Substrate processing method, method of manufacturing semiconductor device, substrate processing apparatus, and recording medium

Abstract

The invention relates to a substrate processing method, a method of manufacturing a semiconductor device, a substrate processing apparatus, and a recording medium. Provided is a technique capable of improving controllability of an etching amount. Comprising the steps of: (a1) supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X, and forming a first product containing the first halogen element and the element X on the substrate by performing a cycle of (a1) and (b1) in this order for a predetermined number of times to remove at least a portion of the substance Y from the substrate; (b1) a step in which a second gas containing a second halogen element is supplied to the substrate, and at least a portion of the first product is converted into a second product containing the element X and having a higher vapor pressure than the first product; (b1) is carried out under conditions such that at least a portion of the substance (Y) can be removed from the substrate when the second gas is supplied to the substance (Y) having no first halogen element present on the surface thereof.

Description

Technical Field

[0001] The present invention relates to a substrate processing method, a method for manufacturing a semiconductor device, a substrate processing apparatus and a recording medium. Background Art

[0002] As one of the steps in the process of manufacturing a semiconductor device, a step of etching a film by performing a cycle of supplying different types of gases a predetermined number of times is sometimes performed (for example, see Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-158142 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention provides a technology capable of improving the controllability of etching amount.

[0008] Means for solving problems

[0009] According to one embodiment of the present invention, there is provided a technique comprising performing a cycle of (a1) and (b1) in sequence a predetermined number of times, thereby removing at least a portion of a substance Y from a substrate, wherein:

[0010] (a1) is a step of supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X, thereby forming a first product containing the first halogen element and the element X on the substrate.

[0011] (b1) is a step of supplying a second gas containing a second halogen element to the substrate to convert at least a portion of the first product into a second product containing the element X and having a higher vapor pressure than the first product,

[0012] When the second gas is supplied to the substance Y having no first halogen element on the surface, (b1) is performed under conditions that at least a portion of the substance Y can be removed from the substrate.

[0013] Effects of the Invention

[0014] According to the present invention, the controllability of the etching amount can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and shows a processing furnace portion in a longitudinal cross-sectional view.

[0016] Figure 2 This is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller in the form of a block diagram.

[0017] Figure 3 This is a flowchart showing a substrate processing step according to one embodiment of the present invention.

[0018] Figure 4 (A) is a schematic diagram of supplying the first gas to the concave portion on the substrate; Figure 4 (B) is a schematic diagram showing when the surface of the substance on the substrate is converted into the first product by the first gas; Figure 4 (C) in the sentence is Figure 4 A schematic diagram of the state (B) of the substrate when the second gas is supplied; Figure 4 (D) in FIG. 1 is a schematic diagram showing a case where a part of the first product is converted into a second product having a higher vapor pressure than the first product.

[0019] Description of Reference Numerals

[0020] 200 wafers (substrate) DETAILED DESCRIPTION

[0021] <One embodiment of the present invention>

[0022] The following mainly refers to Figure 1 to Figure 4 One embodiment of the present invention is described. It should be noted that the drawings used in the following description are schematic, and the relationship between the dimensions of the elements shown in the drawings, the ratio of the elements, etc. may not be consistent with reality. In addition, the relationship between the dimensions of the elements, the ratio of the elements, etc. may not be consistent between multiple drawings.

[0023] (1) Configuration of substrate processing apparatus

[0024] like Figure 1 As shown, a processing furnace 202 as a substrate processing device has a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat. A reaction tube 203 is arranged inside the heater 207. A processing chamber 201 capable of accommodating a wafer 200 as a substrate is formed in the hollow portion of the reaction tube 203. The wafer 200 is processed in the processing chamber 201. In the processing chamber 201, nozzles 249a and 249b are arranged in a manner that penetrates the lower side wall of the reaction tube 203. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively.

[0025] On the gas supply pipes 232a and 232b, mass flow controllers (MFCs) 241a and 241b as flow controllers (flow control units) and valves 243a and 243b as opening and closing valves are respectively provided in sequence from the upstream side of the gas flow. Gas supply pipes 232c and 232e are respectively connected to the downstream side of the gas supply pipe 232a relative to the valve 243a. Gas supply pipe 232d is connected to the downstream side of the gas supply pipe 232b relative to the valve 243b. On the gas supply pipes 232c, 232d, and 232e, MFCs 241c, 241d, and 241e and valves 243c, 243d, and 243e are respectively provided in sequence from the upstream side of the gas flow.

[0026] The nozzles 249a and 249b are respectively provided in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, so as to stand up from the lower part of the inner wall of the reaction tube 203 along the upper part toward the upper side of the arrangement direction of the wafer 200. Gas supply holes 250a and 250b for supplying gas are respectively provided on the side surfaces of the nozzles 249a and 249b. The gas supply holes 250a and 250b are respectively opened toward the center of the reaction tube 203, and can supply gas toward the wafer 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.

[0027] The first gas including the first halogen element is supplied into the processing chamber 201 from the gas supply pipe 232 a via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0028] The second gas containing the second halogen element is supplied into the processing chamber 201 from the gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the nozzle 249 b .

[0029] Inert gas is supplied from gas supply pipes 232c and 232d into the processing chamber 201 via MFCs 241c and 241d, valves 243c and 243d, gas supply pipes 232a and 232b, and nozzles 249a and 249b. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0030] A modifier is supplied from the gas supply pipe 232e via the MFC 241e, the valve 243e, the gas supply pipe 232a, and the nozzle 249a into the processing chamber 201. The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. It should be noted that 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.

[0031] The first gas supply system for supplying the first gas is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The second gas supply system for supplying the second gas is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The inert gas supply system for supplying the inert gas is mainly composed of the gas supply pipes 232c, 232d, MFC241c, 241d, valves 243c, 243d. The modifier supply system for supplying the modifier is mainly composed of the gas supply pipe 232e, MFC241e, and valve 243e.

[0032] Any one or all of the above-mentioned various supply systems may also be configured as an integrated supply system 248 in which valves 243a to 243e, MFCs 241a to 241e, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232e, and is configured to control the supply of various gases to the gas supply pipes 232a to 232e, i.e., the opening and closing of the valves 243a to 243e, the flow rate adjustment based on the MFCs 241a to 241e, etc., through the controller 121 described later.

[0033] An exhaust pipe 231 for exhausting the atmosphere in 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 regulation unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust and vacuum exhaust stop in the processing chamber 201. Furthermore, while the vacuum pump 246 is in operation, the valve opening is adjusted based on the pressure information detected by the pressure sensor 245, thereby enabling the pressure in the processing chamber 201 to be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the pressure sensor 245, and the APC valve 244. The vacuum pump 246 may also be included in the exhaust system.

[0034] A sealing cover 219 capable of hermetically sealing the lower end opening of the reaction tube 203 is provided below the reaction tube 203. An O-ring 220 as a sealing member abutting against the lower end of the reaction tube 203 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating a wafer boat 217 described later is provided below the sealing cover 219. A rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by a wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The wafer boat elevator 115 is configured as a conveying device (conveying mechanism) for carrying in and out (conveying) the wafer 200 into and out of the processing chamber 201 by lifting and lowering the sealing cover 219.

[0035] The wafer boat 217 as a substrate support is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal posture and arranged in a vertical direction with their centers aligned with each other in multiple layers, that is, arranged at intervals. At the lower part of the wafer boat 217, a heat insulation plate 218 is supported in a horizontal posture in multiple layers. It should be noted that the expression of a numerical range such as "25 to 200 sheets" in the present invention means that the lower limit and the upper limit are included in the range. Therefore, "25 to 200 sheets" means "more than 25 sheets and less than 200 sheets". The same applies to other numerical ranges.

[0036] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is set to a desired temperature distribution by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263.

[0037] like Figure 2As shown, the controller 121 as a control unit (control mechanism) is configured as a computer having a CPU (Central Processing Unit; Central Processing Unit) 121a, a RAM (Random Access Memory; Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. RAM121b, a storage device 121c, and an I / O port 121d are configured to be able to exchange data with the CPU121a via an internal bus 121e. An input and output device 122 such as a touch panel is connected to the controller 121. In addition, an external storage device 123 can be connected to the controller 121. It should be noted that the substrate processing device can have one control unit or multiple control units. That is, the control for performing the substrate processing process described later can be performed using one control unit or multiple control units. When the term control unit is used in this specification, in addition to the case where one control unit is included, multiple control units are sometimes included.

[0038] 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 device, a process recipe recording the steps and conditions of the etching process described later, etc., are stored in a readable manner in the storage device 121c. The process recipe is a combination of a method that enables the controller 121 to execute each step in the etching process described later and obtain a specified result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are also collectively referred to as a program. In addition, the process recipe is also referred to as a recipe. When the term "program" is used in this specification, sometimes only the recipe is included alone, sometimes only the control program is included alone, or sometimes both are included. RAM121b is configured as a memory area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0039] The I / O port 121 d is connected to the above-mentioned MFCs 241 a to 241 e , valves 243 a to 243 e , pressure sensor 245 , APC valve 244 , vacuum pump 246 , temperature sensor 263 , heater 207 , rotation mechanism 267 , boat elevator 115 , and the like.

[0040] The CPU 121a is configured to read and execute a control program from the storage device 121c, and read a process from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control flow rate adjustment operations of various gases by the MFCs 241a to 241e, opening and closing operations of the valves 243a to 243e, opening and closing operations of the APC valve 244 and pressure adjustment operations by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 by the temperature sensor 263, rotation of the wafer boat 217 and rotation speed adjustment operations by the rotation mechanism 267, and lifting and lowering operations of the wafer boat 217 by the wafer boat elevator 115, etc., according to the contents of the read process.

[0041] The controller 121 can be constructed by installing the above-mentioned program stored in the external storage device 123 into the computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory, etc. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium on which a program is recorded. Hereinafter, they are also collectively referred to as recording media. When the term "recording medium" is used in this specification, sometimes only the storage device 121c is included alone, sometimes only the external storage device 123 is included alone, or sometimes both are included. In addition, the provision of the program to the computer can also be carried out without using the external storage device 123, but using a communication unit such as the Internet or a dedicated line.

[0042] (2) Substrate processing step

[0043] use Figure 3 and Figure 4 , an example of etching a substance Y containing an element X formed on the surface of a concave portion of a wafer 200 using the processing furnace 202 of the substrate processing apparatus as one of the steps of manufacturing a semiconductor device will be described. In the following description, the operations of the various components constituting the substrate processing apparatus are configured to be controllable by the controller 121.

[0044] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer, etc. formed on the wafer. When the term "a predetermined layer is formed on the wafer" is recorded in this specification, it may refer to a case where a predetermined layer is directly formed on the surface of the wafer itself or to a case where a predetermined layer is formed on a layer, etc. The use of the term "substrate" in this specification is also synonymous with the use of the term "wafer".

[0045] (Wafer filling and wafer boat loading)

[0046] A plurality of wafers 200 having a substance Y to be etched are loaded into the wafer boat 217 (wafer filling). Then, the wafer boat 217 supporting the plurality of wafers 200 is lifted by the wafer boat elevator 115 and carried into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 is in a state of sealing the lower end of the reaction tube 203 via the O-ring 220.

[0047] (Pressure regulation and temperature regulation)

[0048] The vacuum pump 246 performs vacuum exhaust (decompression exhaust) to make the space in the processing chamber 201, that is, the space where the wafer 200 exists, to be at the desired processing pressure (vacuum degree). In addition, the heater 207 performs heating to make the wafer 200 in the processing chamber 201 to be at the desired processing temperature. In addition, the rotation of the wafer 200 by the rotation mechanism 267 is started. The operation of the vacuum pump 246 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0049] In this specification, the processing temperature refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the time during which the processing is continued. This also applies to the following description.

[0050] Thereafter, the substance Y formed on the wafer 200 is subjected to the following steps S11 to S19 .

[0051] Here, as the material Y to be etched, for example, oxide films, nitride films, carbide films, etc. As the oxide film, for example, at least one metal oxide film (oxide film containing a metal element) selected from aluminum oxide (Al2O3) film, zirconium oxide (ZrO2) film, hafnium oxide (HfO2) film, silicon oxide (SiO2) film, titanium oxide (TiO2) film, yttrium oxide (Y2O3) film, lanthanum oxide (La2O3) film, tantalum oxide (Ta2O5) film, niobium oxide (Nb2O5, Nb2O3, NbO) film, ruthenium oxide (RuO2, RuO) film, vanadium oxide (V2O5) film, zinc oxide (ZnO) film, manganese oxide (MnO, Mn2O3) film, cobalt oxide (CoO) film, etc. can be cited.

[0052] (First Gas Supply, Step S11)

[0053] In this step, the first gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243a is opened, and the first gas flows into the gas supply pipe 232a. The first gas is flow-regulated by the MFC 241a, supplied to the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the valves 243c and 243d are opened, and the inert gas flows into the gas supply pipes 232c and 232d.

[0054] In this step, if Figure 4 As shown in (A) of FIG. 1 , a first gas containing a first halogen element is supplied to a wafer 200 having a surface of a substance Y containing an element X. Thus, as Figure 4 As shown in (B) in FIG. 2 , for example, one atomic layer of substance Y on the wafer 200 is modified into a first product Z1 including a first halogen element and element X, thereby forming the first product Z1 on the wafer 200 .

[0055] This step is preferably performed under the condition that the amount of the first product Z1 formed is saturated. In other words, in this step, the formation of the first product Z1 is preferably self-controlled. In this case, the difference in the amount of the first product Z1 formed can be reduced between the opening side and the deep side of the concave portion of the wafer 200. As a result, the uniformity of the etching amount in the concave portion of the wafer 200 can be improved.

[0056] As the processing conditions when the first gas is supplied in this step, the following can be exemplified:

[0057] Processing temperature: 200~900℃

[0058] Processing pressure: 10~7000Pa

[0059] Each gas supply time: 20 to 600 seconds

[0060] Partial pressure of the first gas: 10~4000Pa.

[0061] In addition, the processing temperature is set to substantially the same temperature in any steps described below.

[0062] In addition, when the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied. This is also the same in other descriptions of the present invention.

[0063] As the first gas, a F-containing gas containing fluorine (F) as the first halogen element can be used. As the F-containing gas, for example, at least one of fluorine (F2) gas, nitrogen trifluoride (NF3) gas, hydrogen fluoride (HF) gas, carbon tetrafluoride (CF4) gas, tungsten hexafluoride (WF6) gas, etc. can be used. In addition, as the first gas, for example, a hydrogen compound can be used. As the hydrogen compound, for example, HF gas can be used. As the first gas, one or more of them can be used.

[0064] As the inert gas, in addition to nitrogen (N2) gas, rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of them can be used.

[0065] Specifically, for example, when the etching target material Y is set to an Al2O3 film and HF gas is used as the first gas, the Al2O3 on the surface of the wafer 200 reacts with HF by the supply of HF gas, and a part of Al and a part of O are separated from the Al2O3 and replaced by F, and converted into AlOF and AlF3. In addition, O separated from the Al2O3 combines with H to generate water vapor (H2O gas). Then, H2O is separated from the surface of the wafer 200 and discharged from the processing chamber 201, thereby the surface of the Al2O3 is etched. That is, by the supply of HF gas, the following reaction occurs between the Al2O3 on the surface of the wafer 200, and an Al-F compound such as AlF3 and AlOF is formed on the wafer 200 as the first product Z1.

[0066] Al2O3+HF→AlF3+AlOF+H2O

[0067] (Exhaust, step S12)

[0068] The valve 243a is closed to stop the supply of the first gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246. In this way, residual gas, for example, unreacted first gas remaining on the wafer 200 and / or in the processing chamber 201, and reaction byproducts are removed from the processing chamber 201. At this time, the processing chamber 201 can be purged by maintaining the supply of inert gas to the processing chamber 201 while keeping the valves 243c and 243d open. The inert gas acts as a purge gas and can improve the effect of removing residual gas from the wafer 200. In this step, for example, unreacted HF gas remaining in the processing chamber 201, H2O as a reaction byproduct, etc. are removed from the processing chamber 201.

[0069] After step S11, it is preferable to perform vacuum exhaust and purge in the processing chamber 201 which is the space where the wafer 200 exists. In this way, the amount of the first halogen element remaining on the wafer 200 after the etching process can be reduced. That is, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the remaining first halogen element. The vacuum exhaust and purge are performed, for example, 1 to 10 times.

[0070] At this time, it is preferable to set the processing time in this step to be longer than the processing time of the above-mentioned step S11. Thus, for example, the unreacted first gas, the reaction byproduct containing the first halogen element, the second product Z2 generated in the later-described step S13, the substance containing the first halogen element, etc. can be removed from the wafer 200. Therefore, the amount of the first halogen element remaining on the wafer 200 can be reduced. That is, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the residual first halogen element.

[0071] In this case, the processing pressure in this step is preferably set to be at least half of the processing pressure in the above step S11. This can reduce the amount of the first halogen element remaining on the wafer 200. That is, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the first halogen element remaining.

[0072] The vacuum exhaust conditions in this step may be:

[0073] Processing pressure: 10~200Pa

[0074] Processing time: 10 to 180 seconds.

[0075] The purge conditions in this step may include:

[0076] Processing pressure: 10~7000Pa

[0077] Processing time: 30 to 180 seconds.

[0078] (Second Gas Supply, Step S13)

[0079] Next, the second gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243b is opened, and the second gas flows into the gas supply pipe 232b. The second gas is flow-regulated by the MFC 241b, supplied to the processing chamber 201 through the nozzle 249b, and exhausted from the exhaust pipe 231. At this time, the valves 243c and 243d are opened, and the inert gas flows into the gas supply pipes 232c and 232d.

[0080] In this step, if Figure 4 As shown in (C) in FIG. 1 , the second gas containing the second halogen element is supplied to the wafer 200 having the first product Z1 formed on the surface. Figure 4As shown in (D) in FIG. 2 , at least a portion of the first product Z1 is converted into a second product Z2 containing the element X and having a higher vapor pressure than the first product Z1. That is, in this step, at least a portion of the first product Z1 on the wafer 200 is removed.

[0081] This step is preferably performed under conditions that when the second gas is supplied to substance Y having no first halogen element on the surface, at least a portion of substance Y can be removed from wafer 200. In other words, this step is preferably performed under conditions that substance Y can be etched by the second gas alone.

[0082] Generally, the second gas is less likely to reach the deep side of the concave portion on the wafer 200 than the open side. Therefore, it is difficult to convert the first product Z1 to the second product Z2 on the deep side of the concave portion of the wafer 200. In this step, since it is carried out under the condition that the substance Y can be etched by the second gas alone, when it is desired to convert all of the first product Z1 on the deep side into the second product Z2, it is expected that the etching of the substance Y by the second gas alone is carried out on the open side. Therefore, the etching amount of the substance Y on the open side becomes larger than that on the deep side, and there is a case where the uniformity of the etching amount in the concave portion of the wafer 200 is reduced. In this method, it is also possible to prevent a part of the first product Z1 from being converted into the second product Z2 in this step. As a result, the etching of the substance Y on the open side by the second gas alone can be suppressed, so that the uniformity of the etching amount in the concave portion on the wafer 200 can be improved.

[0083] In this step, it is preferred that the exposure amount of the second gas to the chip 200 is smaller than the exposure amount at which all of the first product Z1 on the chip 200 is converted into the second product Z2. Thus, this step can be performed under the condition that at least a portion of the first product Z1 on the chip 200 is not converted into the second product Z2. Here, the "exposure amount of the second gas to the chip 200" is calculated, for example, as "a value obtained by integrating the partial pressure of the second gas in the space where the chip 200 exists at a certain time through the time from the start to the end of this step." In addition, the "partial pressure of the second gas" is calculated, for example, as "the product of the mole fraction of the second gas at a certain time and the pressure (total pressure) in the space where the chip 200 exists."

[0084] Therefore, for example, at least one of the time for supplying the second gas to the wafer 200 (hereinafter also referred to as the supply time), the mole fraction of the second gas in the gas supplied to the wafer 200, and the pressure in the processing chamber 201 when the second gas is supplied to the wafer 200 is made smaller than the case where all the first product Z1 on the wafer 200 is converted into the second product Z2. Thus, the exposure amount of the second gas to the wafer 200 can be made smaller than the exposure amount at which all the first product Z1 on the wafer 200 is converted into the second product Z2.

[0085] The molar fraction of the second gas in the gas supplied to the wafer 200 may be controlled, for example, by the ratio of the flow rate of the second gas supplied into the processing chamber 201 (also referred to as the supply flow rate of the second gas) and the flow rate of the inactive gas (also referred to as the supply flow rate of the inactive gas) in this step. For example, one or both of the supply flow rate of the second gas in this step may be made smaller than the case where all of the first product Z1 on the wafer 200 is converted into the second product Z2, and the supply flow rate of the inactive gas in this step may be made larger than the case where all of the first product Z1 on the wafer 200 is converted into the second product Z2. Thus, the molar fraction of the second gas can be made smaller than the molar fraction of the second gas at which all of the first product Z1 on the wafer 200 is converted into the second product Z2.

[0086] In addition, in this step, it is preferred to prioritize the conversion from the first product Z1 to the second product Z2 over the removal of the substance Y. This can suppress the progress of the etching of the substance Y on the opening side by the second gas alone, thereby improving the uniformity of the etching amount in the recessed portion on the wafer 200.

[0087] As the processing conditions when the second gas is supplied in this step, the following can be exemplified:

[0088] Processing pressure: 10~7000Pa

[0089] Each gas supply time: 60 to 600 seconds

[0090] Partial pressure of the second gas: 10~4000Pa.

[0091] As the second gas, for example, a gas containing a second halogen element can be used. As the second halogen element, for example, a gas containing a second halogen element different from the first halogen element can be used. Here, it is preferred that the atomic number of the second halogen element contained in the second gas is greater than the atomic number of the first halogen element contained in the first gas. Specifically, for example, when the first halogen element is F, the second halogen element contained in the second gas is Cl. Thus, it becomes easy to perform this step under the condition that the substance Y is etched by the second gas alone.

[0092] As the second gas, a Cl-containing gas containing, for example, chlorine (Cl) as the second halogen element can be used. As the Cl-containing gas, for example, chlorine (Cl2) gas, boron trichloride (BCl3) gas, carbon tetrachloride (CCl4) gas, thionyl chloride (SOCl2) gas, sulfuryl chloride (SO2Cl2) gas, phosgene (COCl2) gas, phosphorus trichloride (PCl3) gas, phosphorus pentachloride (PCl5) gas, etc. can be cited. Preferably, as the Cl-containing gas, SOCl2 gas, COCl2 gas, etc., which are oxygen (O)-containing gases, are used. By using an O-containing gas, O can be replaced with F, so that F can be separated from the wafer 200. In addition, as the second gas, for example, a compound of a Group 13 element or a Group 15 element can be used. As a compound of a Group 13 element, for example, a compound of boron (B), aluminum (Al), gallium (Ga), indium (In), etc. can be used. As a compound of a Group 15 element, for example, a compound of N, phosphorus (P), arsenic (As), etc. can be used. As the second gas, one or more of these may be used.

[0093] For example, when BCl3 gas is used as the second gas, by supplying BCl3 gas to the wafer 200 under the above conditions, AlF3 on the surface of the wafer 200 reacts with BCl3, and a portion of F is separated from AlF3 and replaced by Cl. As a result, the AlF3 molecular layer formed on the surface of the wafer 200 is converted into volatile AlCl x F y , and is separated from the surface of the wafer 200. In addition, the F separated from AlF3 combines with the B separated from BCl3 to generate BF2. Then, AlCl x F y BF3 is separated from the surface of the wafer 200 and discharged from the processing chamber 201, thereby the surface of Al2O3 is etched. That is, by the supply of BCl3 gas, the following reaction occurs on the surface of the wafer 200, and at least a part of the first product Z1 is converted into AlCl3F or the like, which contains the element X and has a higher vapor pressure than AlF3, AlOF or other Al-F compounds as the first product Z1, as the second product Z2, and is separated from the surface of the wafer 200.

[0094] AlF3+AlOF+BCl3→AlCl3F+BF2+AlOF

[0095] (Exhaust, step S14)

[0096] The valve 243b is closed to stop the supply of the second gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246. As a result, residual gas, for example, unreacted second gas remaining on the wafer 200 and / or in the processing chamber 201, and reaction byproducts are removed from the processing chamber 201. At this time, the supply of inert gas to the processing chamber 201 can also be maintained while the valves 243c and 243d are kept open, thereby purging the processing chamber 201. In this step, for example, unreacted BCl3 gas remaining in the processing chamber 201, AlCl3F, BF2, etc. as reaction byproducts are removed from the processing chamber 201.

[0097] After step S13, it is preferred to perform vacuum exhaust and purge in the processing chamber 201. In this way, at least a portion of the first product Z1 containing the first halogen element and the second product Z2 can be removed from the wafer 200. Therefore, the amount of the first halogen element remaining on the wafer 200 can be reduced. In other words, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the remaining first halogen element. The vacuum exhaust and purge are performed, for example, 1 to 10 times.

[0098] At this time, it is preferable that the processing time in this step is longer than the processing time of the above-mentioned step S13. Thus, at least a part of the first product Z1 and the second product Z2 containing the first halogen element can be removed from the wafer 200. Therefore, the amount of the first halogen element remaining on the wafer 200 after the etching process can be reduced. That is, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the remaining first halogen element.

[0099] In addition, at this time, it is preferable to make the processing pressure in this step more than half of the processing pressure in the above-mentioned step S13. In this way, the substance containing the first halogen element can be removed from the wafer 200. Therefore, the amount of the first halogen element remaining on the wafer 200 after the etching process can be reduced. That is, it is possible to prevent the electrical characteristics of the wafer 200 from being deteriorated due to the residual first halogen element.

[0100] As the conditions for vacuum exhaust and purging in this step, the conditions exemplified as the conditions for vacuum exhaust and purging in step S12 can be used.

[0101] (Perform a specified number of times, step S15)

[0102] By performing the cycle of steps S11 to S14 a predetermined number of times (n times, where n is an integer greater than or equal to 1 or 2), at least a portion of the substance Y on the wafer 200 can be etched (hereinafter also referred to as etching).

[0103] As described above, in this embodiment, step S13 is performed under the condition that when the second gas is supplied to substance Y having no first halogen element on the surface, at least a portion of substance Y can be removed from wafer 200. In other words, step S13 is performed under the condition that substance Y is etched by the second gas alone.

[0104] In such a case, the amount of substance Y etched per cycle (hereinafter referred to as etching rate) tends to change in a linear function manner relative to the number of etching cycles. Thus, the amount of substance Y etched can be accurately predicted based on the number of cycles. For example, in the case where substance Y is a film, the thickness of the etched film tends to increase linearly (or in a linear function manner) relative to the increase in the number of cycles. That is, the controllability of the etching amount can be improved. In addition, in such a case, it is easy to convert from the first product Z1 to the second product Z2 in step S13. Therefore, the number of wafers 200 that can be processed per unit time (productivity) can be increased.

[0105] As described above, if the first gas supply step (S11) to the step (S15) for the predetermined number of times are performed, the first product Z1 may remain on the wafer 200, and the first halogen element may remain in the film. In other words, the first halogen element may remain on the wafer 200. Therefore, after the step (S15) for the predetermined number of times, the modification step S16 for removing the remaining first halogen element may be performed.

[0106] (Supply of Modifying Agent, Step S16)

[0107] Next, a modifier is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243e is opened, and the modifier flows into the gas supply pipe 232a. The modifier is flow-regulated by the MFC 241e, supplied into the processing chamber 201 through the nozzle 249a, and exhausted by the exhaust pipe 231. At this time, the valves 243c and 243d are opened, and an inert gas flows into the gas supply pipes 232c and 232d.

[0108] By supplying the modifier, the bond between the substance Y on the surface of the wafer 200 and the first halogen element is cut, and the first halogen element is converted into a volatile, easily desorbed gas and exhausted from the processing chamber 201. That is, the modifier is supplied to the wafer 200 to convert at least a portion of the first product Z1 into a third product containing the element X and having a higher vapor pressure than the first product Z1. Thus, the amount of the first halogen element remaining on the wafer 200 can be further reduced.

[0109] When a modifier is supplied to a substance Y having no first halogen element on its surface, this step is preferably performed under conditions that can remove at least a portion of the substance Y from the wafer 200. As a result, the conversion of the first product Z1 in this step becomes easier, thereby increasing the number of wafers 200 that can be processed per unit time (productivity).

[0110] The reactivity of the modifier to the substance Y and the first product Z1 is preferably higher than the reactivity of the second gas to the substance Y and the first product Z1. In this case, in the cycle of steps S11 to S14, it is easy to improve the uniformity of the etching amount in the concave portion of the wafer 200, but on the other hand, the conversion of the first product Z1 becomes difficult. In contrast, in this step, after the cycle of steps S11 to S14, the conversion of the first product Z1 remaining on the wafer 200 becomes easy. Therefore, it is possible to simultaneously achieve an improvement in the uniformity of the etching amount and a reduction in the amount of the first halogen element remaining on the wafer 200 after the etching process.

[0111] In this step, it is preferred to prioritize the conversion from the first product Z1 to the third product over the removal of the substance Y. This can suppress the progress of the etching of the substance Y on the opening side by the second gas alone, thereby improving the uniformity of the etching amount in the recessed portion of the wafer 200.

[0112] The modifier may be in liquid phase or gas phase. As the modifier, for example, a gas containing a third halogen element (also referred to as a gas containing a third halogen element), the second gas, an oxidant (also referred to as an oxidizing gas), a nitriding agent (also referred to as a nitriding gas), etc. may be used.

[0113] When a gas containing a third halogen element is used as a modifier, it is preferred that the atomic numbers of the second halogen element and the third halogen element are greater than the atomic number of the first halogen element. Specifically, for example, the halogen element contained in the first gas is F, and the second halogen element and the third halogen element are Cl. In this case, the gas exemplified as the second gas can be used as a modifier, and the gas used as the second gas in step S13 can also be used as a modifier.

[0114] In this step, the processing conditions when supplying the gas containing the third halogen element as the modifier may be as follows:

[0115] Processing temperature: 200~900℃

[0116] Processing pressure: 10~7000Pa

[0117] Each gas supply time: 60 to 600 seconds

[0118] Partial pressure of modifier: 10~4000Pa.

[0119] When the gas containing the third halogen element is used as a modifier in this step, it is preferred that the exposure amount of the gas containing the third halogen element to the wafer 200 in this step is greater than the exposure amount of the second gas to the wafer 200 in step S13. In this case, it is easy to improve the uniformity of the etching amount in the concave portion of the wafer 200 during the cycle of steps S11 to S14, while on the other hand, the conversion of the first product Z1 becomes difficult. In contrast, in this step, after the cycle of steps S11 to S14, the conversion of the first product Z1 remaining on the wafer 200 becomes easy. Therefore, it is possible to simultaneously achieve improvement in the uniformity of the etching amount and reduction in the amount of the first halogen element remaining on the wafer 200 after the etching process.

[0120] When the substance Y is an oxide, an oxidizing agent is preferably used as the modifier. When the substance Y is a nitride, a nitriding agent is preferably used as the modifier.

[0121] As an oxidant (oxidizing gas), for example, a gas containing oxygen (O) and hydrogen (H) can be used. As a gas containing O and H, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, H2 gas + ozone (O3) gas, etc. can be used. In addition, as an oxidant, in addition to a gas containing O and H, for example, a gas containing oxygen (O) can also be used. As a gas containing O, for example, O2 gas, O3 gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc. can be cited. It should be noted that a gas containing O and H is also a type of gas containing O. As an oxidant, one or more of them can be used. In addition, as a nitriding agent, for example, a hydrogen nitride gas can be used. As hydrogen nitride-based gases, for example, ammonia (NH3) gas, diazine (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas, etc. can be cited. As nitriding agents, one or more of them can be used. As oxidizing agents and nitriding agents, substances obtained by activating one or more of these gases by plasma can be used.

[0122] In addition, when O3 gas, for example, which is an oxidant (oxidizing gas), is used as a modifier, the AlOF on the surface of the wafer 200 reacts with O3, and the F bond of the AlOF is cut. Then, F is separated from the AlOF and replaced by O. That is, the AlOF formed on the wafer 200 is modified into Al2O3, so that F X That is, F XThe residual F is removed by detaching from the surface of the wafer 200 and being exhausted from the processing chamber 201. Thus, F can be removed by etching each layer containing F. The supply of O3 gas causes the following reaction with AlOF on the surface of the wafer 200.

[0123] AlOF+O3→Al2O3+F X

[0124] In this step, the treatment conditions when supplying an oxidizing gas as a modifier include:

[0125] Processing temperature: 200~900℃

[0126] Processing pressure: 10~200Pa

[0127] Each gas supply time: 0.1 to 300 seconds.

[0128] (Exhaust, step S17)

[0129] The valve 243e is closed to stop the supply of the modifier. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246. In this way, residual gas, such as unreacted modifier and reaction byproducts remaining on the wafer 200 and / or in the processing chamber 201, is removed from the processing chamber 201. At this time, the processing chamber 201 can also be purged by maintaining the supply of inert gas to the processing chamber 201 while the valves 243c and 243d are kept open.

[0130] As the conditions for vacuum exhaust and purging in this step, the conditions exemplified as the conditions for vacuum exhaust and purging in step S12 can be used.

[0131] (Perform a specified number of times, step S18)

[0132] The above steps S16 to S17 are cycled a predetermined number of times (m times, where m is an integer greater than or equal to 1 or 2). For example, when a gas containing a halogen element is used as a modifier, m is 1 to 50. For example, when an oxidizing gas or a nitriding gas is used as a modifier, m is 60 to 300.

[0133] (Perform a specified number of times, step S19)

[0134] The loop of steps S11 to S18 is performed a predetermined number of times (N times, where N is an integer greater than or equal to 1 or 2). For example, N is 1 to 100.

[0135] (Post-purge and atmospheric pressure recovery)

[0136] Inert gas is supplied from the gas supply pipes 232c and 232d to the processing chamber 201, and the gas is exhausted from the exhaust pipe 231. Thus, the processing chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purging). Then, 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 restored to normal pressure (atmospheric pressure restoration).

[0137] (Wafer boat unloading and wafer removal)

[0138] Then, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafer 200 is carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported on the wafer boat 217 (wafer boat unloading). The processed wafer 200 is taken out of the wafer boat 217 (wafer taking out).

[0139] <Other aspects of the present invention>

[0140] The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the gist of the present invention.

[0141] (Variation Example)

[0142] This modification is different from the second gas supply step (S13) in the above-mentioned substrate processing step. In this modification, in addition to the same effects as the above-mentioned embodiment, the following effects can be obtained.

[0143] In this modification, in the second gas supply process (S13), the second gas is supplied to the wafer 200 multiple times, and the processing chamber 201 is exhausted during the multiple supply of the second gas. That is, the cycle of supplying the second gas and removing the second product Z2 and the like by exhausting the gas is repeated multiple times. That is, the second gas is supplied in pulses. In other words, the second gas is supplied intermittently. As a result, the second product Z2 generated by the second gas supply becomes less likely to be adsorbed on the wafer 200 again, so the amount of the first halogen element remaining on the wafer 200 can be reduced. Therefore, the characteristics of the substance Y, such as electrical characteristics, can be further improved.

[0144] As the exhaust in this step, the processing chamber 201 may be purged or vacuum-exhausted, or only one of them may be performed. As the exhaust in this step, it is preferred to perform only vacuum-exhaust in the processing chamber 201. In this way, the amount of the first halogen element remaining on the wafer 200 can be reduced while improving productivity.

[0145] The processing conditions in step S13 of this modification example may be:

[0146] Processing pressure: 10~7000Pa

[0147] Each gas supply time: 20 to 600 seconds

[0148] Partial pressure of the second gas: 10~4000Pa

[0149] Second gas supply times: 2 to 10 times

[0150] Exhaust time: 10 to 180 seconds

[0151] Processing pressure during exhaust: 10~200Pa.

[0152] (Other methods)

[0153] In the above description, the case where at least a portion of the substance Y on the wafer 200 is etched by performing the first gas supply step (S11) to the step (S19) of performing the predetermined number of times is described. The present invention is not limited to this, and even in the case where the first gas supply step (S11) to the step (S15) of performing the predetermined number of times are performed, the controllability of the etching of the substance Y on the wafer 200 can be improved. That is, in this method, the same effect as the above method can be obtained.

[0154] In addition, in the above-mentioned method, the case where the amount of the first product Z1 formed in step S11 is saturated is used for explanation. The present invention is not limited to this, and step S11 can also be performed under the condition that the amount of the first product Z1 formed is not saturated. In other words, in step S11, the formation of the first product Z1 may not be self-controlled. In this method, the same effect as in the above-mentioned method can also be obtained. In addition, in this method, the time required for step S11 can be further shortened.

[0155] In addition, in the above-mentioned method, the case where the first gas supply process (S11) to the step of implementing the predetermined number of times (S19) are continuously (in-situ) performed in the same processing furnace 202 is described, but it is not limited to this, and the first gas supply process (S11) to the step of implementing the predetermined number of times (S15) and the modification process (S16) to the step of implementing the predetermined number of times (S18) can also be performed in different processing furnaces (ex-situ). In this method, the same effect as the above-mentioned method can also be obtained.

[0156] In addition, in the above description, the process of etching the substance Y formed on the wafer 200 is described as an example. However, the present invention is not limited to this. For example, it can also be appropriately applied to the process of etching the substance Y formed on the inner wall of the processing chamber 201, the surface of the wafer boat 217, etc. (cleaning process in the processing chamber 201). In this method, the same effect as the above method can be obtained.

[0157] It should be noted that the process for substrate processing is preferably prepared individually according to the processing content, and is pre-stored in the storage device 121c via the electrical communication line and the external storage device 123. In addition, when starting the substrate processing, it is preferred that the CPU 121a appropriately selects an appropriate process from the multiple processes stored in the storage device 121c according to the processing content. Thus, the substrate processing device can be used to process films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility. In addition, the burden on the operator can be reduced, and the substrate processing can be started quickly while avoiding operational errors.

[0158] The above-mentioned process is not limited to the case of new preparation, and can also be prepared by, for example, changing an existing process already installed in a substrate processing device. In the case of changing the process, the changed process can also be installed in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing process already installed in the substrate processing device.

[0159] In the above-mentioned manner, an example of a substrate processing apparatus using a batch type that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned aspect. For example, in the case of a substrate processing apparatus using a single-wafer type that processes one or more substrates at a time, the present invention can also be appropriately applied. In addition, in the above-mentioned manner, an example of a substrate processing apparatus using a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned aspect. For example, in the case of a substrate processing apparatus using a cold-wall type processing furnace, the present invention can also be appropriately applied.

[0160] Also when these substrate processing apparatuses are used, film formation processing can be performed in the same processing steps and processing conditions as those in the above-mentioned embodiment, and the same effects as those in the above-mentioned embodiment can be obtained.

[0161] In addition, the above-mentioned aspects and modifications can be used in combination as appropriate. The processing steps and processing conditions in this case can be, for example, the same as the processing steps and processing conditions in the above-mentioned aspects and modifications.

Claims

1. A substrate processing method, comprising performing a cycle of (a1) and (b1) in sequence for a predetermined number of times, thereby removing at least a portion of a substance Y from a substrate, (a1) is a step of supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X, thereby forming a first product containing the first halogen element and the element X on the substrate. (b1) is a step of supplying a second gas containing a second halogen element to the substrate to convert at least a portion of the first product into a second product containing the element X and having a higher vapor pressure than the first product, in, (b1) is performed under the condition that when the second gas is supplied to the substance Y having no first halogen element on the surface, at least a part of the substance Y can be removed from the substrate.

2. The substrate processing method according to claim 1, wherein: In (b1), a part of the first product is not converted into the second product.

3. The substrate processing method according to claim 2, wherein: In (b1), the exposure amount of the second gas to the substrate is set to be smaller than the exposure amount at which all of the first product on the substrate is converted into the second product.

4. The substrate processing method according to claim 1, wherein: In (b1), the conversion from the first product to the second product is performed preferentially over the removal of the substance Y.

5. The substrate processing method according to claim 1, wherein: (a1) is carried out under the conditions where the amount of the first product formed reaches saturation.

6. The substrate processing method according to claim 1, wherein: The cycle further includes: (a2) performing a step of vacuum exhausting and purging the space where the substrate is located after step (a1).

7. The substrate processing method according to claim 1, wherein: The cycle further includes: (a2) after (a1) and for a period of time longer than (a1) the step of exhausting the space in which the substrate is located.

8. The substrate processing method according to claim 1, wherein: The cycle further includes: (b2) after step (b1), performing a step of vacuum exhausting and purging the space where the substrate is located.

9. The substrate processing method according to claim 1, wherein: The cycle further includes: (b2) after (b1) and for a period of time longer than (b1) the step of exhausting the space in which the substrate is located.

10. The substrate processing method according to claim 1, wherein: In (b1), the second gas is supplied to the substrate a plurality of times, and while the second gas is supplied a plurality of times, exhaust is performed from within a space where the substrate is present.

11. The substrate processing method according to claim 1, wherein: The cycle further includes: (c) supplying a modifying agent to the substrate to convert at least a portion of the first product into a third product containing the element X and having a higher vapor pressure than the first product.

12. The substrate processing method according to claim 11, wherein: (c) is performed under conditions such that when the modifying agent is supplied to the substance Y having no first halogen element on the surface, at least a portion of the substance Y can be removed from the substrate.

13. The substrate processing method according to claim 12, wherein: In (c), the conversion from the first product to the third product is performed preferentially over the removal of the substance Y.

14. The substrate processing method according to claim 12, wherein: The modifier has a higher reactivity with the substance Y and the first product than with the second gas.

15. The substrate processing method according to claim 12, wherein: The modifier is a gas containing a third halogen element.

16. The substrate processing method according to claim 15, wherein: The exposure amount of the gas containing the third halogen element to the substrate in (c) is made greater than the exposure amount of the second gas to the substrate in (b1).

17. The substrate processing method according to claim 1, wherein: The atomic number of the second halogen element is greater than that of the first halogen element.

18. A method for manufacturing a semiconductor device, comprising performing a cycle of (a1) and (b1) in sequence for a predetermined number of times, thereby removing at least a portion of a substance Y from a substrate, (a1) is a step of supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X, thereby forming a first product containing the first halogen element and the element X on the substrate. (b1) is a step of supplying a second gas containing a second halogen element to the substrate to convert at least a portion of the first product into a second product containing the element X and having a higher vapor pressure than the first product, in, (b1) is performed under the condition that when the second gas is supplied to the substance Y having no first halogen element on the surface, at least a part of the substance Y can be removed from the substrate.

19. A substrate processing device comprising: a first gas supply system for supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X; a second gas supply system for supplying a second gas containing a second halogen element to the substrate; and A control unit configured to control the first gas supply system and the second gas supply system to perform the following process, the process comprising performing a cycle of (a1) and (b1) in sequence for a predetermined number of times to remove at least a portion of substance Y from the substrate, (a1) being a process of supplying the first gas to the substrate to form a first product containing the first halogen element and the element X on the substrate, and (b1) being a process of supplying the second gas to the substrate to convert at least a portion of the first product into a second product containing the element X and having a higher vapor pressure than the first product, wherein: (b1) is performed under the condition that when the second gas is supplied to the substance Y having no first halogen element on the surface, at least a part of the substance Y can be removed from the substrate.

20. A computer-readable recording medium having a program recorded thereon for causing a substrate processing apparatus to execute the following steps, the steps comprising performing a cycle of (a1) and (b1) in sequence a predetermined number of times, thereby removing at least a portion of a substance Y from a substrate, (a1) is a step of supplying a first gas containing a first halogen element to a substrate having a surface of a substance Y containing an element X, thereby forming a first product containing the first halogen element and the element X on the substrate. (b1) is a step of supplying a second gas containing a second halogen element to the substrate to convert at least a portion of the first product into a second product containing the element X and having a higher vapor pressure than the first product. in, (b1) is performed under the condition that when the second gas is supplied to the substance Y having no first halogen element on the surface, at least a part of the substance Y can be removed from the substrate.

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