto a substrate by supplying substance M, which has been filled in a first storage unit in a gaseous state, to a substrate under reduced pressure a predetermined number of times; (b) a procedure to desorb a portion of substance M while leaving a portion of the substance M adsorbed onto the substrate by supplying a purge gas to the substrate and exhausting the space in which the substrate is located; (c) a procedure to generate etching species by supplying an etching agent to the substrate to react the substance M adsorbed onto and left on the substrate with the etching agent; and (d) a procedure to etch the surface of the substrate by performing at least one of purging the space and exhausting the space a predetermined number of times.

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