Substrate processing method, method of manufacturing a semiconductor device, program, and substrate processing apparatus

Abstract

To provide a substrate processing method, a method for manufacturing a semiconductor device, programs, and a substrate processing apparatus that improve device characteristics.SOLUTION: A substrate processing method comprises a step for processing a substrate by performing steps for supplying gas containing a first halogen element to the substrate, and supplying gas containing a second halogen element to the substrate a predetermined number of times, and a step for processing the substrate by performing steps for supplying reforming gas to the substrate and supplying gas containing a third halogen element to the substrate a predetermined number of times.SELECTED DRAWING: Figure 7

Description

Technical Field

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

Background Art

[0002] As one step in the manufacturing process of a semiconductor device, a step of etching a thin film may be performed by performing a step of supplying a boron-containing gas and a step of supplying a halide gas a predetermined number of times (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When etching a thin film using the apparatus as described above, halogen elements may remain, and the device characteristics may deteriorate.

[0005] The present disclosure provides a technology capable of improving device characteristics.

Means for Solving the Problems

[0006] According to one aspect of the present disclosure, (a) a step of supplying a first halogen element-containing gas to a substrate; (b) a step of supplying a second halogen element-containing gas to the substrate; (c) a step of supplying a reforming gas to the substrate; (d) a step of supplying a third halogen element-containing gas to the substrate; (e) a step of performing (a) and (b) a predetermined number of times to process the substrate; Performing (f), (c), and (d) a predetermined number of times to process the substrate; A technique having [it] is provided.

Advantages of the Invention

[0007] According to the present disclosure, it becomes possible to improve device characteristics.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0009] <One Aspect of the Present Disclosure> Hereinafter, one aspect of the present disclosure will be described mainly with reference to FIGS. 1 to 5. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships of the respective elements shown in the drawings, the ratios of the respective elements, etc. do not necessarily match the actual ones. Also, even between a plurality of drawings, the dimensional relationships of the respective elements, the ratios of the respective elements, etc. do not necessarily match.

[0010] (1) Configuration of the substrate processing apparatus As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) for activating (exciting) the gas with heat.

[0011] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open. A processing chamber 201 is formed in the hollow portion of the cylinder of the reaction tube 203. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing on the wafer 200 is performed within this processing chamber 201.

[0012] In the processing chamber 201, nozzles 249a and 249b are provided so as to penetrate the lower side wall of the reaction tube 203. Gas supply pipes 232a and 232b are respectively connected to the nozzles 249a and 249b.

[0013] In the gas supply pipes 232a and 232b, a mass flow controller (MFC) 241a and 241b, which are flow rate controllers (flow rate control units), and valves 243a and 243b, which are on-off valves, are respectively provided in order from the upstream side of the gas flow. On the downstream side of the valve 243a in the gas supply pipe 232a, gas supply pipes 232c and 232e are respectively connected. On the downstream side of the valve 243b in the gas supply pipe 232b, a gas supply pipe 232d is connected. In the gas supply pipes 232c, 232d, and 232e, an MFC 241c, 241d, and 241e and valves 243c, 243d, and 243e are respectively provided in order from the upstream side of the gas flow.

[0014] As shown in FIG. 2, the nozzles 249a and 249b are respectively provided in an annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part from the lower part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a and 249b are respectively provided in a region on the side of the wafer arrangement region where the wafers 200 are arranged, in a region that horizontally surrounds the wafer arrangement region, along the wafer arrangement region. 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 so as to face the center of the reaction tube 203, and it is possible to 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.

[0015] From the gas supply pipe 232a, a first halogen element-containing gas containing a first halogen element is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a.

[0016] From the gas supply pipe 232b, a second halogen element-containing gas containing a second halogen element, which is an element different from the first halogen element, is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b.

[0017] From the gas supply pipes 232c and 232d, an inert gas is supplied into the processing chamber 201 via the MFCs 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

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

[0019] Primarily, the gas supply pipe 232a, the MFC 241a, and the valve 243a constitute a first halogen element-containing gas supply system for supplying a first halogen element-containing gas. Primarily, the gas supply pipe 232b, the MFC 241b, and the valve 243b constitute a second halogen element-containing gas supply system for supplying a second halogen element-containing gas. Primarily, the gas supply pipes 232c and 232d, the MFCs 241c and 241d, and the valves 243c and 243d constitute an inert gas supply system for supplying an inert gas. Primarily, the gas supply pipe 232e, the MFC 241e, and the valve 243e constitute a reformed gas supply system for supplying a reformed gas. When the second halogen element-containing gas supply system uses the second halogen element-containing gas as a third halogen element-containing gas, it can be referred to as a third halogen element-containing gas supply system.

[0020] Among the above various supply systems, any one or all of them may 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 the supply operations of various gases into the gas supply pipes 232a to 232e, that is, the opening and closing operations of the valves 243a to 243e and the flow rate adjustment operations by the MFCs 241a to 241e, etc. are configured to be controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and can be attached to and detached from the gas supply pipes 232a to 232e, etc. in units of integrated units, and maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of integrated units.

[0021] An exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is connected to the lower part of the 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 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 operating, and further, with the vacuum pump 246 operating, the valve opening degree can be adjusted based on the pressure information detected by the pressure sensor 245, so that the pressure in the processing chamber 201 can be adjusted. Mainly, the exhaust system is composed of the exhaust pipe 231, the pressure sensor 245, and the APC valve 244. The vacuum pump 246 may be included in the exhaust system.

[0022] Below the reaction tube 203, a seal cap 219 is provided as a furnace port lid that can airtightly close the lower end opening of the reaction tube 203. The seal cap 219 is made of a metal material such as SUS, for example, and is formed in a disk shape. An O-ring 220 is provided on the upper surface of the seal cap 219 as a seal member that contacts the lower end of the reaction tube 203. Below the seal cap 219, a rotation mechanism 267 for rotating a boat 217 described later is installed. The rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically moved up and down by a boat elevator 115 as an elevating 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 moving the seal cap 219 up and down.

[0023] The boat 217 as a substrate support tool is configured to support a plurality of wafers 200, for example, 25 to 200 wafers, in a horizontal posture and vertically aligned in a multi-stage manner with their centers aligned with each other, that is, arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC, for example. Below the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are horizontally supported in multiple stages.

[0024] Inside the reaction tube 203, a temperature sensor 263 is installed as a temperature detector. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0025] 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 or the like is connected to the controller 121.

[0026] The storage device 121c is configured of, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of an etching process described later are described, and the like are stored in a readable manner. The process recipe is a combination that causes the controller 121 to execute each procedure in the etching process described later so as to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, and the like are collectively referred to simply as a program. Also, the process recipe is simply referred to as a recipe. When the term "program" is used in this specification, it may include only a single recipe, only a single control program, or both of them. The RAM 121b is configured as a memory area (work area) that temporarily holds programs, data, and the like read by the CPU 121a.

[0027] The I / O port 121d is connected to the above-described MFCs 241a to 241e, valves 243a to 243e, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, and the like.

[0028] The CPU 121a reads and executes a control program from the storage device 121c, and is configured to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a is configured to control various gas flow adjustment operations 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, 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 based on the temperature sensor 263, rotation and rotation speed adjustment operations of the boat 217 by the rotation mechanism 267, lifting and lowering operations of the boat 217 by the boat elevator 115, etc. so as to conform to the content of the read recipe.

[0029] The controller 121 can be configured by installing the above-described program stored in the external storage device 123 on 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, a semiconductor memory such as a USB memory, and the like. 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, these are collectively referred to simply as a recording medium. When the term "recording medium" 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. Note that the program may be provided to the computer without using the external storage device 123, but by using a communication means such as the Internet or a dedicated line.

[0030] (2) Substrate processing step Using the processing furnace 202 of the substrate processing apparatus described above, as one step of the manufacturing process of the semiconductor device, an atomic layer etching step and a residual first halogen element removing step are performed, and an example of etching the oxide film formed on the surface of the wafer 200 will be described with reference to FIGS. 4 and 5. In the following description, the operations of each part constituting the substrate processing apparatus are configured to be controllable by the controller 121.

[0031] As used herein, the term "wafer" may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. As used herein, the term "surface of the wafer" may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is described herein that "a predetermined layer is formed on the wafer", it may mean that the predetermined layer is directly formed on the surface of the wafer itself or that the predetermined layer is formed on a layer or the like formed on the wafer. When the term "substrate" is used herein, it has the same meaning as when the term "wafer" is used.

[0032] (2-1) Atomic layer etching process (step S10) (Wafer charge and boat load) A plurality of wafers 200 on which an oxide 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). In this state, the seal cap 219 seals the lower end of the reaction tube 203 via an O-ring 220.

[0033] (Pressure adjustment and temperature adjustment) The inside of the processing chamber 201, that is, the space where the wafers 200 are present, is evacuated (depressurized) by a vacuum pump 246 so as to reach a desired processing pressure (degree of vacuum). Also, the wafers 200 in the processing chamber 201 are heated by a heater 207 so as to reach a desired processing temperature. Also, rotation of the wafers 200 by a rotation mechanism 267 is started. The operation of the vacuum pump 246, the heating, and the rotation of the wafers 200 are all continuously performed until at least the processing of the wafers 200 is completed.

[0034] The processing temperature in this specification means the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure means the pressure in the processing chamber 201. Also, the processing time means the time for which the processing is continued. The same applies in the following explanations.

[0035] Thereafter, the following steps S110 to S150 are performed on the oxide film formed on the wafer 200.

[0036] Here, as the oxide film to be etched, for example, at least one or more metal oxide films (oxide films containing metal elements) such as 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 mentioned.

[0037] (Supply of the first halogen element-containing gas, step S110) In this step, a first halogen element-containing gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243a is opened, and the first halogen element-containing gas is flowed into the gas supply pipe 232a. The first halogen element-containing gas is flow-rate adjusted by the MFC241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the valves 243c and 243d are opened, and an inert gas is flowed into the gas supply pipes 232c and 232d.

[0038] As the first halogen element-containing gas, an F-containing gas containing, for example, fluorine (F) as the first halogen element can be used. As the F-containing gas, for example, at least one or more of fluorine (F2) gas, nitrogen trifluoride (NF3) gas, hydrogen fluoride (HF) gas, carbon tetrafluoride (CF4) gas, tungsten hexafluoride (WF6) gas, etc. can be used. Further, as the first halogen element-containing gas, for example, a hydrogen compound can be used. As the hydrogen compound, for example, HF gas can be used. As the first halogen element-containing gas, one or more of these can be used.

[0039] As the inert gas, in addition to nitrogen (N2) gas, noble gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc. can be used. As the inert gas, one or more of these can be used.

[0040] Specifically, for example, when the film to be etched is an Al2O3 film and HF gas is used as the first halogen element-containing gas, by supplying HF gas, the Al2O3 on the surface of the wafer 200 reacts with HF, and a part of Al and a part of O are desorbed from Al2O3 and replaced by F, being converted into AlOF and AlF3. Also, the O desorbed from Al2O3 combines with H to generate water vapor (H2O gas). Then, by desorbing H2O from the surface of the wafer 200 and discharging it from the inside of the processing chamber 201, the surface of Al2O3 is etched. That is, by supplying HF gas, the following reaction occurs between the HF gas and the Al2O3 on the surface of the wafer 200.

[0041] Al2O3 + HF → AlF3 + AlOF + H2O

[0042] In addition, as the processing conditions in this step, HF gas supply flow rate: 0.1 to 10 slm N2 gas supply flow rate (each gas supply pipe): 0 to 10 slm Each gas supply time: 0.1 to 200 seconds, preferably 5 to 150 seconds Processing temperature: 200°C or higher and lower than 900°C, preferably 300 - 800°C, more preferably 300 - 450°C Processing pressure: 150 - 400 Pa, preferably 200 - 300 Pa are exemplified.

[0043] In addition, the notation of a numerical range such as "0.1 - 10 slm" in the present disclosure means that the lower limit value and the upper limit value are included in the range. Therefore, "0.1 - 10 slm" means "0.1 slm or more and 10 slm or less". The same applies to other numerical ranges.

[0044] In addition, when 0 slm is included in the supply flow rate, 0 slm means a case where the substance (gas) is not supplied. This also applies to other descriptions in the present disclosure.

[0045] In the present disclosure, the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure means the pressure inside the processing chamber 201. Also, the processing time means the time for which the processing is continued. These are the same in other descriptions of the present disclosure.

[0046] (Purge, step S120) Close the valve 243a and stop the supply of the first halogen element-containing gas. At this time, keep the APC valve 244 of the exhaust pipe 231 open, evacuate the inside of the processing chamber 201 with the vacuum pump 246, remove the residual gas from above the wafer 200, and remove the unreacted first halogen element-containing gas and reaction by-products remaining in the processing chamber 201 from the inside of the processing chamber 201. At this time, keep the valves 243c and 243d open and maintain the supply of the inert gas into the processing chamber 201. The inert gas acts as a purge gas, removes the residual gas from above the wafer 200, and can enhance the effect of removing the unreacted first halogen element-containing gas and reaction by-products remaining in the processing chamber 201 from the inside of the processing chamber 201. Specifically, for example, unreacted HF gas remaining in the processing chamber 201 and H2O, which is a reaction by-product, are removed from the inside of the processing chamber 201.

[0047] (Second Halogen Element-Containing Gas Supply, Step S130) Next, a second halogen element-containing gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243b is opened, and the second halogen element-containing gas is caused to flow into the gas supply pipe 232b. The second halogen element-containing gas is adjusted in flow rate by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and exhausted through the exhaust pipe 231. At this time, the valves 243c and 243d are opened, and an inert gas is caused to flow into the gas supply pipes 232c and 232d.

[0048] As the second halogen element-containing 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 used. Preferably, as the Cl-containing gas, a gas containing oxygen (O), such as SOCl2 gas, COCl2 gas, etc. is used. By using a gas containing O, O can be substituted for F, and F can be desorbed from the wafer 200. Further, as the second halogen element-containing gas, for example, a compound of a Group 13 element or a Group 15 element can be used. As the compound of the Group 13 element, for example, compounds of boron (B), aluminum (Al), gallium (Ga), indium (In), etc. can be used. As the compound of the Group 15 element, for example, compounds of N, phosphorus (P), arsenic (As), etc. can be used. As the second halogen element-containing gas, one or more of these can be used.

[0049] Specifically, for example, when BCl3 gas is used as the second halogen element-containing gas, by supplying BCl3 gas to the wafer 200 under the above conditions, on the surface of the wafer 200, AlF3 reacts with BCl3, and a part of F is desorbed from AlF3 and replaced by Cl. As a result, the molecular layer of AlF3 formed on the surface of the wafer 200 becomes volatile AlCl x Fy It is converted and desorbed from the surface of the wafer 200. Also, the F desorbed from AlF3 combines with the B desorbed from BCl3 to generate BF2. Then, AlCl x F y and BF3 are desorbed and discharged from the processing chamber 201, whereby the surface of Al2O3 is etched. That is, the following reaction occurs on the surface of the wafer 200 by the supply of BCl3 gas.

[0050] AlF3+AlOF+BCl3→AlCl3F+BF2+AlOF

[0051] Incidentally, as the processing conditions in this step, BCl3 gas supply flow rate: 0.1~10 slm N2 gas supply flow rate (each gas supply pipe): 0~10 slm Each gas supply time: 0.1~300 seconds, preferably 5~200 seconds Processing temperature: 200°C or higher and less than 900°C, preferably 300~800°C, more preferably 300~450°C Processing pressure: 150~400 Pa, preferably 200~300 Pa are exemplified.

[0052] (Purge, Step S140) Close valve 243b and stop the supply of the second halogen element-containing gas. At this time, keep the APC valve 244 in the exhaust pipe 231 open, evacuate the inside of the processing chamber 201 with the vacuum pump 246 to remove the residual gas from the wafer 200, and remove the unreacted second halogen element-containing gas remaining in the processing chamber 201 and the reaction by-products from the processing chamber 201. At this time, keep valves 243c and 243d open to maintain the supply of the inert gas into the processing chamber 201. The inert gas acts as a purge gas, can remove the residual gas from the wafer 200, and enhance the effect of removing the unreacted second halogen element-containing gas remaining in the processing chamber 201 and the reaction by-products from the processing chamber 201. Specifically, for example, unreacted BCl3 gas remaining in the processing chamber 201, reaction by-products such as AlCl3F and BF2 are removed from the processing chamber 201.

[0053] (Performed a predetermined number of times, step S150) By performing the cycle of performing the above-described steps S110 to S140 a predetermined number of times (n times, n is an integer of 1 or more), the wafer 200 can be etched to process the wafer 200. That is, in this step (S10), supply of the first halogen element-containing gas (S110) and supply of the second halogen element-containing gas (S130) are performed. When n is 2 or more, these may be performed alternately.

[0054] As described above, when the atomic layer etching step S10 is performed, volatile reaction by-products such as AlCl3F and BF2 are desorbed from the surface of the wafer 200, but AlOF may remain and F may remain. That is, the first halogen element contained in the etching gas used in the atomic layer etching step may remain on the wafer 200. When the first halogen element remains on the wafer 200, the device characteristics may deteriorate. For this reason, in this embodiment, after the atomic layer etching step S10 described above, a residual first halogen element removal step S20 for removing the remaining first halogen element is performed.

[0055] (2-2) Residual first halogen element removal step (S20) Next, the details of the residual first halogen element removal process will be described with reference to FIG. 5. That is, the following steps S210 to S250 are performed on the wafer 200 etched using the first halogen element-containing gas. That is, this process is applicable when performed in the same processing furnace following the above-described atomic layer etching process S10, and is also applicable when the wafer 200 etched using the first halogen element-containing gas is carried into the processing furnace 202 for processing.

[0056] (Supply of reforming gas, step S210) In this step, a reforming gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243e is opened, and the reforming gas is caused to flow into the gas supply pipe 232a. The reforming gas is adjusted in flow rate by the MFC241e, supplied into 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 an inert gas is caused to flow into the gas supply pipes 232c and 232d.

[0057] As the reforming gas, for example, an oxygen (O)-containing gas or a hydrogen (H)-containing gas can be used. As the O-containing gas, for example, oxygen (O2) gas, ozone (O3) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, activated O2 gas, etc. can be used. Also, as the H-containing gas, for example, hydrogen (H2) gas, deuterium (D2), H2O gas, H2O2 gas, activated H2 gas, ammonia (NH3) gas, hydrazine (N2H4) gas, etc. can be used. As the reforming gas, one or more of these can be used.

[0058] By supplying the reforming gas, the bond between the oxide film on the surface of the wafer 200 and the first halogen element is broken, and the first halogen element is converted into a volatile and easily desorbed gas and discharged from the processing chamber 201.

[0059] Specifically, when using, for example, O3 gas as the reformed gas, by supplying O3 gas to the wafer 200, the AlOF on the surface of the wafer 200 reacts with O3, and the F bond of AlOF is broken. Then, F desorbs from AlOF and is replaced by O. That is, the AlOF formed on the wafer 200 is reformed into Al2O3 and F X desorbs. That is, F X desorbs from the surface of the wafer 200 and is discharged from the processing chamber 201, whereby the residual F is removed. In this way, by etching each layer containing F, F can be removed. When O3 gas is supplied, the following reaction occurs between O3 and AlOF on the surface of the wafer 200.

[0060] AlOF + O3 → Al2O3 + F X

[0061] Note that as the processing conditions in this step, O3 gas supply flow rate: 0.1~10 slm N2 gas supply flow rate (each gas supply pipe): 0~10 slm Each gas supply time: 0.1~200 seconds, preferably 5~150 seconds Processing temperature: 200°C or higher and less than 900°C, preferably 300~800°C, more preferably 300~450°C Processing pressure: 150~400 Pa, preferably 200~300 Pa are exemplified.

[0062] (Purge, step S220) Close valve 243e to stop the supply of the reformed gas. At this time, keep the APC valve 244 in the exhaust pipe 231 open, evacuate the inside of the processing chamber 201 with the vacuum pump 246, remove the residual gas from above the wafer 200, and exclude the unreacted reformed gas and reaction by-products remaining in the processing chamber 201 from the processing chamber 201. At this time, keep valves 243c and 243d open to maintain the supply of the inert gas into the processing chamber 201. The inert gas acts as a purge gas, can remove the residual gas from above the wafer 200, and enhance the effect of excluding the unreacted reformed gas and reaction by-products remaining in the processing chamber 201 from the processing chamber 201. Specifically, for example, the unreacted O3 gas remaining in the processing chamber 201 and F X etc. are excluded from the processing chamber 201.

[0063] (Supply of the third halogen element-containing gas, step S230) Next, supply the third halogen element-containing gas to the wafer 200 in the processing chamber 201. Specifically, open valve 243b and flow the third halogen element-containing gas into the gas supply pipe 232b. The flow rate of the third halogen element-containing gas is adjusted by MFC241b, supplied into the processing chamber 201 through nozzle 249b, and exhausted from the exhaust pipe 231. At this time, open valves 243c and 243d and flow the inert gas into the gas supply pipes 232c and 232d.

[0064] As the third halogen element-containing gas, a gas containing a third halogen element that is different from the above-described first halogen element and the same as the above-described second halogen element can be used. As the gas containing the third halogen element, the second halogen element-containing gas can be used. Note that the third halogen element-containing gas may be a gas different from the second halogen element-containing gas. The gas type used in this step is selected according to the processing temperature.

[0065] Specifically, when using, for example, the same BCl3 gas as the second halogen element-containing gas as the third halogen element-containing gas, by supplying BCl3 gas to the wafer 200, the AlOF on the surface of the wafer 200 reacts with BCl3, O desorbs from AlOF, and is replaced by Cl. That is, the AlOF formed on the wafer 200 is converted into volatile AlCl x F y and desorbs from the surface of the wafer 200. Also, the O desorbed from AlOF combines with BCl X to generate and desorb BOCl X . That is, AlCl x F y and BOCl X desorb from the surface of the wafer 200 and are discharged from the processing chamber 201, thereby removing the residual F. In this way, by etching each layer containing F, F can be removed. The following reaction occurs between BCl3 gas and AlOF on the surface of the wafer 200 due to the supply of BCl3 gas.

[0066] AlOF + BCl3 → AlCl x F y + BOCl X

[0067] Note that the processing conditions in this step may be the same as those in the above step S130.

[0068] (Purge, step S240) Close valve 243b and stop the supply of the third halogen element-containing gas. At this time, keep the APC valve 244 in the exhaust pipe 231 open, evacuate the inside of the processing chamber 201 with the vacuum pump 246, remove the residual gas from the wafer 200, and remove the unreacted third halogen element-containing gas remaining in the processing chamber 201 and the reaction by-products from the processing chamber 201. At this time, keep valves 243c and 243d open and maintain the supply of the inert gas into the processing chamber 201. The inert gas acts as a purge gas, can remove the residual gas from the wafer 200, and enhance the effect of removing the unreacted third halogen element-containing gas remaining in the processing chamber 201 and the reaction by-products from the processing chamber 201. Specifically, for example, unreacted BCl3 gas remaining in the processing chamber 201 and reaction by-products such as AlCl x F y , BOCl X etc. are removed from the processing chamber 201.

[0069] (Perform a predetermined number of times, step S250) By performing the cycle of performing the above steps S210 to S240 a predetermined number of times (m times, where m is an integer of 1 or more), the first halogen element remaining on the wafer 200 can be removed and the wafer 200 can be processed. That is, in this step (S20), a reforming gas supply (S210) and a third halogen element-containing gas supply (S230) are performed. When m is 2 or more, these may be performed alternately.

[0070] (After purge and atmospheric pressure recovery) After the above-mentioned step of removing the residual first halogen element is completed, supply an inert gas into the processing chamber 201 from each of the gas supply pipes 232c and 232d and exhaust from the exhaust pipe 231. Thereby, the inside of 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 (after purge). Then, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0071] (Boat unloading and wafer discharge) Thereafter, the seal cap 219 is lowered by the 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 (boat unloading) while being supported by the boat 217. The processed wafer 200 is taken out from the boat 217 (wafer discharge).

[0072] (3) Effects according to this aspect According to this aspect, one or more of the following effects can be obtained.

[0073] (a) By removing the first halogen element remaining in the atomic layer etching, it becomes possible to improve the device characteristics.

[0074] (b) Even for a film formed on the surface of a structure having a high aspect ratio, it becomes possible to etch with good step coverage.

[0075] (c) By performing a step of removing the remaining first halogen element separately from the atomic layer etching step, the processing time can be shortened and the throughput can be improved.

[0076] (d) The above effects can also be obtained similarly when using an oxide film other than the Al2O3 film, a first halogen element-containing gas other than HF gas, a second halogen element-containing gas other than BCl3 gas, a reforming gas other than O3 gas, a third halogen element-containing gas other than BCl3 gas, or an inert gas other than N2 gas.

[0077] <Other aspects of the present disclosure> As described above, the aspects of the present disclosure have been specifically described. However, the present disclosure is not limited to the above aspects, and various modifications can be made without departing from the gist thereof.

[0078] (Second aspect) Next, the atomic layer etching step S30, which is a substrate processing step according to the second aspect, will be described with reference to FIG. 6.

[0079] In this aspect, after steps S310 to S340, which are performed in the same manner as steps S110 to S140 in the above-described atomic layer etching process (step S10), steps S350 and S360, which are performed in the same manner as steps S210 and S220 in the above-described residual first halogen element removal process (S20), are performed. Then, as step S370, a cycle of performing steps S310 to S360 is performed a predetermined number of times (p times, where p is an integer of 1 or more). That is, a modified gas is supplied for each cycle (also referred to as each etching) to remove the first halogen element for each layer. In this way, while etching the oxide film formed on the surface of the wafer 200, a process of removing the first halogen element is performed. Also in this aspect, the same effect as the above-described aspect can be obtained.

[0080] Note that after performing steps S310 to S370 described above, the above-described residual first halogen element removal process (S20) may be performed. Also in this aspect, the same effect as the above-described aspect can be obtained, and furthermore, the amount of the remaining first halogen element can be reduced.

[0081] (Third Aspect) Next, the atomic layer etching process S40, which is a substrate processing process according to the third aspect, will be described with reference to FIG. 7.

[0082] In this aspect, after steps S410 to S440, which are performed in the same manner as steps S110 to S140 in the above-described atomic layer etching process (step S10), steps S450 to S480, which are performed in the same manner as steps S210 to S240 in the above-described residual first halogen element removal process (S20), are performed. Then, as step S490, a cycle of performing steps S410 to S480 is performed a predetermined number of times (q times, where q is an integer of 1 or more). That is, a modified gas and a third halogen element-containing gas are supplied for each cycle (also referred to as each etching) to remove the first halogen element for each layer. In this way, while etching the oxide film formed on the surface of the wafer 200, a process of removing the first halogen element is performed. Also in this aspect, the same effect as the above-described aspect can be obtained.

[0083] In addition, after performing the above-described steps S410 to S490, the above-described residual first halogen element removal step (S20) may be performed. Also in this embodiment, the same effects as those of the above-described embodiment can be obtained, and furthermore, the amount of the remaining first halogen element can be reduced.

[0084] (Fourth Embodiment) In this embodiment, in the atomic layer etching step (S10), the order of the supply of the first halogen element-containing gas (S110) and the supply of the second halogen element-containing gas (S130) is reversed. That is, a cycle of performing the supply of the second halogen element-containing gas (S130), the purge (S120), the supply of the first halogen element-containing gas (S110), and the purge (S140) is performed a predetermined number of times. When, for example, HF gas is used as the first halogen element-containing gas and BCl3 gas is used as the second halogen element-containing gas, by supplying BCl3 gas first, the following reaction occurs between the Al2O3 on the surface of the wafer 200.

[0085] Al2O3 + 2BCl3 → 2AlCl3 + B2O3

[0086] After supplying BCl3 gas, by supplying HF gas, the following reaction occurs on the wafer 200. AlCl3 + 2HF → AlClF2 + 2HCl AlCl3 + HF → AlCl2F + HCl AlCl3 + 3HF → AlF3 + HCl

[0087] In addition, B2O3 that has not volatilized may remain on the surface of Al2O3, and in this case, the following reaction occurs. B2O3 + 6HF → 2BF3 + 3H2O

[0088] In addition, a part of the wafer 200 is in a state where Al2O3 is exposed, and the following reaction occurs.

[0089] Al2O3 + HF → AlOF + H2O

[0090] That is, AlCl X F y and H2O and HCl are desorbed from the surface of the wafer 200, but AlF3 and AlOF are difficult to desorb and F remains.

[0091] As described above, even for the wafer 200 that has been etched using the first halogen element-containing gas, by performing the above-described residual first halogen element removal step (S20), the residual first halogen element is removed, and the same effect as the above-described embodiment is obtained.

[0092] (Other embodiments) In the above embodiment, the case where the residual first halogen element removal step (S20) is performed after the atomic layer etching step (S10) has been described. However, the present disclosure is not limited to this, and the residual first halogen element removal step (S20) may be performed before the atomic layer etching step (S10).

[0093] In the above embodiment, the case where the reforming gas supply (S210) and the third halogen element-containing gas supply (S230) are alternately performed in the residual first halogen element removal step (S20) has been described. The present disclosure is not limited to this, and the reforming gas supply (S210) and the third halogen element-containing gas supply (S230) may be performed in parallel. This is particularly suitable when an H-containing gas is used as the reforming gas.

[0094] In the above embodiment, the case where the atomic layer etching step (S10) and the residual first halogen element removal step (S20) are continuously performed (in-situ) in the same processing furnace has been described. However, the present disclosure is not limited to this, and the atomic layer etching step (S10) and the residual first halogen element removal step (S20) may be performed (ex-situ) in different processing furnaces.

[0095] Note that the recipe used for substrate processing is preferably prepared individually according to the processing content and stored in the storage device 121c via a telecommunication line or an external storage device 123. When starting substrate processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the processing content from among a plurality of recipes stored in the storage device 121c. Thereby, it becomes possible to form films with various film types, composition ratios, film qualities, and film thicknesses with good reproducibility on a single substrate processing apparatus. In addition, the burden on the operator can be reduced, operation mistakes can be avoided, and substrate processing can be started quickly.

[0096] The above-mentioned recipe is not limited to the case of newly creating it. For example, it may be prepared by modifying an existing recipe already installed in the substrate processing apparatus. When modifying the recipe, the modified recipe may be installed in the substrate processing apparatus via a telecommunication line or a recording medium on which the recipe is recorded. Alternatively, the input / output device 122 provided in the existing substrate processing apparatus may be operated to directly modify the existing recipe already installed in the substrate processing apparatus.

[0097] In the above aspect, an example of processing a film using a batch-type substrate processing apparatus that processes a plurality of substrates at once has been described. The present disclosure is not limited to the above aspect. For example, it can also be suitably applied when processing a film using a single-wafer-type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above aspect, an example of processing a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above aspect and can also be suitably applied when processing a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0098] Even when using these substrate processing apparatuses, film formation processing can be performed under the same processing procedures and processing conditions as in the above aspect, and the same effects as in the above aspect can be obtained.

[0099] In addition, the above aspects can be used in appropriate combinations. The processing procedures and processing conditions at this time can be, for example, the same as the processing procedures and processing conditions of the above aspects.

Explanation of Symbols

[0100] 200 wafers (substrates)

Claims

1. (a) a step of supplying a gas containing a first halogen element to a substrate; (b) a step of supplying a gas containing a second halogen element to the substrate; (c) a step of supplying a reforming gas to the substrate; (d) a step of supplying a gas containing a third halogen element to the substrate; (e) a step of performing (a) and (b) a predetermined number of times to process the substrate; (f) a step of performing (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e), and having, wherein the first halogen element is fluorine A substrate processing method.

2. (a) a step of supplying a gas containing a first halogen element to a substrate; (b) a step of supplying a gas containing a second halogen element to the substrate; (c) a step of supplying a reforming gas to the substrate; (d) a step of supplying a gas containing a third halogen element to the substrate; (e) a step of performing (a) and (b) a predetermined number of times to process the substrate; (f) a step of performing (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e), and having, (f) is performed after (e) A substrate processing method.

3. In (e), (a) and (b) are performed alternately. The substrate processing method according to Claim 1.

4. In (f), (c) and (d) are performed alternately. The substrate processing method according to Claim 1.

5. (a) a step of supplying a gas containing a first halogen element to a substrate; (b) a step of supplying a gas containing a second halogen element to the substrate; (c) a step of supplying a reforming gas to the substrate; (d) a step of supplying a gas containing a third halogen element to the substrate; (e) a step of performing (a) and (b) a predetermined number of times to process the substrate; (f) a step of performing (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e), and having, In (f), it has a timing of performing (c) and (d) in parallel A substrate processing method.

6. The first halogen element and the second halogen element are different elements. The substrate processing method according to Claim 1.

7. The second halogen element is chlorine. The substrate processing method according to Claim 1.

8. The gas containing the first halogen element is a hydrogen compound. The substrate processing method according to Claim 1.

9. The gas containing the second halogen element is a compound of a Group 13 element or a Group 15 element. The substrate processing method according to Claim 1.

10. The substrate processing method according to claim 1, wherein the third halogen element is an element different from the first halogen element.

11. The substrate processing method according to claim 1, wherein the third halogen element is the same element as the second halogen element.

12. An oxide film is formed on the substrate, and (e) is a step of etching the oxide film. The substrate processing method according to claim 1.

13. The substrate processing method according to claim 12, wherein the oxide film is an oxide film containing a metal element.

14. (a) A step of supplying a gas containing a first halogen element to a substrate on which an oxide film is formed; (b) A step of supplying a gas containing a second halogen element to the substrate; (c) A step of supplying a reforming gas to the substrate; (d) A step of supplying a gas containing a third halogen element to the substrate; (e) Repeating (a) and (b) a predetermined number of times to etch the oxide film; (f) Repeating (c) and (d) a predetermined number of times to remove the halogen element remaining on the substrate in (e). A substrate processing method having the above steps.

15. (a) A step of supplying a gas containing a first halogen element to a substrate; (b) A step of supplying a gas containing a second halogen element to the substrate; (c) A step of supplying a reforming gas to the substrate; (d) A step of supplying a gas containing a third halogen element to the substrate; (e) Repeating (a) and (b) a predetermined number of times to process the substrate; (f) Repeating (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e). The first halogen element is fluorine. A method for manufacturing a semiconductor device.

16. (a) A step of supplying a gas containing a first halogen element to a substrate; (b) A step of supplying a gas containing a second halogen element to the substrate; (c) A step of supplying a reforming gas to the substrate; (d) A step of supplying a gas containing a third halogen element to the substrate; (e) Repeating (a) and (b) a predetermined number of times to process the substrate; (f) After (e), repeating (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e). A method for manufacturing a semiconductor device having the above steps.

17. (a) A step of supplying a gas containing a first halogen element to a substrate; (b) A step of supplying a gas containing a second halogen element to the substrate; (c) A step of supplying a reforming gas to the substrate; (d) A step of supplying a gas containing a third halogen element to the substrate; Step (e): Performing steps (a) and (b) a predetermined number of times to process the substrate; Step (f): Having a timing for performing steps (c) and (d) in parallel, performing steps (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in step (e); A method for manufacturing a semiconductor device having the above steps.

18. Step (a): Supplying a gas containing a first halogen element to a substrate on which an oxide film is formed; Step (b): Supplying a gas containing a second halogen element to the substrate; Step (c): Supplying a reforming gas to the substrate; Step (d): Supplying a gas containing a third halogen element to the substrate; Step (e): Performing steps (a) and (b) a predetermined number of times to etch the oxide film; Step (f): Performing steps (c) and (d) a predetermined number of times to remove the halogen element remaining on the substrate in step (e); A method for manufacturing a semiconductor device having the above steps.

19. Step (a): A procedure for supplying a gas containing a first halogen element to a substrate; Step (b): A procedure for supplying a gas containing a second halogen element to the substrate; Step (c): A procedure for supplying a reforming gas to the substrate; Step (d): A procedure for supplying a gas containing a third halogen element to the substrate; Step (e): Performing steps (a) and (b) a predetermined number of times to process the substrate; Step (f): Performing steps (c) and (d) a predetermined number of times and a procedure for removing the first halogen element remaining on the substrate in step (e), and causing a computer to execute the procedure on a substrate processing apparatus, wherein the first halogen element is fluorine.

20. Step (a): A procedure for supplying a gas containing a first halogen element to a substrate; Step (b): A procedure for supplying a gas containing a second halogen element to the substrate; Step (c): A procedure for supplying a reforming gas to the substrate; Step (d): A procedure for supplying a gas containing a third halogen element to the substrate; Step (e): Performing steps (a) and (b) a predetermined number of times to process the substrate; Step (f): After step (e), performing steps (c) and (d) a predetermined number of times and a procedure for removing the first halogen element remaining on the substrate in step (e); A program for causing a computer to execute the procedure on a substrate processing apparatus.

21. Step (a): A procedure for supplying a gas containing a first halogen element to a substrate; Step (b): A procedure for supplying a gas containing a second halogen element to the substrate; Step (c): A procedure for supplying a reforming gas to the substrate; Step (d): A procedure for supplying a gas containing a third halogen element to the substrate; Step (e): Performing steps (a) and (b) a predetermined number of times to process the substrate; (f) a step of performing steps (c) and (d) in parallel a predetermined number of times, and removing the first halogen element remaining on the substrate in (e); A program for causing a computer to execute the above in a substrate processing apparatus.

22. (a) supplying a first halogen element-containing gas to a substrate having an oxide film formed thereon; (b) supplying a second halogen-containing gas to the substrate; (c) supplying a modifying gas to the substrate; (d) supplying a third halogen-containing gas to the substrate; (e) performing steps (a) and (b) a predetermined number of times to etch the oxide film; (f) performing steps (c) and (d) a predetermined number of times, and removing the halogen element remaining on the substrate in step (e); A program for causing a computer to execute the above in a substrate processing apparatus.

23. A first halogen element-containing gas supply system that supplies a first halogen element-containing gas to the substrate; a second halogen element-containing gas supply system for supplying a second halogen element-containing gas to the substrate; a modifying gas supply system that supplies a modifying gas to the substrate; a third halogen element-containing gas supply system for supplying a third halogen element-containing gas to the substrate; (a) supplying the first halogen element-containing gas; (b) supplying the second halogen element-containing gas; (c) supplying the reformed gas; (d) supplying the third halogen element-containing gas; (e) performing steps (a) and (b) a predetermined number of times to process the substrate; and (f) performing (c) and (d) a predetermined number of times, and removing the first halogen element remaining on the substrate in (e); a control unit configured to be able to control the first halogen element-containing gas supply system, the second halogen element-containing gas supply system, the modifying gas supply system, and the third halogen element-containing gas supply system so as to perform The substrate processing apparatus, wherein the first halogen element is fluorine.

24. A first halogen element-containing gas supply system that supplies a first halogen element-containing gas to the substrate; a second halogen element-containing gas supply system for supplying a second halogen element-containing gas to the substrate; a modifying gas supply system that supplies a modifying gas to the substrate; a third halogen element-containing gas supply system for supplying a third halogen element-containing gas to the substrate; (a) supplying the first halogen element-containing gas; (b) a process of supplying the second halogen element-containing gas, and (c) a process of supplying the reformed gas, and (d) a process of supplying the third halogen element-containing gas, and (e) a process of performing (a) and (b) a predetermined number of times to process the substrate, and (f) after (e), a process of performing (c) and (d) a predetermined number of times to remove the first halogen element remaining on the substrate in (e), and a control unit configured to be able to control the first halogen element-containing gas supply system, the second halogen element-containing gas supply system, the reformed gas supply system, and the third halogen element-containing gas supply system so as to perform the above, a substrate processing apparatus having the same.

25. A first halogen element-containing gas supply system for supplying a first halogen element-containing gas to a substrate, a second halogen element-containing gas supply system for supplying a second halogen element-containing gas to the substrate, a reformed gas supply system for supplying a reformed gas to the substrate, a third halogen element-containing gas supply system for supplying a third halogen element-containing gas to the substrate, (a) a process of supplying the first halogen element-containing gas, (b) a process of supplying the second halogen element-containing gas, (c) a process of supplying the reformed gas, (d) a process of supplying the third halogen element-containing gas, (e) a process of performing (a) and (b) a predetermined number of times to process the substrate, (f) having a timing of performing (c) and (d) in parallel, performing (c) and (d) a predetermined number of times, and a process of removing the first halogen element remaining on the substrate in (e), and a control unit configured to be able to control the first halogen element-containing gas supply system, the second halogen element-containing gas supply system, the reformed gas supply system, and the third halogen element-containing gas supply system so as to perform the above, a substrate processing apparatus having the same.

26. A first halogen element-containing gas supply system for supplying a first halogen element-containing gas to a substrate on which an oxide film is formed, a second halogen element-containing gas supply system for supplying a second halogen element-containing gas to the substrate, a reformed gas supply system for supplying a reformed gas to the substrate, a third halogen element-containing gas supply system for supplying a third halogen element-containing gas to the substrate, (a) a process of supplying the first halogen element-containing gas, (b) a process of supplying the second halogen element-containing gas, (c) a process of supplying the reformed gas, (d) a process of supplying the third halogen element-containing gas; (e) a process of performing (a) and (b) a predetermined number of times to etch the oxide film; (f) a process of performing (c) and (d) a predetermined number of times to remove the halogen element remaining on the substrate in (e); a control unit configured to be capable of controlling the first halogen element-containing gas supply system, the second halogen element-containing gas supply system, the reformed gas supply system, and the third halogen element-containing gas supply system so as to perform the above; A substrate processing apparatus having the above.

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