Method for processing substrate, method for manufacturing semiconductor device, substrate processor, and program

Abstract

To provide a technique of reducing the amount of impurities in a film after etching.SOLUTION: The method for processing a substrate includes the step (a) of: removing at least a part of a film on a substrate by performing at least two cycles of steps (a1) and (a2), the step (a1) being supplying a first fluorine-containing gas to the substrate (a1) and the step (a2) being supplying a reaction gas containing a predetermined element to the substrate (a2); and the step (b) of supplying a second fluorine-containing gas to the substrate after the step (a). In the step (a), a substance X containing the predetermined element is generated. In the step (b), the second fluorine-containing gas is supplied under the condition that the substance X is converted to a substance with a lower vapor pressure.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step of a substrate processing process (a manufacturing process of a semiconductor device), a step of etching a film may be performed by performing a cycle of supplying different types of gases a predetermined number of times (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-158142 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique capable of reducing the amount of impurities contained in a film after etching. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) As (a1) supplying a first fluorine-containing gas to a substrate; (a2) supplying a reaction gas containing a predetermined element to the substrate; two or more cycles comprising the steps of: removing at least a portion of the film on the substrate; (b) after (a), supplying a second fluorine-containing gas to the substrate; In (a), a substance X containing the predetermined element is generated; In (b), the second fluorine-containing gas is supplied under conditions in which the substance X is further converted into a substance with a lower vapor pressure. Technology is provided. Effect of the Invention

[0006] According to the present disclosure, it is possible to reduce the amount of impurities contained in a film after etching. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller. [Figure 4] FIG. 4 is a flow diagram illustrating a substrate processing process according to one embodiment of the present disclosure. [Diagram 5] 5A is an image of the film in the experimental example, and FIG 5B is a diagram showing the SIMS analysis results in the experimental example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 4. Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0009] (1) Configuration of the substrate processing device As shown in FIG. 1, a processing furnace 202 serving as a substrate processing apparatus has a heater 207 serving as a heating mechanism (temperature adjustment unit). The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas with heat. A reaction tube 203 is disposed inside the heater 207. A processing chamber 201 capable of accommodating a wafer 200 serving as a substrate is formed in a cylindrical hollow portion of the reaction tube 203. The wafer 200 is processed in the processing chamber 201. Nozzles 249a to 249c are provided in the processing chamber 201 so as to penetrate a lower sidewall of the reaction tube 203. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.

[0010] Gas supply pipes 232a-232c are provided with mass flow controllers (MFCs) 241a-241c, which are flow rate controllers (flow rate control parts), and valves 243a-243c, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipe 232d is connected to the downstream side of valve 243a of gas supply pipe 232a. Gas supply pipe 232e is connected to the downstream side of valve 243b of gas supply pipe 232b. Gas supply pipe 232f is connected to the downstream side of valve 243c of gas supply pipe 232c. Gas supply pipes 232d-232f are provided with MFCs 241d-241f and valves 243d-243f, in order from the upstream side of the gas flow.

[0011] The nozzles 249a and 249b are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, and are provided so as to rise upward in the arrangement direction of the wafers 200 along the inner wall of the reaction tube 203 from the lower part to the upper part. Gas supply holes 250a and 250b for supplying gas are provided on the side of the nozzles 249a and 249b. The gas supply holes 250a and 250b are each opened to face the center of the reaction tube 203, and can supply gas toward the wafers 200. A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

[0012] The nozzle 249c is provided in the buffer chamber 237. The buffer chamber 237 is provided in the space between the inner wall of the reaction tube 203 and the wafers 200 along the arrangement direction of the wafers 200. A gas supply hole 250d opening toward the center of the reaction tube 203 is provided in a part of the wall constituting the buffer chamber 237. The gas supplied from the nozzle 249c into the buffer chamber 237 is supplied to the wafers 200 through the gas supply hole 250d. A plurality of gas supply holes 250d are provided from the lower part to the upper part of the wall constituting the buffer chamber 237.

[0013] The nozzle 249c is provided at the end of the buffer chamber 237 opposite to the end where the gas supply holes 250d are provided, along the inner wall of the reaction tube 203 from the lower part to the upper part, so as to rise upward in the arrangement direction of the wafers 200. Gas supply holes 250c for supplying gas are provided on the side of the nozzle 249c. The gas supply holes 250c are open so as to face the center of the buffer chamber 237. Similar to the gas supply holes 250d, a plurality of gas supply holes 250c are provided from the lower part to the upper part of the reaction tube 203.

[0014] In this manner, in this embodiment, gas is transported (supplied) through the nozzles 249a-249c and the buffer chamber 237 into a space defined by the inner wall of the sidewall of the reaction tube 203 and the ends (peripheral parts) of the multiple wafers 200 arranged in the reaction tube 203. Then, gas is supplied toward the wafers 200 in the reaction tube 203 from gas supply holes 250a-250d opened in the nozzles 249a-249c and the buffer chamber 237, respectively.

[0015] A first fluorine-containing gas or a second fluorine-containing gas containing fluorine (F) is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

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

[0017] The modifying agent is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, the nozzle 249c, and the buffer chamber 237.

[0018] The term "modifier" used in this specification includes at least one of a gaseous substance and a liquid substance. The liquid substance includes a mist substance. That is, the modifier may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0019] From the gas supply pipes 232d to 232f, an inert gas is supplied into the processing chamber 201 via the MFCs 241d to 241f, the valves 243d to 243f, the gas supply pipes 232a to 232c, the nozzles 249a to 249c, and the buffer chamber 237. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0020] A first fluorine-containing gas supply system for supplying a first fluorine-containing gas or a second fluorine-containing gas supply system for supplying a second fluorine-containing gas is mainly constituted by the gas supply pipe 232a, the MFC 241a, and the valve 243a. A reactive gas supply system for supplying a reactive gas is mainly constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. A modifying agent supply system for supplying a modifying agent is mainly constituted by the gas supply pipe 232c, the MFC 241c, and the valve 243c. An inert gas supply system for supplying an inert gas is mainly constituted by the gas supply pipes 232d to 232f, the MFCs 241d to 241f, and the valves 243d to 243f.

[0021] As shown in FIG. 2, in the buffer chamber 237, two rod-shaped electrodes 269, 270 made of a conductor are arranged from the lower part to the upper part of the reaction tube 203 along the stacking direction of the wafers 200. Each of the rod-shaped electrodes 269, 270 is provided in parallel with the nozzle 249c. Each of the rod-shaped electrodes 269, 270 is covered from the upper part to the lower part by an electrode protection tube 275. One of the rod-shaped electrodes 269, 270 is connected to a high-frequency power source 273 via a matching device 272, and the other is connected to earth, which is a reference potential. By applying high-frequency (RF) power from the high-frequency power source 273 between the rod-shaped electrodes 269, 270 via the matching device 272, plasma is generated in the plasma generation region 224 between the rod-shaped electrodes 269, 270. The rod-shaped electrodes 269, 270 and the electrode protection tube 275 mainly constitute a plasma source as a plasma generator (plasma generating unit). The plasma source may include the matching box 272 and the high frequency power supply 273. As described below, the plasma source functions as an excitation unit (activation mechanism) that excites a gas into plasma, that is, excites (activates) the gas into a plasma state.

[0022] An exhaust pipe 231 for exhausting gas from the processing chamber 201 is connected to the lower side wall of the reaction tube 203. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to perform evacuation and stop evacuation in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation, and further, to adjust the pressure in the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation. An exhaust system is mainly configured by the exhaust pipe 231, the pressure sensor 245, and the APC valve 244. The vacuum pump 246 may be included in the exhaust system.

[0023] A seal cap 219 capable of airtightly closing the lower end opening of the reaction tube 203 is provided below the reaction tube 203. A rotation mechanism 267 for rotating a boat 217, which will be described later, is provided below the seal cap 219. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) for loading and unloading (transferring) the wafer 200 into and out of the processing chamber 201 by lifting and lowering the seal cap 219.

[0024] The boat 217 as a substrate support is configured to support multiple wafers 200, for example 25 to 200, in multiple stages in a horizontal position. At the bottom of the boat 217, heat insulating plates 218 are supported in multiple stages in a horizontal position. Note that in this disclosure, a numerical range such as "25 to 200 sheets" means that the lower limit and upper limit are included in the range. Thus, "25 to 200 sheets" means "25 sheets or more and 200 sheets or less." The same applies to other numerical ranges.

[0025] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the processing chamber 201 is configured to be as desired.

[0026] As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. An external storage device 123 can also be connected to the controller 121. The substrate processing apparatus may include one or more control units. That is, the control for performing the substrate processing step described later may be performed using one control unit or multiple control units. When the term "control unit" is used in this specification, it may include one control unit or multiple control units.

[0027] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. A control program for controlling the operation of the substrate processing apparatus, a process recipe in which the procedure and conditions of the etching process described later are described, etc. are readably stored in the storage device 121c. The process recipe is a combination of procedures in the etching process described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.

[0028] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, matching box 272, high frequency power supply 273, rotation mechanism 267, boat elevator 115, and the like.

[0029] 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 an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be capable of controlling the flow rate adjustment operation of various gases by the MFCs 241a to 241f, the opening and closing operations of the valves 243a to 243f, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the power supply by the high frequency power source 273, the impedance adjustment operation by the matching device 272, 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, etc., in accordance with the contents of the read recipe.

[0030] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 in a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory. The storage device 121c and the external storage device 123 are configured as computer-readable recording media on which a program is recorded. Hereinafter, these are collectively referred to as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] (2) Substrate processing An example of etching at least a part of a film formed on a surface of a wafer 200 as one step of a semiconductor device manufacturing process using the above-mentioned processing furnace 202 will be described with reference to Fig. 4. In the following description, the operation of each part constituting the processing furnace 202 can be controlled by the controller 121.

[0032] In this specification, for convenience, the substrate processing sequence shown in Fig. 4 may be expressed as follows: Similar notations will be used in the following description.

[0033] (First fluorine-containing gas → reaction gas) × n → second fluorine-containing gas × m → modifier

[0034] The term "wafer" used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0035] (Wafer charge and boat load) A plurality of wafers 200 on which a film to be etched is formed are loaded (wafer charge) into a boat 217. Thereafter, the boat 217 supporting the plurality of wafers 200 is lifted by a boat elevator 115 and carried into the processing chamber 201 (boat load).

[0036] (Pressure and temperature regulation) The inside of the processing chamber 201, i.e., the space in which the wafer 200 exists, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so as to reach a desired processing pressure (vacuum level). The wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature. The rotation mechanism 267 also starts to rotate the wafer 200. The operation of the vacuum pump 246 and the heating and rotation of the wafer 200 continue at least until the processing of the wafer 200 is completed.

[0037] In this specification, the process temperature means the temperature of the wafer 200 or the temperature inside the process chamber 201, and the process pressure means the pressure inside the process chamber 201. Furthermore, the process time means the time the process continues. These terms also apply to the following explanations.

[0038] Thereafter, the following steps S11 to S20 are performed on the wafer 200 on which the film to be etched is formed.

[0039] Here, examples of the film to be etched include metal oxide films and metal nitride films. Examples of the metal elements contained in the metal oxide film and metal nitride film include aluminum (Al), zirconium (Zr), hafnium (Hf), titanium (Ti), yttrium (Y), lanthanum (La), tantalum (Ta), niobium (Nb), ruthenium (Ru), vanadium (V), zinc (Zn), manganese (Mn), cobalt (Co), indium (In), and gallium (Ga). The metal oxide film and metal nitride film may be films containing two or more of these metal elements. In particular, the technology disclosed herein can be suitably applied when etching high dielectric constant films (high-k films) such as aluminum oxide (Al2O3) film, zirconium oxide (ZrO2) film, hafnium oxide (HfO2) film, titanium oxide (TiO2) film, lanthanum oxide (La2O3) film, and tantalum oxide (Ta2O5) film.

[0040] (First fluorine-containing gas supply, step S11) In this step, a first fluorine-containing gas is supplied to the wafers 200 in the processing chamber 201. Specifically, the valve 243a is opened to allow the first fluorine-containing gas to flow into the gas supply pipe 232a. The first fluorine-containing gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the valves 243d to 243f are opened to allow an inert gas to flow into the gas supply pipes 232d to 232f.

[0041] In this step, the first fluorine-containing gas is supplied to the wafer 200 on which the film to be etched is formed. As a result, at least a part of the atomic layer on the top surface of the wafer 200 is converted into a substance containing F. That is, the atomic layer on the top surface of the film on the wafer 200 is modified into a layer containing F or the like.

[0042] The processing conditions for supplying the first fluorine-containing gas in this step are as follows: Processing temperature: 200~900℃ Processing pressure: 10~7000Pa Each gas supply time: 20 to 1000 seconds Treatment partial pressure of first fluorine-containing gas: 10 to 4000 Pa The processing temperature is substantially the same in each of the steps described below.

[0043] In this disclosure, the supply time of a certain gas means the time during which the gas is supplied to the wafer 200 or the inside of the processing chamber 201. In addition, the processing partial pressure of a certain gas means the partial pressure of the gas in the processing chamber 201. These terms also apply to the following explanations.

[0044] As the first fluorine-containing gas, for example, at least one of fluorine (F2), nitrogen trifluoride (NF3), hydrogen fluoride (HF), carbon tetrafluoride (CF4), tungsten hexafluoride (WF6), chlorine trifluoride (ClF3), sulfur tetrafluoride (SF4), xenon difluoride (XeF2), etc. can be used. As the first fluorine-containing gas, one or more of these can be used. In addition, it is preferable to use a gas that does not contain a metal element as the first fluorine-containing gas. This makes it difficult for impurities derived from the first fluorine-containing gas to be contained in the film, and the electrical properties of the film can be improved. In addition, it is preferable to use a gas that contains F and an element that does not constitute a film by itself, such as F2, NF3, HF, XeF2, etc., as the first fluorine-containing gas. This makes it possible to further reduce the amount of impurity elements contained in the film, and therefore it is possible to suppress the deterioration of the electrical properties of the film.

[0045] As the inert gas, in addition to nitrogen (N2) gas, rare gases such as argon (Ar), helium (He), neon (Ne), xenon (Xe), etc., can be used. As the inert gas, one or more of these can be used.

[0046] (Exhaust, step S12) The valve 243a is closed to stop the supply of the first fluorine-containing gas. At this time, the APC valve 244 of the exhaust pipe 231 is left open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. This removes residual gas, for example, unreacted first fluorine-containing gas and reaction by-products remaining on the wafer 200 and / or in the processing chamber 201, from the inside of the processing chamber 201. At this time, the valves 243d to 243f may be left open to maintain the supply of an inert gas into the processing chamber 201, thereby purging the inside of the processing chamber 201. The inert gas acts as a purge gas, and can enhance the effect of removing the residual gas from above the wafer 200.

[0047] In this step, it is preferable to evacuate and purge the processing chamber 201, which is the space in which the wafer 200 exists. This can reduce the amount of impurities contained in the film after the etching process. In other words, it is possible to suppress the deterioration of the electrical properties of the film due to the impurities in the film.

[0048] The conditions for evacuation in this step are as follows: Processing pressure: 10~200Pa Processing time: 10 to 180 seconds Examples include:

[0049] The purging conditions in this step are as follows: Processing pressure: 10~7000Pa Processing time: 30 to 180 seconds Examples include:

[0050] (Reaction gas supply, step S13) Next, a reactive gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243b is opened to allow the reactive gas to flow into the gas supply pipe 232b. The reactive gas has a flow rate adjusted by the MFC 241b, is supplied into the processing chamber 201 through the nozzle 249b, and is exhausted from the exhaust pipe 231. At this time, the valves 243d to 243f are opened to allow an inert gas to flow into the gas supply pipes 232d to 232f.

[0051] In this step, the reactive gas is supplied to the wafer 200 having a layer of F-containing material formed on the surface. This allows at least a part of the F-containing material on the wafer 200 to be converted into a volatile product containing an element derived from the film to be etched. In other words, at least a part of the film on the wafer 200 can be removed.

[0052] The process conditions for supplying the reaction gas in this step are as follows: Processing pressure: 10~7000Pa Each gas supply time: 60 to 600 seconds Reactive gas partial pressure: 10~4000Pa Examples include:

[0053] As the reactive gas, for example, a gas containing a predetermined element and chlorine (Cl) can be used. As the predetermined element, for example, one or more of boron (B), carbon (C), sulfur (S), phosphorus (P), titanium (Ti), silicon (Si), aluminum (Al), tin (Sn), etc. can be used. As the gas containing these predetermined elements and Cl, for example, boron trichloride (BCl3), carbon tetrachloride (CCl4), thionyl chloride (SOCl2), sulfuryl chloride (SO2Cl2), phosgene (COCl2), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), titanium tetrachloride (TiCl4), silicon tetrachloride (SiCl4), chlorodimethylaluminum (C2H6AlCl), etc. can be used.

[0054] Moreover, a gas containing a predetermined element and an organic ligand can be used as the reaction gas. In this case, C contained in the organic ligand may be considered as one of the predetermined elements. As the gas containing the predetermined element and the organic ligand, for example, trimethylaluminum ((CH3)3Al), C2H6AlCl, tin(II) acetylacetonate (Sn(acac)2), etc. can be used. As the reaction gas, one or more of these gases can be used.

[0055] When a reaction gas containing a metalloid element or a metal element (e.g., B, Ti, Si, Al, Sn) is used as the predetermined element, the predetermined element is likely to remain in the film. According to the technology of the present disclosure, the amount of the predetermined element contained in the film can be reduced, and therefore the technology of the present disclosure can be suitably applied. Furthermore, among the metalloid elements or metal elements as the predetermined element, elements belonging to the second or third period (e.g., B, C, P, Si, Al) are easily removed by a fluorine-containing gas, and therefore the technology of the present disclosure can be suitably applied.

[0056] At this time, a substance (hereinafter, also referred to as substance X) containing a predetermined element contained in the reaction gas may be generated on the surface of the film. The substance X may be, for example, a simple substance of the predetermined element, a compound of oxygen and fluorine, an oxide, a compound of nitrogen and fluorine, or a nitride. Depending on the selection of the type of the predetermined element and the type of reaction gas, a volatile substance X may be generated. However, even in such a case, a part of the substance X may not be removed from the wafer 200, and the predetermined element may remain in the film. Depending on the selection of the type of the predetermined element and the type of reaction gas, the substance X may be removed from the wafer 200 as a volatile substance. However, even in such a case, a part of the substance X may not be removed from the wafer 200, and the predetermined element may remain in the film.

[0057] (Exhaust, step S14) The valve 243b is closed to stop the supply of the reactive gas. At this time, the APC valve 244 of the exhaust pipe 231 is left open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. This removes residual gas, for example, unreacted reactive gas and reaction by-products remaining on the wafer 200 and / or in the processing chamber 201, from the inside of the processing chamber 201. At this time, the valves 243d to 243f may be left open to maintain the supply of an inert gas into the processing chamber 201, thereby purging the inside of the processing chamber 201.

[0058] In this step, it is preferable to evacuate and purge the processing chamber 201, which is the space in which the wafer 200 exists. This makes it possible to reduce the amount of substance X contained in the film of the wafer 200 after the etching process. In other words, it is possible to prevent the electrical properties of the film from deteriorating due to the inclusion of a specific element in the film.

[0059] The conditions for evacuation and purging in this step may be the same as those exemplified as the conditions for evacuation and purging in step S12.

[0060] (Performed a predetermined number of times, step S15) By performing a cycle (hereinafter also referred to as an etching cycle) in which the above steps S11 to S14 are performed in this order a predetermined number of times (n times, n being an integer of 2 or more), at least a part of the film on the wafer 200 can be removed (hereinafter also referred to as etching). For example, n is 2 to 100.

[0061] In step S11 of the second or subsequent etching cycles, it is preferable to supply the first fluorine-containing gas under conditions in which the substance X is converted into a substance with a lower vapor pressure, thereby reducing the amount of the predetermined element remaining in the film to be etched.

[0062] Here, in the second and subsequent etching cycles, it is preferable to perform step S11 under conditions in which a part of the substance X containing the predetermined element that becomes an impurity is not removed from the wafer 200. This makes it possible to shorten the time required for the etching process. The substance X that remains on the wafer 200 without being removed in this step can be removed from the film in step S16, which will be described later. Therefore, it is possible to reduce the amount of the predetermined element remaining in the film to be etched while improving the throughput.

[0063] For example, in step S11 of the second or subsequent etching cycle, the exposure amount of the first fluorine-containing gas may be smaller than the exposure amount of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed. In such a case, step S11 can be performed under conditions in which a part of the substance X is not removed from the wafer 200.

[0064] Here, the "exposure amount of the first fluorine-containing gas in step S11" is calculated, for example, as "a value obtained by integrating the process partial pressure of the first fluorine-containing gas in the space (in the process chamber 201) in which the wafer 200 exists in step S11 by the time from the start to the end of step S11." Also, the "process partial pressure of the first fluorine-containing gas" is calculated, for example, as "the product of the mole fraction of the first fluorine-containing gas and the pressure (total pressure) in the space in which the wafer 200 exists at a certain time." Also, when the process partial pressure of the first fluorine-containing gas in the space in which the wafer 200 exists in step S11 can be considered to be constant, it is calculated as "the product of the process partial pressure of the first fluorine-containing gas and the time from the start to the end of step S11."

[0065] That is, in step S11 of the second or later etching cycle, the supply time of the first fluorine-containing gas may be shorter than the supply time of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed. Also, the process partial pressure of the first fluorine-containing gas may be lower than the process partial pressure of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed. By one or both of these, in step S11 of the second or later etching cycle, the exposure amount of the first fluorine-containing gas can be made smaller than the exposure amount of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed.

[0066] Furthermore, in step S11 of the second or subsequent etching cycle, the process pressure may be made higher than the process pressure of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed. Alternatively, the molar fraction of the first fluorine-containing gas in the process chamber 201 may be made higher than the molar fraction of the first fluorine-containing gas in the process chamber 201 when all of the substance X on the wafer 200 is removed. By one or both of these, in step S11 of the second or subsequent etching cycle, the process partial pressure of the first fluorine-containing gas can be made higher than the process partial pressure of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed.

[0067] Furthermore, in step S11 of the second or subsequent etching cycle, the supply flow rate of the first fluorine-containing gas may be set to be greater than the supply flow rate of the first fluorine-containing gas when all of the substance X on the wafer 200 is removed. Alternatively, the supply flow rate of the inert gas in this step may be set to be smaller than the supply flow rate of the inert gas when all of the substance X on the wafer 200 is removed. By using one or both of these, the molar fraction of the first fluorine-containing gas in the processing chamber 201 in step S11 of the second or subsequent etching cycle can be made higher than the molar fraction of the first fluorine-containing gas in the processing chamber 201 when all of the substance X on the wafer 200 is removed.

[0068] In this disclosure, the supply flow rate of a certain gas means the flow rate of that gas supplied to the wafer 200 or the processing chamber 201. This also applies to the following description.

[0069] In this embodiment, after the etching cycle is performed a predetermined number of times, the second fluorine-containing gas is supplied (S16).

[0070] (Second fluorine-containing gas supply, step S16) In this step, a second fluorine-containing gas is supplied to the wafers 200 in the processing chamber 201. Specifically, the valve 243a is opened to allow the second fluorine-containing gas to flow into the gas supply pipe 232a. The second fluorine-containing gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the valves 243d to 243f are opened to allow an inert gas to flow into the gas supply pipes 232d to 232f.

[0071] In this step, the second fluorine-containing gas is supplied to the wafer 200 under conditions in which the substance X is further converted into a substance with a lower vapor pressure. That is, in this step, the substance X containing the predetermined element is converted into a volatile substance and discharged from the processing chamber 201. This can further reduce the amount of the predetermined element contained in the film of the wafer 200, thereby improving the electrical properties of the film.

[0072] Here, it is preferable to make the exposure amount of the second fluorine-containing gas in this step larger than the exposure amount of the first fluorine-containing gas in the above-mentioned step S11. This can reduce the amount of a specific element that becomes an impurity contained in the film, and improve the electrical properties of the film. For example, when the first fluorine-containing gas is used as the second fluorine-containing gas, the exposure amount of the second fluorine-containing gas in this step is made larger than the exposure amount of the first fluorine-containing gas in the above-mentioned step S11. This can reduce the amount of a specific element contained in the film.

[0073] Here, the supply time of the second fluorine-containing gas in this step may be longer than the supply time of the first fluorine-containing gas in step S11. Alternatively, the processing partial pressure of the second fluorine-containing gas in this step may be higher than the processing partial pressure of the first fluorine-containing gas in step S11. By using one or both of these, the exposure amount of the second fluorine-containing gas in this step can be made larger than the exposure amount of the first fluorine-containing gas in step S11.

[0074] Here, the process pressure in this step may be set higher than the process pressure in step S11. Alternatively, the molar fraction of the second fluorine-containing gas in the process chamber 201 in this step may be set higher than the molar fraction of the first fluorine-containing gas in the process chamber 201 in step S11. By using one or both of these, the process partial pressure of the second fluorine-containing gas in this step can be set higher than the process partial pressure of the first fluorine-containing gas in step S11.

[0075] Here, the supply flow rate of the second fluorine-containing gas in this step may be set to be higher than the supply flow rate of the first fluorine-containing gas in step S11. Alternatively, the supply flow rate of the inert gas in this step may be set to be lower than the supply flow rate of the inert gas in step S11. By using one or both of these, the molar fraction of the second fluorine-containing gas in the processing chamber 201 in this step can be made higher than the molar fraction of the first fluorine-containing gas in the processing chamber 201 in step S11.

[0076] The processing conditions for supplying the second fluorine-containing gas in this step are as follows: Processing temperature: 200~900℃ Processing pressure: 10~10000Pa Each gas supply time: 20 to 1200 seconds Processing partial pressure of second fluorine-containing gas: 10 to 5000 Pa Examples include:

[0077] As the second fluorine-containing gas, for example, one or more of the gases exemplified as the first fluorine-containing gas can be used. Also, as the second fluorine-containing gas, the same type of gas as the first fluorine-containing gas (gas having the same molecular structure as the first fluorine-containing gas) can be used. This can simplify the gas supply system and the processing sequence. Also, as the second fluorine-containing gas, it is preferable to use a gas that does not contain a metal element. This makes it difficult for impurities derived from the second fluorine-containing gas to be contained in the film, and the electrical properties of the film can be improved. Also, as the second fluorine-containing gas, it is preferable to use a gas that contains F and an element that does not constitute a film by itself. This can further reduce the amount of impurity elements contained in the film, and therefore it is possible to suppress the deterioration of the electrical properties of the film.

[0078] (Exhaust, step S17) The valve 243a is closed to stop the supply of the second fluorine-containing gas. At this time, the APC valve 244 of the exhaust pipe 231 is left open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. This removes residual gas, for example, unreacted second fluorine-containing gas remaining on the wafer 200 and / or in the processing chamber 201 and reaction by-products from the inside of the processing chamber 201. At this time, the valves 243d to 243f may be left open to maintain the supply of an inert gas into the processing chamber 201, thereby purging the inside of the processing chamber 201.

[0079] In this step, it is preferable to evacuate and purge the processing chamber 201, which is the space in which the wafer 200 exists. This makes it possible to reduce the amount of substance X contained in the film of the wafer 200 after the etching process. In other words, it is possible to prevent the electrical properties of the film from deteriorating due to the inclusion of a specific element in the film.

[0080] The conditions for evacuation and purging in this step may be the same as those exemplified as the conditions for evacuation and purging in step S12.

[0081] (Performed a predetermined number of times, step S18) The cycle of performing the above steps S16 to S17 in this order is repeated a predetermined number of times (m times, where m is an integer of 1 or 2 or more).

[0082] In this embodiment, after steps S11 to S18, a modifying agent supplying step (S19) may be performed to remove a substance (hereinafter, referred to as substance Y) containing a predetermined element such as F contained in the film of the next wafer 200.

[0083] (Modifier supply, step S19) Next, a modifying agent for removing the substance Y contained in the film of the wafer 200 is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243c is opened to allow the modifying agent to flow into the gas supply pipe 232c. The modifying agent has a flow rate adjusted by the MFC 241c, is supplied into the processing chamber 201 via the nozzle 249c and the buffer chamber 237, and is exhausted from the exhaust pipe 231. At this time, the valves 243d to 243f are opened to allow an inert gas to flow into the gas supply pipes 232d to 232f.

[0084] Supplying the modifier removes the substance Y contained in the film of the wafer 200. This makes it possible to remove the substance Y contained in the film of the wafer 200 after steps S11 to S18 described above. This makes it possible to reduce the amount of impurities such as F contained in the film on the wafer 200, thereby improving the electrical characteristics of the film.

[0085] Here, the modifying agent may be in a liquid phase or a gas phase. For example, an oxidizing gas or the like can be used as the modifying agent. In this embodiment, an example in which an oxidizing gas is used as the modifying agent will be described.

[0086] In this step, the processing conditions for supplying the oxidizing gas to the wafer 200 are as follows: Processing temperature: 300~1000℃ Processing pressure: 10~1000Pa Gas supply time: 0.5~10h Examples include:

[0087] As the oxidizing gas, for example, a gas containing oxygen (O) and hydrogen (H) can be used. As the O and H containing gas, for example, water vapor (H2O), hydrogen peroxide (H2O2), formic acid (HCOOH), hydrogen (H2) + oxygen (O2), H2 + ozone (O3), etc. can be used. In addition to the O and H containing gas, for example, a gas containing oxygen (O) can be used as the oxidizing gas. As the O containing gas, for example, O2, O3, nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), carbon dioxide (CO2), etc. can be used. Note that the O and H containing gas is also a type of O containing gas. As the oxidizing gas, one or more of these can be used. When the O and H containing gas is used as the oxidizing gas, it is possible to suppress excessive oxidation of the film on the wafer 200 and its underlying film.

[0088] In this specification, the description of two gases together, such as "H2+O2", means a mixed gas of H2 and O2. When supplying a mixed gas, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be separately supplied into the processing chamber 201 through different supply pipes and mixed (postmixed) in the processing chamber 201.

[0089] (Exhaust, step S20) The valve 243c is closed to stop the supply of the modifying agent. At this time, the APC valve 244 of the exhaust pipe 231 is left open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246. This removes residual gas, for example, unreacted modifying agent and reaction by-products remaining on the wafer 200 and / or in the processing chamber 201, from the inside of the processing chamber 201. At this time, the valves 243d to 243f may be left open to maintain the supply of an inert gas into the processing chamber 201, thereby purging the inside of the processing chamber 201.

[0090] The conditions for evacuation and purging in this step may be the same as those exemplified as the conditions for evacuation and purging in step S12.

[0091] (After purging and atmospheric pressure recovery) An inert gas is supplied into the processing chamber 201 from each of the gas supply pipes 232d to 232f, and exhausted from the exhaust pipe 231. This causes the processing chamber 201 to be purged, and residual gas and reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purging). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0092] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115 to open the bottom end of the reaction tube 203. Then, the processed wafers 200 supported by the boat 217 are unloaded from the bottom end of the reaction tube 203 to the outside of the reaction tube 203 (boat unloading). The processed wafers 200 are removed from the boat 217 (wafer discharging).

[0093] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0094] (Modification) This modification is different from the above-mentioned substrate processing step in the modifying agent supplying step (S19). This modification can provide the same effects as the above-mentioned embodiment.

[0095] In this modification, in the above-described modifying agent supplying step (S19), a modifying agent activated by plasma is used instead of a modifying agent activated by heat, that is, a plasma treatment is performed.

[0096] Specifically, the valve 243c is opened to allow the modifying agent to flow into the gas supply pipe 232c. The modifying agent has a flow rate adjusted by the MFC 241c, is plasma-excited in the nozzle 249c and the buffer chamber 237, and is supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, the modifying agent activated by plasma excitation is supplied to the wafer 200. At the same time, the valves 243d to 243f are opened to allow an inert gas to flow into the gas supply pipes 232d to 232f.

[0097] In this step, the processing conditions for supplying the plasma-activated modifier are as follows: Processing pressure: 1~100Pa Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Modifier treatment partial pressure: 0.01 to 100 Pa High frequency power: 50~1000W Examples include:

[0098] The substrate processing sequence of this modified example can be shown as follows. For convenience, the modifier activated by plasma is referred to as modifier * This indicates that.

[0099] (First fluorine-containing gas → reaction gas) × n → second fluorine-containing gas × m → modifier *

[0100] As the modifier, for example, reactive species generated by activating a gas containing at least one of a rare gas, an O-containing gas, and an H-containing gas by plasma can be used. This allows the substance Y contained in the film to be desorbed and removed. Therefore, the amount of impurities contained in the film can be reduced, and the electrical properties of the film can be improved.

[0101] The rare gas may be, for example, one or more of Ar, He, Ne, Xe, etc. The O-containing gas may be, for example, one or more of O2, O3, N2O, NO, NO2, CO, CO2, H2O, H2O2, H2+O2, H2+O3, etc. The H-containing gas may be, for example, one or more of H2, H2O, H2O2, H2+O2, H2+O3, etc.

[0102] (Other Aspects) In the above embodiment, the first fluorine-containing gas supply step (S11) to the exhaust step (S20) are performed continuously (in situ) in the same processing chamber 201, but the first fluorine-containing gas supply step (S11) to the predetermined number of times execution step (S18) and the modifier supply step (S19) to the exhaust step (S20) may be performed in different processing chambers (ex situ). In this embodiment, the same effects as those in the above embodiment can be obtained. In addition, when the first fluorine-containing gas supply step (S11) to the exhaust step (S20) are performed in the same processing chamber 201, the time required for transporting the wafer 200 between the processing chambers is further reduced, thereby improving productivity.

[0103] In the above description, the process of etching a film formed on the wafer 200 has been described as an example. However, the present disclosure is not limited to this. For example, the technology of the present disclosure can be suitably applied to a process of etching a film formed on the surface of the inner wall of the processing chamber 201, the boat 217, etc. (cleaning process in the processing chamber 201). For example, the technology of the present disclosure can be suitably applied to a case where a process of forming a film on the wafer 200 is performed in the processing chamber 201 and the film is etched in the processing chamber 201. In these embodiments, the same effects as those of the above-mentioned embodiment can be obtained.

[0104] In the above description, the etching cycle is performed in the order of the first fluorine-containing gas supply step (S11), the exhaust step (S12), the reactive gas supply step (S13), and the exhaust step (S14). However, the present disclosure is not limited to this. For example, the etching cycle may be performed in the order of the reactive gas supply step (S13), the exhaust step (S14), the first fluorine-containing gas supply step (S11), and the exhaust step (S12). In this embodiment, the same effect as the above embodiment can be obtained.

[0105] It is preferable that the recipes used for the substrate processing are prepared individually according to the processing contents and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting the substrate processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the processing contents from among the multiple recipes stored in the storage device 121c. This makes it possible to process films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility in the substrate processing device. In addition, it is possible to reduce the burden on the operator and quickly start the substrate processing while avoiding operational errors.

[0106] The above-mentioned recipes may not only be newly created, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. In addition, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0107] In the above-mentioned embodiment, an example of using a batch-type substrate processing apparatus that processes a plurality of substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment. For example, the present disclosure can be suitably applied to a case where a single-wafer type substrate processing apparatus that processes one or several substrates at a time is used. In addition, in the above-mentioned embodiment, an example of using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment. For example, the present disclosure can be suitably applied to a case where a substrate processing apparatus having a cold-wall type processing furnace is used.

[0108] When using these substrate processing apparatuses, the film formation process can be performed under the same processing procedures and processing conditions as those in the above-mentioned aspects and modifications, and the same effects as those in the above-mentioned aspects and modifications can be obtained.

[0109] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in this case may be the same as those of the above-mentioned aspects and modifications.

[0110] Examples will now be described. EXAMPLES

[0111] As shown in Fig. 5(A), Samples 1 to 3 were prepared in which a metal oxide film 300 was formed on the surface of a wafer 200. Sample 1 was a wafer 200 in which a metal oxide film 300 was formed on the surface. Sample 2 was a wafer 200 in which a metal oxide film 300 was formed on the surface under the same conditions as Sample 1, to which a reactive gas was supplied using the above-mentioned substrate processing apparatus, and then a fluorine-containing gas was supplied. Sample 3 was a wafer 200 in which a metal oxide film 300 was formed on the surface under the same conditions as Sample 1, to which a reactive gas was supplied using the above-mentioned substrate processing apparatus.

[0112] Fig. 5(B) shows the results of analyzing the concentration of a predetermined element in the metal oxide film 300 of each of Samples 1 to 3 by secondary ion mass spectrometry (SIMS). The processing conditions in each step in producing Samples 2 and 3 were set to predetermined processing conditions within the range of processing conditions in each step of the above-mentioned embodiment. The horizontal axis of Fig. 5(B) shows the depth from the surface of the metal oxide film 300, and the vertical axis shows the concentration of the predetermined element.

[0113] Comparing Sample 1 and Sample 3, it can be seen that Sample 3 has a higher concentration of the predetermined element near the surface of the metal oxide film 300. This shows that the predetermined element is incorporated into the metal oxide film 300 by supplying a reactive gas.

[0114] Moreover, when Sample 2 and Sample 3 are compared, it can be seen that Sample 2 has a lower concentration of the predetermined element near the surface of the metal oxide film 300. This shows that the supply of the fluorine-containing gas removes a part of the substance containing the predetermined element that was incorporated into the metal oxide film 300.

[0115] Therefore, as explained in the substrate processing process in the above-mentioned embodiment, it can be seen that the amount of a specific element contained in the film can be reduced by supplying a fluorine-containing gas after supplying a fluorine-containing gas and a reactive gas two or more times. [Explanation of symbols]

[0116] 200 wafers (substrates)

Claims

1. (a) as (a1) supplying a first fluorine-containing gas to a substrate; (a2) supplying a reaction gas containing a predetermined element to the substrate; two or more cycles comprising the steps of: removing at least a portion of the film on the substrate; (b) after (a), supplying a second fluorine-containing gas to the substrate; In (a), a substance X containing the predetermined element is generated; In (b), the second fluorine-containing gas is supplied under conditions in which the substance X is further converted into a substance with a lower vapor pressure. A method for processing a substrate.

2. 2. The substrate processing method according to claim 1, wherein in (a1), the first fluorine-containing gas is supplied under conditions in which the substance X is further converted into a substance with a lower vapor pressure.

3. The method for processing a substrate according to claim 2 , wherein (a1) is carried out under conditions in which a portion of the substance X is not removed from the substrate.

4. 4. The substrate processing method according to claim 3, wherein in (a1), an exposure amount of the first fluorine-containing gas is set to be smaller than an exposure amount of the first fluorine-containing gas when all of the substance X on the substrate is removed.

5. 5. The substrate processing method according to claim 4, wherein in (a1), a supply time of the first fluorine-containing gas is set shorter than a supply time of the first fluorine-containing gas when all of the substance X on the substrate is removed.

6. 5. The substrate processing method according to claim 4, wherein in (a1), a process partial pressure of the first fluorine-containing gas is set lower than a process partial pressure of the first fluorine-containing gas when all of the substance X on the substrate is removed.

7. 2. The substrate processing method according to claim 1, wherein an exposure amount of the second fluorine-containing gas in (b) is set to be greater than an exposure amount of the first fluorine-containing gas in (a1).

8. 8. The substrate processing method according to claim 7, wherein a supply time of the second fluorine-containing gas in (b) is set longer than a supply time of the first fluorine-containing gas in (a1).

9. 8. The substrate processing method according to claim 7, wherein a process partial pressure of the second fluorine-containing gas in (b) is set higher than a process partial pressure of the first fluorine-containing gas in (a1).

10. 2. The method of claim 1, wherein the second fluorine containing gas is the first fluorine containing gas.

11. 2. The substrate processing method according to claim 1, wherein the second fluorine-containing gas is a gas that does not contain a metal element.

12. The substrate processing method according to claim 1 , wherein the predetermined element is a metal element or a semi-metal element.

13. The substrate processing method according to claim 1 , further comprising the step of: (c) after (b), supplying to the substrate a modifier that removes substances containing fluorine on the substrate.

14. The substrate processing method according to claim 13 , wherein (a), (b) and (c) are carried out in the same processing chamber.

15. The substrate processing method according to claim 13 , wherein the modifying agent is an oxidizing gas.

16. 14. The substrate processing method according to claim 13, wherein the modifying agent is a reactive species generated by activating a gas containing at least one of a rare gas, an oxygen-containing gas, and a hydrogen-containing gas with plasma.

17. (a) as (a1) supplying a first fluorine-containing gas to a substrate; (a2) supplying a reaction gas containing a predetermined element to the substrate; two or more cycles comprising the steps of: removing at least a portion of the film on the substrate; (b) after (a), supplying a second fluorine-containing gas to the substrate; In (a), a substance X containing the predetermined element is generated; In (b), the second fluorine-containing gas is supplied under conditions in which the substance X is further converted into a substance with a lower vapor pressure. A method for manufacturing a semiconductor device.

18. a first fluorine-containing gas supply system for supplying a first fluorine-containing gas; a reaction gas supply system for supplying a reaction gas containing a predetermined element; a second fluorine-containing gas supply system for supplying a second fluorine-containing gas; (a) as (a1) supplying the first fluorine-containing gas to a substrate; (a2) supplying the reaction gas to the substrate; a process for removing at least a portion of the film on the substrate by performing a cycle including the steps of: (b) after (a), supplying the second fluorine-containing gas to the substrate; In (a), a substance X containing the predetermined element is generated; (b) a process of supplying the second fluorine-containing gas under conditions in which the substance X is further converted into a substance having a lower vapor pressure; a control unit configured to be able to control the first fluorine-containing gas supply system, the reaction gas supply system, and the second fluorine-containing gas supply system so that A substrate processing apparatus comprising:

19. (a) as (a1) supplying a first fluorine-containing gas to a substrate; (a2) supplying a reaction gas containing a predetermined element to the substrate; two or more cycles comprising the steps of: (b) after (a), supplying a second fluorine-containing gas to the substrate; In (a), a substance X containing the predetermined element is generated; (b) supplying the second fluorine-containing gas under conditions in which the substance X is further converted into a substance with a lower vapor pressure; A program for causing a computer to execute the above in a substrate processing apparatus.

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