Semiconductor device manufacturing method, recording medium and substrate processing device

Abstract

The present invention provides a method for manufacturing a semiconductor device, a recording medium, and a substrate processing device, which can suppress the generation of particles due to film peeling in a processing chamber. The method for manufacturing a semiconductor device of the present invention comprises: (a) a step of moving a substrate formed with an oxide film into a processing chamber formed with a metal-containing film, (b) a step of supplying at least one of a gas containing a Group 14 element and hydrogen or an oxygen-containing gas into the processing chamber, and (c) a step of forming a metal-containing film on the substrate after step (b).

Description

Technical Field

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

[0002] As a row address line (wordline) of a NAND flash memory or DRAM having a three-dimensional structure, for example, a low-resistance tungsten (W) film is used. In addition, a titanium nitride (TiN) film is sometimes provided between the W film and the insulating film as a barrier film (for example, see Patent Documents 1 and 2). The TiN film has the function of improving the adhesion between the W film and the insulating film, and sometimes a nucleation film for W film growth is formed on the TiN film.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-66263

[0006] Patent Document 2: International Publication No. 2019 / 058608 Pamphlet Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, such a nucleation film is also formed on the inner wall of the processing chamber, a dummy substrate, etc. If the cumulative film thickness increases, it may grow abnormally as large crystal grains, and film peeling may occur.

[0009] An object of the present disclosure is to provide a technology capable of suppressing the generation of particles caused by film peeling in a processing chamber.

[0010] Solution to the problem

[0011] According to one aspect of the present disclosure, a method for manufacturing a semiconductor device is provided, comprising: (a) a step of moving a substrate formed with an oxide film into a processing chamber formed with a metal-containing film, (b) a step of supplying at least one of a gas containing a Group 14 element and hydrogen or an oxygen-containing gas into the processing chamber, and (c) a step of forming the metal-containing film on the substrate after step (b).

[0012] Effects of the Invention

[0013] According to the present disclosure, generation of particles caused by film peeling in a processing chamber can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a longitudinal sectional view schematically showing a vertical processing furnace of a substrate processing apparatus in one embodiment of the present disclosure.

[0015] Figure 2 yes Figure 1 Schematic cross-section diagram along line AA.

[0016] Figure 3 This is a schematic configuration diagram of a controller of a substrate processing apparatus in one embodiment of the present disclosure, and is a diagram showing a control system of the controller using a block diagram.

[0017] Figure 4 It is a figure which shows the film formation stage in one embodiment of this disclosure.

[0018] Figure 5 It is a diagram showing a modification example of the film forming stage in one embodiment of the present disclosure.

[0019] Figure 6 This is a diagram showing a comparison of the surface roughness of the TiN film formed on the dummy substrate in the comparative example and the example.

[0020] Explanation of symbols

[0021] 10: substrate processing device, 121: controller, 200: wafer (substrate), 201: processing chamber. DETAILED DESCRIPTION

[0022] Below, refer to Figures 1 to 4 To explain.

[0023] (1) Configuration of substrate processing apparatus

[0024] The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating device (heating mechanism, heating system). The heater 207 has a cylindrical shape and is supported by a heater base (not shown) as a holding plate and installed vertically.

[0025] An outer tube 203 constituting a reaction tube (reaction container, processing container) is provided inside the heater 207 in a concentric circle with the heater 207. The outer tube 203 is made of, for example, quartz (SiO 2 ), silicon carbide (SiC) and other heat-resistant materials, and are formed into a cylindrical shape with a closed upper end and an open lower end. A header (inlet flange) 209 is arranged concentrically with the outer tube 203 below the outer tube 203. The header 209 is made of a metal such as stainless steel (SUS) and is formed into a cylindrical shape with both the upper and lower ends open. An O-ring 220a is provided as a sealing member between the upper end of the header 209 and the outer tube 203. The header 209 is supported by the heater base so that the outer tube 203 is installed vertically.

[0026] An inner tube 204 constituting a reaction vessel is disposed inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz or SiC, and is formed into a cylindrical shape with a closed upper end and an open lower end. The processing vessel (reaction vessel) is mainly composed of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing vessel (inside the inner tube 204).

[0027] The processing chamber 201 is configured to accommodate wafers 200 as substrates in a horizontal posture in a state where wafer cassettes 217 described later are arranged in multiple stages in the vertical direction.

[0028] Nozzles 410, 420, 430 are provided in the processing chamber 201 so as to penetrate the side wall of the header 209 and the inner tube 204. The nozzles 410, 420, 430 are respectively connected to the gas supply pipes 310, 320, 330. However, the processing furnace 202 of this embodiment is not limited to the above.

[0029] In the gas supply pipes 310, 320, 330, mass flow controllers (MFCs) 312, 322, 332 as flow controllers (flow control units) are respectively provided in order from the upstream side. In addition, valves 314, 324, 334 as switch valves are respectively provided in the gas supply pipes 310, 320, 330. Downstream sides of the valves 314, 324, 334 of the gas supply pipes 310, 320, 330 are connected to gas supply pipes 510, 520, 530 for supplying inert gas. In the gas supply pipes 510, 520, 530, MFCs 512, 522, 532 as flow controllers (flow control units) and valves 514, 524, 534 as switch valves are respectively provided in order from the upstream side.

[0030] The front ends of the gas supply pipes 310, 320, 330 are connected to the nozzles 410, 420, 430, respectively. The nozzles 410, 420, 430 are configured as L-shaped nozzles, and the horizontal portions thereof are provided to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, 430 are provided inside the preparatory chamber 201a formed in a channel shape (groove shape) protruding outward in the radial direction of the inner tube 204 and extending in the vertical direction, and are provided inside the preparatory chamber 201a to face upward (above the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

[0031] The nozzles 410, 420, 430 are arranged to extend from the lower area of ​​the processing chamber 201 to the upper area of ​​the processing chamber 201, and a plurality of gas supply holes 410a, 420a, 430a are respectively arranged at positions opposite to the wafer 200. Thus, the processing gas is respectively supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430. The gas supply holes 410a, 420a, 430a are arranged in plurality from the lower part to the upper part of the inner tube 204, each having the same opening area, and further arranged at the same opening spacing. However, the gas supply holes 410a, 420a, 430a are not limited to the above-mentioned manner. For example, the opening area may gradually increase from the lower part to the upper part of the inner tube 204. Thus, the flow rate of the gas supplied from the gas supply holes 410a, 420a, 430a can be more uniform.

[0032] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in a plurality of height positions from the lower part to the upper part of the wafer box 217 described later. Therefore, the processing gas supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 into the processing chamber 201 is supplied to all the wafers 200 accommodated from the lower part to the upper part of the wafer box 217. The nozzles 410, 420, 430 only need to be provided to extend from the lower area to the upper area of ​​the processing chamber 201, but are preferably provided to extend to the vicinity of the top of the wafer box 217.

[0033] A raw material gas (metal-containing gas) containing a metal element as a processing gas is supplied from a gas supply pipe 310 into the processing chamber 201 via an MFC 312, a valve 314, and a nozzle 410. As a raw material, titanium tetrachloride (TiCl4) which is a halogen-based raw material (halide, halogen-based titanium raw material) containing titanium (Ti) as a metal element is used. 4 ).

[0034] A gas containing a Group 14 element and hydrogen (H) as a processing gas is supplied from a gas supply pipe 320 into the processing chamber 201 via an MFC 322, a valve 324, and a nozzle 420. As the gas containing a Group 14 element and H, for example, monosilane (SiH) as a silane-based gas, which is a gas containing silicon (Si) and H, can be used. 4 )gas.

[0035] A reaction gas that reacts with the metal-containing gas is supplied from the gas supply pipe 330 into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 430. As the reaction gas, a N-containing gas such as ammonia (NH 3 )gas.

[0036] Inert gas such as nitrogen (N) is supplied from gas supply pipes 510, 520, 530 through MFCs 512, 522, 532, valves 514, 524, 534, and nozzles 410, 420, 430, respectively. 2 ) gas is supplied into the processing chamber 201. 2 Gas is described as an example of an inert gas, but as an inert gas, except N 2 In addition to the gas, an inert gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc. can also be used.

[0037] The processing gas supply system is mainly composed of gas supply pipes 310, 320, 330, MFC312, 322, 332, valves 314, 324, 334, and nozzles 410, 420, 430. It is also possible to consider only nozzles 410, 420, 430 as the processing gas supply system. The processing gas supply system can be simply referred to as the gas supply system. When the raw gas flows in from the gas supply pipe 310, the raw gas supply system is mainly composed of the gas supply pipe 310, MFC312, and valve 314. It is also possible to consider incorporating the nozzle 410 into the raw gas supply system. In addition, when the silane-based gas flows in from the gas supply pipe 320, the silane-based gas supply system is mainly composed of the gas supply pipe 320, MFC322, and valve 324, but it is also possible to consider incorporating the nozzle 420 into the silane-based gas supply system. In addition, when the reaction gas flows from the gas supply pipe 330, the reaction gas supply system is mainly composed of the gas supply pipe 330, the MFC 332, and the valve 334. It is also possible to consider incorporating the nozzle 430 into the reaction gas supply system. When the nitrogen-containing gas is supplied as the reaction gas from the gas supply pipe 330, the reaction gas supply system can also be called a nitrogen-containing gas supply system. In addition, the inert gas supply system is mainly composed of the gas supply pipes 510, 520, 530, the MFCs 512, 522, 532, and the valves 514, 524, 534.

[0038] In the gas supply method of this embodiment, the gas is transported through the nozzles 410, 420, 430 arranged in the preparatory chamber 201a in the annular vertical space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200. In addition, the gas is ejected into the inner tube 204 from the plurality of gas supply holes 410a, 420a, 430a provided at the positions where the nozzles 410, 420, 430 are opposite to the wafers. More specifically, the raw material gas and the like are ejected in a direction parallel to the surface of the wafer 200 through the gas supply holes 410a of the nozzle 410, the gas supply holes 420a of the nozzle 420, and the gas supply holes 430a of the nozzle 430.

[0039] The exhaust hole (exhaust port) 204a is a through hole formed at a position where the side wall of the inner tube 204 is opposite to the nozzles 410, 420, 430, for example, a slit-shaped through hole opened in a vertical direction. The gas supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 into the processing chamber 201 and flowing over the surface of the wafer 200 flows through the gap (inside the exhaust path 206) formed between the inner tube 204 and the outer tube 203 via the exhaust hole 204a. Then, the gas flowing into the exhaust path 206 flows into the exhaust pipe 231 and is discharged to the outside of the processing furnace 202.

[0040] The exhaust hole 204a is provided at a position opposite to the plurality of wafers 200. The gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafers 200 in the processing chamber 201 flows in a horizontal direction and then flows into the exhaust path 206 through the exhaust hole 204a. The exhaust hole 204a is not limited to being a slit-shaped through hole, but may be composed of a plurality of holes.

[0041] An exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is provided on the manifold 209. In the exhaust pipe 231, the pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, the APC (Auto Pressure Controller) valve 243, and the vacuum pump 246 as a vacuum exhaust device are connected in sequence from the upstream side. The APC valve 243 can perform vacuum exhaust and stop vacuum exhaust in the processing chamber 201 by opening and closing the valve when the vacuum pump 246 is working, and can adjust the pressure in the processing chamber 201 by adjusting the valve opening when the vacuum pump 246 is working. The exhaust system is mainly composed of an exhaust hole 204a, an exhaust path 206, an exhaust pipe 231, an APC valve 243 and a pressure sensor 245. It is also conceivable to incorporate the vacuum pump 246 into the exhaust system.

[0042] Below the manifold 209, a sealing cap 219 is provided as a furnace port cover body capable of hermetically closing the lower end opening of the manifold 209. The sealing cap 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. The sealing cap 219 is made of a metal material such as SUS, for example, and is formed in a disc shape. On the upper surface of the sealing cap 219, an O-ring 220b is provided as a sealing member abutting against the lower end of the manifold 209. A rotating mechanism 267 for rotating the wafer box 217 containing the wafer 200 is provided on the opposite side of the sealing cap 219 from the processing chamber 201. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cap 219 and is connected to the wafer box 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer box 217. The sealing cap 219 is configured to be lifted and lowered in the vertical direction by a wafer box elevator 115 as a lifting mechanism vertically provided outside the outer tube 203. The wafer box elevator 115 is configured to be able to move the wafer box 217 into and out of the processing chamber 201 by lifting and lowering the sealing cap 219. The wafer box elevator 115 is configured as a conveying device (conveying mechanism, conveying system) that conveys the wafer box 217 and the wafers 200 contained in the wafer box 217 to inside and outside the processing chamber 201.

[0043] The wafer box 217 as a substrate support is configured to be able to arrange multiple (for example, 25 to 200) wafers 200 in a horizontal posture and in a state where the centers are aligned with each other in the vertical direction at intervals. The wafer box 217 is composed of a heat-resistant material such as quartz, SiC, etc. In the lower part of the wafer box 217, a heat insulation plate 218 composed of a heat-resistant material such as quartz, SiC, etc. is supported in multiple stages (not shown) in a horizontal posture. Through such a structure, it is difficult for the heat from the heater 207 to be conducted to the sealing cap 219 side. However, the present embodiment is not limited to the above method. For example, instead of setting the heat insulation plate 218 at the lower part of the wafer box 217, an insulation cylinder composed of a cylindrical member composed of a heat-resistant material such as quartz, SiC, etc. may be set.

[0044] like Figure 2 As shown, the structure is as follows: a temperature sensor 263 as a temperature detector is provided in the inner tube 204, and the amount of power supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 reaches a desired temperature distribution. The temperature sensor 263 is L-shaped like the nozzles 410, 420, 430, and is provided along the inner wall of the inner tube 204.

[0045] like Figure 3As shown, the controller 121 as a control unit (control device) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, the storage device 121c, and the I / O interface 121d are configured to be able to exchange data with the CPU 121a via an internal bus. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel.

[0046] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), etc. A control program for controlling the operation of the substrate processing device is stored in the storage device 121c, and a process recipe that records the process, conditions, etc. of the manufacturing method of the semiconductor device described later and can be read out. The process recipe is a combination of each process (step) in the manufacturing method of the semiconductor device described later so that it is executed by the controller 121 and a predetermined result is obtained, and functions as a program. Hereinafter, these process recipes, control programs, etc. are simply collectively referred to as programs. When the term "program" is used in this specification, it includes the case of only a single process recipe, the case of only a single control program, and the case of a combination of a process recipe and a control program. RAM121b is configured as a storage area (working area) for temporarily storing programs, data, etc. read by CPU121a.

[0047] The I / O interface 121d is connected to the above-mentioned MFC312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, wafer box elevator 115, etc.

[0048] The CPU 121a is configured to read out a control program from the storage device 121c and execute it, and to read out a recipe from the storage device 121c in response to input of an operation command from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 512, 522, 532, the opening and closing operation of the valves 314, 324, 334, 514, 524, 534, the opening and closing operation of the APC valve 243 and the pressure adjustment operation by the pressure sensor 245 by the APC valve 243, the temperature adjustment operation of the heater 207 by the temperature sensor 263, the start and stop of the vacuum pump 246, the rotation and rotation speed adjustment operation of the wafer cassette 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer cassette 217 by the wafer cassette elevator 115, the operation of accommodating the wafer 200 in the wafer cassette 217, etc., according to the contents of the read out recipe.

[0049] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a magnetic tape, a floppy disk, a hard disk, an optical disk such as a CD, a DVD, an optical magnetic disk such as an MO, a USB memory, a semiconductor memory such as a memory card) 123 into a computer. The storage device 121c and the external storage device 123 are configured as a recording medium that can be read by a computer. Hereinafter, these are also simply collectively referred to as recording media. In this specification, the recording medium includes a case where there is only a single storage device 121c, a case where there is only a single external storage device 123, or a case where both are included. Providing a program to a computer may not use an external storage device 123, but may also be done using the Internet or a dedicated line communication method.

[0050] (2) Substrate processing steps

[0051] As one example of a process for manufacturing a semiconductor device (equipment), a TiN film is formed on a wafer 200 on which an insulating film and an oxide film are formed. Figure 4 The process of forming a TiN film is performed using the processing furnace 202 of the substrate processing device 10 described above. By performing the film forming process described later at least once in the processing furnace 202, a TiN film is formed in the processing chamber 201. In the following description, the operation of each part constituting the substrate processing device 10 is controlled by the controller 121. The product wafer manufactured in this process is, for example, a SiO2 film formed in a groove formed on a Si substrate used as a shallow trench isolation (STI) of a semiconductor device. 2 Film and SiO 2 Wafer with TiN film embedded in the film. It should be noted that the TiN film is used as a gate electrode.

[0052] The substrate processing step (semiconductor device manufacturing step) of the present embodiment includes (a) forming a silicon oxide (SiO 2 ) film is moved into a processing chamber 201 on which a TiN film as a metal-containing film is formed, and (b) a silane-based gas as a gas containing a Group 14 element and H or an O as a gas containing oxygen (O) is supplied into the processing chamber 201. 2 (c) a step of forming a TiN film as a metal-containing film on the wafer 200 after the step (b).

[0053] In step (b), in the processing furnace 202, a film containing a Group 14 element or an oxide film is formed on the wall in the processing chamber 201, the dummy substrate used as the heat shield 218, and the like.

[0054] In the step (c), TiCl is supplied as a metal-containing gas to the wafer 200 by alternately repeating the process. 4 Gas process and supply of NH as a reaction gas 3 In the process of the gas, a TiN film as a metal-containing film is formed on the wafer 200 .

[0055] Here, when a TiN film is formed on a wafer, a nucleation film is also formed on the walls, pseudo substrates, etc. in the processing chamber 201. Furthermore, if the cumulative film thickness of the film formed on the walls, etc. in the processing chamber 201 increases, it will grow abnormally into large grains, and film peeling will occur, which will become a cause of particle generation. In this embodiment, a wafer 200 formed with an oxide film is moved into a processing chamber 201 formed with a TiN film, and before the process of forming a TiN film is performed in the processing chamber 201, a process of supplying a gas containing a Group 14 element and H or a process of supplying an O-containing gas is performed as a treatment process described later. As a result, the grains of the TiN film formed on the walls, pseudo substrates, etc. in the processing chamber 201 can be divided, thereby suppressing the occurrence of film peeling. That is, the surface of the TiN film formed on the wall, dummy substrate, etc. in the processing chamber 201 is subjected to titanium silicide (TiSiN) or oxidation (titanium oxynitride (TiNO) or titanium oxide (TiO)) to form a grain dividing film that divides the grains. That is, the growth of the nucleation film of the TiN film formed on the wall, dummy substrate, etc. in the processing chamber 201 can be stopped, the nucleation film can be flattened, and the film peeling can be suppressed. It should be noted that during the treatment process, since the SiO 2 The wafer with the TiN film is carried into the processing chamber 201, so there is no influence on the wafer 200. That is, only the grains of the TiN film formed on the wall, the dummy substrate, etc. in the processing chamber 201 can be selectively divided, and the grain dividing film is formed only on the surface of the TiN film formed on the wall, the dummy substrate, etc. in the processing chamber 201.

[0056] In this specification, when the term "wafer" is used, it includes the case where it means "the wafer itself" and the case where it means "a stack of a wafer and a predetermined layer, film, etc. formed on its surface." In this specification, when the term "wafer surface" is used, it includes the case where it means "the surface of the wafer itself" and the case where it means "the surface of a predetermined layer, film formed on the wafer." In this specification, when the term "substrate" is used, it has the same meaning as when the term "wafer" is used.

[0057] (Wafer loading)

[0058] After a plurality of wafers 200 having oxide films formed thereon are loaded into a wafer cassette 217 (wafer loading), Figure 1 As shown, the wafer cassette 217 supporting a plurality of wafers 200 is lifted by the wafer cassette elevator 115 and carried into the processing chamber 201 where the TiN film is formed (wafer cassette loading). In this state, the sealing cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0059] (Pressure adjustment and temperature adjustment)

[0060] The vacuum pump 246 performs vacuum exhaust so that the processing chamber 201, that is, the space where the wafer 200 is located, reaches the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback controlled (pressure adjusted) based on the measured pressure information. The vacuum pump 246 is kept in a working state at least until the processing of the wafer 200 is completed. In addition, the heater 207 heats the processing chamber 201 so that it reaches the desired temperature. At this time, the amount of power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263, so that the desired temperature distribution (temperature adjustment) is achieved in the processing chamber 201. The heating of the processing chamber 201 by the heater 207 continues at least until the processing of the wafer 200 is completed.

[0061] [Treatment process] (Supply of SiH 4 gas)

[0062] The valve 324 is opened to allow SiH2O2, a silane-based gas, to flow into the gas supply pipe 320. 4 The gas is a gas containing a Group 14 element and H. SiH 4 The gas is supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420 at a flow rate adjusted by the MFC 322, and then exhausted from the exhaust pipe 231. At this time, SiH2O2 is supplied to the wafer 201. 4 At the same time, valve 524 is opened to allow N2 to flow into the gas supply pipe 520. 2N flowing in the gas supply pipe 520 2 The gas flow rate is adjusted by MFC522 and SiH 4 The gases are supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, the valves 514 and 534 are closed, and the supply of N from the nozzles 410 and 430 is stopped. 2 gas.

[0063] At this time, the APC valve 243 is fully opened. The SiH controlled by the MFC 322 4 The supply flow rate of the gas is, for example, within the range of 0.1 to 10 slm, and is set to, for example, 2 slm. 2 The supply flow rate of the gas is, for example, in the range of 0.1 to 20 slm. It should be noted that the pressure in the processing chamber 201 in this process is set to be lower than the pressure in the processing chamber 201 in the film forming process described later. In addition, the flow rate of the gas supplied in this process is set to be less than the flow rate of the gas supplied in the film forming process described later. Thus, SiH 4 The gas spreads throughout the entire processing chamber 201 , and can selectively treat only the TiN film formed on the wall and the like in the processing chamber 201 without affecting the wafer 200 , which is a product wafer.

[0064] At this time, the temperature of the heater 207 is set so that the temperature of the wafer 200 is stably maintained at a temperature within a range of, for example, 350 to 500° C. It should be noted that the temperature in this process is set higher than the temperature in the film forming process described later. The temperature in this process is preferably 500° C. or less. This is because if the temperature in this process is higher than 500° C., the incubation time becomes shorter and a Si film is formed on the wafer 200.

[0065] At this time, the gas flowing in the processing chamber 201 is SiH 4 Gas. By supplying SiH 4 The gas forms a titanium silicide nitride (TiSiN) film as a crystal layer dividing film on the surface of the TiN film such as the wall in the processing chamber 201, so that the surface of the TiN film is flattened. SiH 4 The gas supply time is about 3 to 5 minutes, for example, during the time when no Si film is formed on the wafer 200 , that is, during the incubation time.

[0066] [Purge process] (removal of residual gas)

[0067] From the beginning of supply of SiH 4 After 3 to 5 minutes from the start of the gas flow, close valve 324 to stop supplying SiH 4At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the vacuum pump 246 performs vacuum exhaust in the processing chamber 201 to remove the remaining unreacted SiH 4 Gas or SiH contributing to the formation of TiSiN film 4 The gas is exhausted from the processing chamber 201. At this time, the valve 524 is kept open, and the valves 514 and 534 are opened to start supplying N into the processing chamber 201. 2 Gas. 2 The gas acts as a purge gas to improve the removal of unreacted SiH 4 Gas or SiH contributing to the formation of TiSiN film 4 The effect of exhausting gas from the processing chamber 201.

[0068] [Film forming process] (supplying TiCl 4 Gas, first step)

[0069] The valve 314 is opened, and TiCl2 as a raw material gas is flowed into the gas supply pipe 310. 4 Gas. TiCl 4 The gas is supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410 at a flow rate adjusted by the MFC 312, and then exhausted from the exhaust pipe 231. At this time, TiCl is supplied to the wafer 200. 4 At the same time, valve 514 is opened to allow N2 to flow into the gas supply pipe 510. 2 N flowing in the gas supply pipe 510 2 The gas flow is adjusted by MFC512 and the TiCl 4 The gas is supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, in order to prevent TiCl 4 The gas enters the nozzles 420 and 430, and the valves 524 and 534 are opened to flow N into the gas supply pipes 520 and 530. 2 Gas. 2 The gas is supplied into the processing chamber 201 through the gas supply pipes 320 , 330 and the nozzles 420 , 430 , and is exhausted from the exhaust pipe 231 .

[0070] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 3990 Pa, for example, 1000 Pa. The TiCl 4 The supply flow rate of the gas is, for example, in the range of 0.1 to 2.0 slm. 2The supply flow rate of the gas is, for example, in the range of 0.1 to 20 slm. It should be noted that the pressure in the processing chamber 201 in this process is set to be higher than the pressure in the processing chamber 201 in the above-mentioned treatment process. In addition, the flow rate of the gas supplied in this process is set to be greater than the flow rate of the gas supplied in the above-mentioned treatment process. At this time, the temperature of the heater 207 is set to make the temperature of the wafer 200 reach, for example, a temperature in the range of 300 to 500°C, for example, a temperature of 475°C.

[0071] At this time, the gas flowing in the processing chamber 201 is only TiCl 4 Gas and N 2 Gas. By supplying TiCl 4 The Ti-containing layer may be a Ti layer containing Cl or a TiCl 4 The adsorption layer may also include both.

[0072] (Removal of residual gas, second step)

[0073] From the beginning of the TiCl supply 4 After a predetermined time, for example, 0.01 to 10 seconds, the gas is closed and the supply of TiCl is stopped. 4 At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the vacuum pump 246 performs vacuum exhaust in the processing chamber 201 to remove the unreacted TiCl 4 Gas or TiCl after the Ti-containing layer is formed 4 The gas is exhausted from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the N is kept supplied to the processing chamber 201. 2 Gas. 2 The gas acts as a purge gas to improve the removal of unreacted TiCl 4 Gas or TiCl after the Ti-containing layer is formed 4 The effect of exhausting gas from the processing chamber 201.

[0074] (Supply NH 3 Gas, third step)

[0075] After the residual gas in the processing chamber 201 is removed, the valve 334 is opened to allow NH 2+ to flow into the gas supply pipe 330 as a reaction gas. 3 Gas. NH 3 The gas is supplied into the processing chamber 201 from the gas supply hole 430a of the nozzle 430 at a flow rate adjusted by the MFC 332, and is exhausted from the exhaust pipe 231. At this time, NH3 At the same time, valve 534 is opened to allow N2 to flow into the gas supply pipe 530. 2 Gas. N flowing in the gas supply pipe 530 2 The gas flow is adjusted by MFC532. 2 Gas and NH 3 The gas is supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, in order to prevent NH 3 The gas enters the nozzles 410 and 420, and the valves 514 and 524 are opened to flow N into the gas supply pipes 510 and 520. 2 Gas. 2 The gas is supplied into the processing chamber 201 through the gas supply pipes 310 , 320 and the nozzles 410 , 420 , and is exhausted from the exhaust pipe 231 .

[0076] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, within the range of 1 to 3990 Pa, for example, 1000 Pa. 3 The supply flow rate of the gas is set to be within the range of 0.1 to 30 slm, for example. 2 The supply flow rate of each gas is set to be, for example, within a range of 0.1 to 30 slm. NH 3 The gas is heated for a period of, for example, 0.01 to 30 seconds. The temperature of the heater 207 is set to be equal to the temperature of the TiCl 4 Same temperature for the gas steps.

[0077] At this time, the gas flowing in the processing chamber 201 is only NH 3 Gas and N 2 Gas. NH 3 The gas undergoes a substitution reaction with at least a portion of the Ti-containing layer formed on the wafer 200 in the first step. During the substitution reaction, Ti and NH 3 N contained in the gas is combined to form a TiN layer on the wafer 200 on which the oxide film is formed.

[0078] (Removal of residual gas, fourth step)

[0079] After the TiN layer is formed, the valve 334 is closed to stop the supply of NH 3 Then, the unreacted NH 3 gas or NH that contributes to the formation of the TiN layer 3 Gases and reaction by-products are exhausted from the processing chamber 201 .

[0080] (Scheduled number of implementations)

[0081] By performing the cycle of sequentially performing the first step to the fourth step a predetermined number of times (n times), a TiN film having a predetermined thickness is formed on the wafer 200 on which the oxide film is formed.

[0082] (Post-purge and atmospheric pressure recovery)

[0083] N is supplied to the processing chamber 201 from gas supply pipes 510, 520, and 530 respectively. 2 The gas is exhausted from the exhaust pipe 231. 2 The gas functions as a purge gas, thereby purging the process chamber 201 with an inert gas, and removing the residual gas and by-products in the process chamber 201 from the process chamber 201 (post-purge). Then, the atmosphere in the process chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the process chamber 201 is restored to normal pressure (atmospheric pressure restoration).

[0084] (Wafer removal)

[0085] Then, the sealing cap 219 is lowered by the wafer box elevator 115 to open the lower end of the outer tube 203. Then, the processed wafer 200 is carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 in a state supported by the wafer box 217 (wafer box removal). Then, the processed wafer 200 is taken out of the wafer box 217 (wafer unloading).

[0086] (3) Effects of this embodiment

[0087] According to the present embodiment, a predetermined film thickness (eg, ), the surface of the TiN film such as the wall in the processing chamber 201 is TiSiNized to form a TiSiN film (grain division film) as a film containing a Group 14 element. The TiSiN film is an amorphous film. By forming the TiSiN film, the grains of the TiN film are divided, and as a result, the growth of the nucleation film is stopped (divided). Thus, it is possible to suppress the film peeling of the TiN film formed in the processing chamber 201, so that it does not adhere to the wafer 200 as a foreign matter. That is, it is possible to suppress the generation of particles caused by film peeling in the processing chamber (inside the reaction tube). In addition, since the treatment process is performed in a state where the wafer box 217 carrying the wafer 200 is moved into the processing chamber 201, it is also possible to suppress the film peeling of the TiN film formed on the wafer box 217, the dummy substrate carried on the wafer box 217, etc., thereby improving the production volume (throughput).

[0088] (4) Modification

[0089] Next, a modification of the above-described embodiment will be described in detail. In the following embodiment, only the differences from the above-described embodiment will be described in detail.

[0090] Figure 5 It is a diagram showing a modification of the film forming stage according to the above-mentioned embodiment.

[0091] In this modification, the treatment process performed before the film forming process is different from that of the above-mentioned embodiment. Specifically, the above-mentioned substrate processing apparatus 10 is used to replace SiH as the silane-based gas in the treatment process of the above-mentioned embodiment. 4 The gas supply is carried out from the gas supply pipe 320 as an oxygen-containing gas containing oxygen (O). 2 Gas supply.

[0092] [Processing process] (supply O 2 gas)

[0093] Open valve 324 to allow oxygen-containing gas to flow into gas supply pipe 320. 2 Gas. 2 The gas is supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420 at a flow rate adjusted by the MFC 322, and is exhausted from the exhaust pipe 231. At this time, O is supplied to the wafer 200. 2 At the same time, valve 524 is opened to allow N2 to flow into the gas supply pipe 520. 2 N flowing in the gas supply pipe 520 2 The gas flow is adjusted by MFC522 and O 2 The gases are supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. At this time, the valves 514 and 534 are closed, and the supply of N from the nozzles 410 and 430 is stopped. 2 gas.

[0094] At this time, the APC valve 243 is fully opened (fully opened). 2 The supply flow rate of the gas is, for example, within the range of 0.1 to 10 slm, and is set to, for example, 2 slm. 2 The supply flow rate of the gas is, for example, in the range of 0.1 to 20 slm. It should be noted that the pressure in the processing chamber 201 in this process is set to be lower than the pressure in the processing chamber 201 in the film forming process. In addition, the flow rate of the gas supplied in this process is set to be less than the flow rate of the gas supplied in the film forming process. 2 The gas spreads throughout the entire processing chamber 201 , and can selectively treat only the TiN film formed on the wall or the like in the processing chamber 201 without affecting the product wafer 200 .

[0095] At this time, the temperature of the heater 207 is set so that the temperature of the wafer 200 is stably maintained at a temperature in the range of, for example, 350 to 500°C. It should be noted that the temperature in this process is set to be higher than the temperature in the film forming process described later. Since the higher the temperature in this process, the better the reactivity, the higher the temperature is preferably. It should be noted that from the perspective of shortening the processing time of the wafer 200 (increasing manufacturing throughput), it is preferred that the temperature in this process be set to a temperature close to the temperature in the film forming process. The smaller the temperature difference, the shorter the temperature adjustment time can be, and the processing time can be shortened.

[0096] At this time, the gas flowing in the processing chamber 201 is O 2 Gas. By supplying O 2 The gas oxidizes the surface of the TiN film such as the wall in the processing chamber 201, and oxygen atoms diffuse in the film, thereby changing the crystallinity. As a result, a titanium oxynitride (TiNO) film and a titanium oxide (TiO) film are formed as a crystal layer dividing film on the surface of the TiN film such as the wall in the processing chamber 201, so that the surface of the TiN film is flattened.

[0097] It should be noted that the pressure at this time can be adjusted to a pressure closer to atmospheric pressure than such a pressure. By approaching atmospheric pressure, the O 2 The contact probability of the gas molecules with the film to be processed (TiN film in this case) can increase the oxygen adsorption rate on the surface of the film to be processed, that is, the uniformity of the oxidation process can be improved.

[0098] [Purge process] (removal of residual gas)

[0099] Supply O from the beginning 2 After a predetermined time has passed, valve 324 is closed to stop supplying O 2 At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the vacuum pump 246 performs vacuum exhaust in the processing chamber 201 to remove the unreacted O 2 Gas or O contributed to the formation of TiNO film and TiO film 2 The gas is exhausted from the processing chamber 201. At this time, the valve 524 is kept open, and the valves 514 and 534 are opened to start supplying N into the processing chamber 201. 2 Gas. 2 The gas acts as a purge gas, which can improve the removal of unreacted O 2 Gas or O contributed to the formation of TiNO film and TiO film 2 The effect of exhausting gas from the processing chamber 201.

[0100] Then, the above-mentioned film forming step is performed to form a TiN film on the wafer 200 on which the oxide film is formed.

[0101] That is, a predetermined film thickness (eg ) before the TiN film is formed, by supplying O 2 The gas oxidizes the surface of the TiN film on the wall of the processing chamber 201, forming a TiNO film or a TiO film (grain segmentation film) as an oxide film. As a result, the grains of the TiN film are segmented, and as a result, the growth of the nucleation film is stopped (segmented). As a result, the film peeling of the TiN film formed in the processing chamber 201 can be suppressed, so that it does not adhere to the wafer 200 as a foreign matter. That is, the generation of particles caused by film peeling in the processing chamber can be suppressed.

[0102] It should be noted that, in the above-mentioned embodiments and variations, a process is described in which a TiN film as a metal-containing film is formed on a wafer on which an oxide film is formed in a processing chamber in which a TiN film is formed as a metal-containing film, but the present disclosure is not limited to this, and can also be well applied when a W film, Mo film, Cu film, Ru film, MoN film or the like is formed on a wafer on which an oxide film is formed in a processing chamber in which a metal-containing film such as tungsten (W), molybdenum (Mo), copper (Cu), ruthenium (Ru), molybdenum nitride (MoN) or the like is formed.

[0103] In the above-mentioned embodiment and modification, the SiO 2 An example of a process of forming a TiN film on a wafer 200 having an oxide film is described, but the present disclosure is not limited thereto and is also applicable to forming a TiN film on a wafer 200 having an oxide film such as an aluminum oxide (AlO) film or a hafnium oxide (HfO) film formed thereon.

[0104] In addition, in the above-mentioned embodiments and variations, as a process of forming a metal-containing film on the wafer 200, an example of alternately repeating the process of supplying a metal-containing gas and the process of supplying a reaction gas is described, but the present disclosure is not limited to this and can be well applied even when a metal-containing film is formed by only supplying a metal-containing gas.

[0105] In the above-mentioned embodiment, SiH 4 The above description uses a gas containing a Group 14 element and H as an example, but the present disclosure is not limited thereto. Disilane (Si 2 H 6 ), trisilane (Si 3 H 8 ) or other silane-based gases. Thus, a TiSiN film, which is a film containing a Group 14 element, can be formed on a wall or the like in the processing chamber.

[0106] In addition, in the above-mentioned embodiment, the silane-based gas as a gas containing a Group 14 element and H is used as an example in the treatment process, but the present disclosure is not limited thereto, and a germane-based gas may also be suitably used as a gas containing a Group 14 element and H. As the germane-based gas, germanium (GeH) as a gas containing germanium (Ge) and H may be used. 4 ), digermane (Ge 2 H 6 ), trigermane (Ge 3 H 8 ) or the like. Thus, a TiGeN film as a film containing a Group 14 element can be formed on a wall or the like in the processing chamber.

[0107] It should be noted that in the above-mentioned modification, O is used as the oxygen-containing gas in the treatment step. 2 The present disclosure is described as an example of gas, but the present disclosure is not limited thereto and can also be applied to gas using O 3 gas, NO gas, N 2 In the case of oxygen-containing gases such as O gas.

[0108] In addition, in the above-mentioned embodiments and modified examples, the case where the treatment process is performed after the wafer formed with the oxide film is moved into the processing chamber formed with the TiN film (after the wafer box is loaded), is used for description, but the present disclosure is not limited to this, and the treatment process can also be performed before the wafer formed with the oxide film is moved into the processing chamber formed with the TiN film (before the wafer box is loaded). That is, it can be well applied even when the treatment process is performed without moving the wafer box 217 into the processing chamber 201. That is, even in the case where the wafer formed with the oxide film is moved into the processing chamber after the treatment process in the processing chamber to perform the film forming process, it can be well applied. Furthermore, the treatment process can also be performed after the wafer box is disassembled after the film forming process.

[0109] In addition, in the above-mentioned embodiment and modification, the case where the film forming process is performed after the treatment process is used for description, but the present disclosure is not limited to this, and the treatment process may be performed each time the film forming process is performed, and the film forming process and the treatment process may be performed alternately and repeatedly. In this way, the grains of the TiN film formed on the wall or the like in the processing chamber 201 may be divided each time the film forming process is performed. In addition, the treatment process may be performed after the film forming process is performed a predetermined number of times.

[0110] Furthermore, in the above-mentioned embodiment, film formation is described by using a substrate processing device that is a batch-type vertical device that processes a plurality of substrates at a time as an example, but the present disclosure is not limited thereto, and can also be well applied when film formation is performed using a single-chip substrate processing device that processes one or several substrates at a time.

[0111] The process recipes (programs recording the treatment process, treatment conditions, etc.) used for forming these various thin films are preferably prepared separately (preparing multiple ones) according to the content of the substrate treatment (film type, composition ratio, film quality, film thickness, treatment process, treatment conditions, etc. of the thin film to be formed). Moreover, it is preferred that when the substrate treatment is started, a suitable process recipe is appropriately selected from multiple process recipes according to the content of the substrate treatment. Specifically, it is preferred that multiple process recipes prepared separately according to the content of the substrate treatment are pre-stored (installed) in the storage device 121c possessed by the substrate processing device via a communication circuit and a recording medium (external storage device 123) recording the process recipes. Moreover, it is preferred that when the substrate treatment is started, the CPU 121a possessed by the substrate processing device appropriately selects a suitable process recipe from the multiple process recipes stored in the storage device 121c according to the content of the substrate treatment. Through such a structure, thin films of various film types, composition ratios, film qualities, and film thicknesses can be formed universally and with good reproducibility by one substrate processing device. In addition, the operator's operational burden (burden of inputting processing procedures, processing conditions, etc.) can be reduced, operational errors can be avoided, and substrate processing can be started quickly.

[0112] In addition, the present disclosure can also be implemented by, for example, changing the process recipe of an existing substrate processing device. When changing the process recipe, the process recipe of the present disclosure can be installed in the existing substrate processing device via a communication circuit or a recording medium recording the process recipe, or the input and output devices of the existing substrate processing device can be operated to change the process recipe itself to the process recipe of the present disclosure.

[0113] Although various typical embodiments of the present disclosure have been described above, the present disclosure is not limited to these embodiments and can be applied in appropriate combinations.

[0114] (5) Embodiment

[0115] First, the substrate processing apparatus 10 is used without performing the above-mentioned substrate processing step. Figure 4 , Figure 5 In the treatment process, a TiN film is formed on the dummy substrate in the processing chamber 201 where no TiN film is formed. The TiN film with a film thickness of 1.5 mm was observed using an atomic force microscope (Atomic Force Microscopy) to observe the surface of the TiN film formed on the pseudo substrate. Figure 6 As shown in FIG. 1 , the square average roughness (Rms) of the surface of the TiN film formed on the pseudo substrate is 1.62 nm, and the maximum height difference (Rmax) is 25.7 nm. A dummy substrate with a TiN film of 0.5 mm thick was carried into the processing chamber 201 on which the TiN film was formed, and the comparative example, Example 1 and Example 2 described below were carried out. The surface of the TiN film formed on the dummy substrate was observed using an atomic force microscope.

[0116] In the comparative example, the substrate processing apparatus 10 is used to form The dummy substrate with a TiN film having a thickness of 0.1 mm is directly carried into the processing chamber 201 with the TiN film formed thereon without the above-mentioned Figure 4 , Figure 5 In the treatment step, a TiN film is further formed on the pseudo substrate. The TiN film was filmed and the surface of the TiN film was observed using an atomic force microscope.

[0117] In Example 1, the substrate processing apparatus 10 is used to form The dummy substrate with a TiN film having a thickness of 100 mm is directly carried into the processing chamber 201 having the TiN film formed thereon, and the dummy substrate is directly carried into the processing chamber 201 having the TiN film formed thereon. Figure 4 Film formation stage (as a treatment process, SiH is supplied before the film formation process) 4 gas), and further formed on the pseudo substrate having the TiN film formed thereon. The TiN film was filmed and the surface of the TiN film was observed using an atomic force microscope.

[0118] In Example 2, the substrate processing apparatus 10 is used to form The dummy substrate with a TiN film having a thickness of 100 mm is directly carried into the processing chamber 201 having the TiN film formed thereon, and the dummy substrate is directly carried into the processing chamber 201 having the TiN film formed thereon. Figure 5 Film formation stage (as a treatment process, supply O before the film formation process 2 gas), and further formed on the pseudo substrate having the TiN film formed thereon. The TiN film was filmed and the surface of the TiN film was observed using an atomic force microscope.

[0119] like Figure 6 As shown in FIG. 1 , the square average roughness (Rms) of the surface of the TiN film on the pseudo substrate in the comparative example is 13.6 nm, and the maximum height difference (Rmax) is 85.5 nm. In addition, the square average roughness (Rms) of the surface of the TiN film on the pseudo substrate in Example 1 is 2.16 nm, and the maximum height difference (Rmax) is 22.9 nm. In addition, the square average roughness (Rms) of the surface of the TiN film on the pseudo substrate in Example 2 is 3.28 nm, and the maximum height difference (Rmax) is 32.3 nm.

[0120] According to the evaluation results of the surface of the TiN film in the comparative example, Example 1 and Example 2, it was confirmed that the surface of the TiN film in the comparative example had a larger square average roughness and a larger height difference than that of Example 1 and Example 2 which underwent a treatment process before the film forming process, and the growth rate of the TiN film was fast.

[0121] That is, it was confirmed that when a film forming process is performed in the processing chamber 201 where a TiN film is formed, by performing a treatment process before the film forming process, the square average roughness and the maximum height difference of the TiN film surface are reduced compared to the case where the treatment process is not performed, and the growth of the TiN film is suppressed. That is, by performing the treatment process before the film forming process, the growth of the nucleation film formed on the wall, the dummy substrate, etc. in the processing chamber 201 can be suppressed.

[0122] In addition, for the formation of SiO 2 In the case where a TiN film is formed on a wafer having a film without performing the above-mentioned treatment step, after performing O as the treatment step, 2 When the TiN film is formed after the gas supply, the SiH 4 When the TiN film is formed after the gas supply, the SiH 4 The case where the TiN film was formed after the gas supply and the SiH film was formed after the treatment process for 7 minutes 4 When a TiN film was formed after the gas supply, the Si distribution in the depth direction of the TiN film was evaluated using secondary ion mass spectrometry (SIMS).

[0123] In any case, the Si distribution in the depth direction of the TiN film did not change. That is, there was no influence of composition change or the like in the depth direction of the TiN film of the wafer due to the treatment process, and it was confirmed that the treatment process was selectively performed on the wall and the like in the processing chamber 201. Therefore, it was confirmed that there was no influence on the product wafer, and the treatment could be selectively applied only to the TiN film formed on the dummy substrate, the wall and the like in the processing chamber 201.

Claims

1. A substrate processing method, comprising: (a) a step of moving the substrate having the oxide film formed thereon into a processing chamber having the metal-containing film formed thereon, (b) supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen into the processing chamber into which the substrate is placed, (d) supplying a metal-containing gas to the substrate, (e) a step of supplying a reaction gas, and (c) After the step (b), the step (d) and (e) are alternately repeated to form the metal-containing film on the substrate.

2. The substrate processing method according to claim 1, wherein: In (b), the gas containing the Group 14 element and hydrogen is supplied to form a film containing the Group 14 element on the wall of the processing chamber.

3. The substrate processing method according to claim 1, wherein: The gas containing Group 14 elements and hydrogen contains at least any one of SiH4, Si2H6, and Si3H8.

4. The substrate processing method according to claim 2, wherein: The gas containing Group 14 elements and hydrogen contains at least any one of SiH4, Si2H6, and Si3H8.

5. The substrate processing method according to claim 1, wherein: In (b), an oxygen-containing gas is supplied to modify the metal-containing film formed on the wall of the processing chamber into a metal oxide film.

6. The substrate processing method according to claim 2, wherein: The pressure in the processing chamber in (b) is lower than the pressure in the processing chamber in (c), The flow rate of the gas supplied in (b) is smaller than the flow rate of the gas supplied in (c).

7. The substrate processing method according to claim 3, wherein: The pressure in the processing chamber in (b) is lower than the pressure in the processing chamber in (c), The flow rate of the gas supplied in (b) is smaller than the flow rate of the gas supplied in (c).

8. The substrate processing method according to claim 1, wherein: Repeat (b) and (c) alternately.

9. The substrate processing method according to claim 1, wherein: The method comprises the steps of (f) exhausting the process chamber to achieve a desired pressure and heating the process chamber to achieve a desired temperature distribution between (a) and (b).

10. The substrate processing method according to claim 1, wherein: In (c), a titanium nitride film is formed as the metal-containing film.

11. A substrate processing method, comprising: (a) a step of moving the substrate having the oxide film formed thereon into a processing chamber having the metal-containing film formed thereon, (b) supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen into the processing chamber into which the substrate is placed, and (c) forming the metal-containing film on the substrate after step (b), The gas containing Group 14 elements and hydrogen contains at least one of GeH4, Ge2H6, and Ge3H8.

12. A substrate processing method, comprising: (a) a step of moving the substrate having the oxide film formed thereon into a processing chamber having the metal-containing film formed thereon, (b) supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen into the processing chamber into which the substrate is placed, and (c) forming the metal-containing film on the substrate after step (b), The pressure in the processing chamber in (b) is lower than the pressure in the processing chamber in (c), The flow rate of the gas supplied in (b) is smaller than the flow rate of the gas supplied in (c).

13. A substrate processing method, comprising: (a) a step of moving the substrate having the oxide film formed thereon into a processing chamber having the metal-containing film formed thereon, (b) supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen into the processing chamber into which the substrate is placed, and (c) forming the metal-containing film on the substrate after step (b), The temperature in the processing chamber in (b) is higher than the temperature in the processing chamber in (c).

14. A method for manufacturing a semiconductor device, comprising the substrate processing method according to claim 1.

15. A method for manufacturing a semiconductor device, comprising the substrate processing method according to claim 11. 16 . A method for manufacturing a semiconductor device, comprising the substrate processing method according to claim 12 .

17. A method for manufacturing a semiconductor device, comprising the substrate processing method according to claim 13.

18. A computer-readable recording medium having a program recorded thereon for causing a substrate processing apparatus to execute the following process via a computer: (a) a process of carrying a substrate having an oxide film formed thereon into a processing chamber having a metal-containing film formed thereon in the substrate processing apparatus, (b) supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen into the processing chamber into which the substrate is placed, (d) supplying a metal-containing gas to the substrate, (e) a step of supplying a reaction gas, and (c) After (b), the steps (d) and (e) are alternately repeated to form the metal-containing film on the substrate.

19. A substrate processing device having forming a processing chamber including a metal film, A transport system for transporting the substrate into the processing chamber, a gas supply system for supplying at least one of a gas containing a Group 14 element and hydrogen or a gas containing oxygen or a gas containing a metal into the processing chamber; an exhaust system for exhausting the process chamber, and A control unit, wherein the control unit is configured to control the transport system, the gas supply system, and the exhaust system so as to perform (a) a process of transporting a substrate having an oxide film formed thereon into the treatment chamber, (b) a process of supplying a gas containing a Group 14 element and hydrogen or an oxygen-containing gas into the treatment chamber into which the substrate has been transported, and (c) a process of forming the metal-containing film on the substrate by alternately and repeatedly performing (d) a process of supplying a metal-containing gas to the substrate and (e) a process of supplying a reaction gas.

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