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

Abstract

The method includes: (a) a step of supplying a first processing gas into the processing container in a state in which exhaust of the atmosphere in the processing container is stopped; a step (b) in which, after (a), the atmosphere in the processing container is discharged to the storage parts of the first exhaust pipe and the second exhaust pipe in a state in which the exhaust valve is closed and the gas supply valve is opened; (c) a step in which, after (b), the atmosphere in the processing container is exhausted by the first exhaust pipe in a state in which the gas supply valve is closed and the exhaust of the atmosphere in the processing container by the storage unit is stopped; (d) after (c), supplying a second processing gas into the processing container in a state in which the gas supply valve is closed and exhaust of the atmosphere in the processing container by the storage unit is stopped; and (e) a step of processing the substrate in the processing container by performing (a) to (d).

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 device. Background Art

[0002] As a word line of a NAND flash memory or DRAM having a three-dimensional structure, for example, a tungsten (W) film is sometimes used. In addition, a titanium nitride (TiN) film is sometimes used as a barrier film between the W film and the insulating film. In addition, a film having a lower resistance than the W film is required. For example, a molybdenum (Mo) film is sometimes used (for example, International Publication No. WO2022 / 064549). Summary of the invention

[0003] Problems to be solved by the invention

[0004] In the formation of a low-resistance film, when a reaction gas with low reactivity is used as the first process gas for film formation, the supply amount of the reaction gas supplied to the process container is sometimes increased. On the other hand, when the supply amount of the reaction gas is increased, a long discharge time is required when the reaction gas is discharged from the process container to the detoxification unit through a pump.

[0005] The present disclosure provides a technology for shortening the exhaust time of gas from an exhaust system and improving processing productivity.

[0006] Means for solving problems

[0007] According to one embodiment of the present disclosure, a substrate processing method is provided, which uses a substrate processing device, wherein the substrate processing device includes: a processing container that processes a substrate; a first exhaust pipe connected to the processing container and an exhaust device that exhausts the atmosphere in the processing container; a second exhaust pipe connected to the exhaust device and the processing container in parallel with the first exhaust pipe; a storage portion provided in the second exhaust pipe; a gas supply valve provided on the gas supply side of the storage portion in the second exhaust pipe; and an exhaust valve provided on the exhaust side of the storage portion in the second exhaust pipe, wherein the substrate processing method includes the following steps:

[0008] (a) step of supplying a first processing gas into the processing container while exhausting the atmosphere in the processing container is stopped;

[0009] (b) step, after step (a), exhausting the atmosphere in the processing container toward the storage portion of the first exhaust pipe and the second exhaust pipe while the exhaust valve is closed and the gas supply valve is opened;

[0010] (c) step, after step (b), exhausting the atmosphere in the processing container by using the first exhaust pipe while the gas supply valve is closed and exhaust of the atmosphere in the processing container by the storage unit is stopped;

[0011] (d) a step of supplying a second process gas into the process container after (c) with the gas supply valve closed and exhaust of the atmosphere in the process container by the storage unit stopped; and

[0012] (e) Step (a) to (d) are performed to process the substrate in the processing container.

[0013] Effects of the Invention

[0014] According to one aspect of the present disclosure, it is possible to shorten the exhaust time of gas from the exhaust system and improve processing productivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic longitudinal sectional view showing a vertical processing furnace of a substrate processing apparatus according to an embodiment of the present disclosure.

[0016] Figure 2 yes Figure 1 AA line schematic cross-sectional view.

[0017] Figure 3 This is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment of the present disclosure, and is a diagram showing a control system of the controller using a block diagram.

[0018] Figure 4 It is a diagram showing a substrate processing step according to one embodiment of the present disclosure.

[0019] Figure 5 (A) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. Figure 5 (B) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. Figure 5 (C) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. Figure 5 (D) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. Figure 5 (E) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. Figure 5 (F) is a diagram showing one of the substrate processing steps according to one embodiment of the present disclosure. DETAILED DESCRIPTION

[0020] Below, refer to Figure 1 to Figure 4In addition, the drawings used in the following description are schematic, and the relationship between the dimensions of the elements and the ratio of the elements shown in the drawings may not be consistent with the actual situation. In addition, the relationship between the dimensions of the elements and the ratio of the elements may not be consistent between multiple drawings.

[0021] (1) Structure of substrate processing apparatus

[0022] The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating unit (heating mechanism, heating system). The heater 207 is cylindrical and is vertically installed by being supported by a heater base (not shown) as a holding plate. In addition, the substrate processing apparatus 10 includes an outer tube 203 as an example of a processing container, a first exhaust pipe 231, a second exhaust pipe 232, a storage unit 234, a gas supply valve 235, an exhaust valve 236, gas supply pipes 310, 320, 330, 510, 520, 530 as an example of a gas supply unit, and a controller 121 as an example of a control unit.

[0023] On the inner side of the heater 207, an outer tube 203 constituting a reaction tube (reaction container, processing container) is arranged concentrically with the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) and silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (intake flange) 209 is arranged concentrically with the outer tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. An O-ring 220a as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. By supporting the manifold 209 on the heater base, the outer tube 203 is installed vertically.

[0024] 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 outer tube 203, the inner tube 204, and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the hollow portion of the processing vessel (inside the inner tube 204).

[0025] The processing chamber 201 is configured to accommodate wafers 200 as substrates arranged in multiple layers in a horizontal posture in the vertical direction via a wafer boat 217 as a support. The wafers 200 are processed in the processing chamber 201 (processing container).

[0026] In the processing chamber 201, nozzles 410, 420, 430 are provided to penetrate the side wall of the manifold 209 and the inner tube 204. Gas supply pipes 310, 320, 330 are connected to the nozzles 410, 420, 430, respectively. However, the processing furnace 202 of this embodiment is not limited to the above.

[0027] Mass flow controllers (MFCs) 312, 322, 332 as flow controllers (flow control units) are provided in order from the upstream side in the gas supply pipes 310, 320, 330, respectively. In addition, valves 314, 324, 334 as on-off valves are provided in the gas supply pipes 310, 320, 330, respectively. Gas supply pipes 510, 520, 530 for supplying inert gas are connected to the downstream sides of the valves 314, 324, 334 of the gas supply pipes 310, 320, 330, respectively. MFCs 512, 522, 532 as flow controllers (flow control units) and valves 514, 524, 534 as on-off valves are provided in order from the upstream side in the gas supply pipes 510, 520, 530, respectively. These gas supply pipes are examples of a gas supply unit that can supply a first process gas (eg, reduction gas) and a second process gas (eg, source gas) to the process chamber 201 (process container).

[0028] Nozzles 410, 420, 430 are connected to the front ends of the gas supply pipes 310, 320, 330, respectively. The nozzles 410, 420, 430 are configured as L-shaped nozzles, and the horizontal portions thereof are provided so as 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 preliminary chamber 201a which is formed in a channel shape (groove shape) so as to protrude radially outwardly of the inner tube 204 and extend in the vertical direction, and are provided upward (above the arrangement direction of the wafers 200) along the inner wall of the inner tube 204 in the preliminary chamber 201a.

[0029] The nozzles 410, 420, 430 are arranged in a manner extending 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 supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430, respectively. 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 are 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 be gradually increased 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 made more uniform.

[0030] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in a plurality of positions at a height from the lower part to the upper part of the wafer boat 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 the entire area of ​​the wafers 200 accommodated from the lower part to the upper part of the wafer boat 217. The nozzles 410, 420, 430 may be provided in a manner extending from the lower area to the upper area of ​​the processing chamber 201, but are preferably provided in a manner extending to the vicinity of the top of the wafer boat 217.

[0031] As a processing gas, a raw material gas (metal-containing gas) containing a metal element is supplied from a gas supply pipe 310 into the processing chamber 201 via an MFC 312 , a valve 314 , and a nozzle 410 .

[0032] Reducing gas is supplied as a processing gas from the gas supply pipe 320 into the processing chamber 201 via the MFC 322 , the valve 324 , and the nozzle 420 .

[0033] A gas including a Group XV element different from the reducing gas is supplied as a processing gas from the gas supply pipe 330 into the processing chamber 201 via the MFC 332 , the valve 334 , and the nozzle 430 .

[0034] Argon (Ar) gas is supplied as an inert gas from gas supply pipes 510, 520, 530, respectively, via MFCs 512, 522, 532, valves 514, 524, 534, and nozzles 410, 420, 430 into the processing chamber 201. Hereinafter, an example in which Ar gas is used as the inert gas will be described, but as the inert gas, in addition to Ar gas, for example, rare gases such as helium (He) gas, neon (Ne) gas, and xenon (Xe) gas may also be used.

[0035] When the raw material gas is mainly circulated from the gas supply pipe 310, the raw material gas supply system is mainly composed of the gas supply pipe 310, MFC312, and valve 314, but the nozzle 410 may be included in the raw material gas supply system. The raw material gas supply system may also be referred to as a metal-containing gas supply system. In addition, when the reducing gas is made to flow from the gas supply pipe 320, the reducing gas supply system is mainly composed of the gas supply pipe 320, MFC322, and valve 324, but the nozzle 420 may be included in the reducing gas supply system. In addition, when the gas containing the fifteenth group element is circulated from the gas supply pipe 330, the gas supply system containing the fifteenth group element is mainly composed of the gas supply pipe 330, MFC332, and valve 334, but the nozzle 430 may be included in the gas supply system containing the fifteenth group element. In addition, the metal-containing gas supply system, the reducing gas supply system, and the gas supply system containing the fifteenth group element may also be referred to as a processing gas supply system. In addition, the nozzles 410, 420, and 430 may also be included in the processing 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 .

[0036] In the gas supply method of the present embodiment, the gas is delivered through the nozzles 410, 420, 430 arranged in the preparatory chamber 201a in the annular longitudinal space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200. Then, the gas is ejected into the inner tube 204 from the plurality of gas supply holes 410a, 420a, 430a provided at the positions of the nozzles 410, 420, 430 facing 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.

[0037] The exhaust hole (exhaust port) 204a is a through hole formed at a position opposite to the nozzles 410, 420, and 430 on the side wall of the inner tube 204, for example, a slit-shaped through hole opened in a vertical direction. The gas supplied from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 into the processing chamber 201 and flowing on the surface of the wafer 200 flows through the exhaust hole 204a into the gap (inside the exhaust path 206) formed between the inner tube 204 and the outer tube 203. Then, the gas flowing into the exhaust path 206 flows into the first exhaust pipe 231 and is exhausted to the outside of the processing furnace 202.

[0038] The exhaust hole 204a is provided at a position opposite to the plurality of wafers 200, and 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 the 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, and may be composed of a plurality of holes.

[0039] The manifold 209 is provided with a first exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The first exhaust pipe 231 is connected to the vacuum pump 246 and the outer tube 203 (processing container). In the first exhaust pipe 231, a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, an APC (AutoPressure Controller: automatic pressure controller) valve 243, and a pump 246 (vacuum pump 246) as an exhaust device (vacuum exhaust device) for exhausting the atmosphere in the processing container are connected in sequence from the upstream side. The APC valve 243 can exhaust (vacuum exhaust) and stop exhaust (vacuum exhaust stop) in the processing chamber 201 by opening and closing the valve in the state where the vacuum pump 246 is operated, and further, the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening in the state where the vacuum pump 246 is operated. The exhaust system is mainly composed of the exhaust hole 204a, the exhaust path 206, the first exhaust pipe 231, the APC valve 243 and the pressure sensor 245. It is also contemplated that a vacuum pump 246 may be included in the exhaust system. Figure 5 As shown in (A) to (F) of FIG. 2 , a detoxification unit 247 (exhaust gas treatment device) for treating exhaust gas to render it harmless may be provided after the vacuum pump 246 .

[0040] The second exhaust pipe 232 is connected to the vacuum pump 246 and the outer tube 203 (processing container) in parallel with the first exhaust pipe 231. The second exhaust pipe 232 is provided with a storage unit 234. The storage unit 234 is a buffer capable of temporarily storing gas, and is composed of, for example, a pressure vessel. A gas supply valve 235 is provided on the gas supply side of the storage unit 234 in the second exhaust pipe 232. In addition, an exhaust valve 236 is provided on the exhaust side of the storage unit 234.

[0041] A sealing cover 219 as a furnace cover body capable of hermetically closing the lower end opening of the manifold 209 is provided below the manifold 209. The sealing cover 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. The sealing cover 219 is made of metal such as SUS and is formed in a disc shape. An O-ring 220b as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the wafer boat 217 containing the wafer 200 is provided on the opposite side of the processing chamber 201 in the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism vertically provided outside the outer tube 203. The boat elevator 115 is configured to move the boat 217 into and out of the processing chamber 201 by raising and lowering the sealing cap 219. The boat elevator 115 is configured as a transport device (transport mechanism, transport system) that transports the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

[0042] The wafer boat 217 is configured to arrange a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and at intervals in the vertical direction with their centers aligned with each other. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. In the lower part of the wafer boat 217, a dummy substrate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple layers in a horizontal position. With this structure, it is difficult for heat from the heater 207 to be transferred to the sealing cover 219 side. However, the present embodiment is not limited to the above-described method. For example, instead of providing the dummy substrate 218 at the lower part of the wafer boat 217, an insulating cylinder as a cylindrical component made of a heat-resistant material such as quartz or SiC may be provided.

[0043] like Figure 2 As shown, a temperature sensor 263 as a temperature detector is provided in the inner tube 204, and the amount of current supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby making the temperature in the processing chamber 201 a desired temperature distribution. The temperature sensor 263 is configured in an L shape similarly to the nozzles 410, 420, and 430, and is provided along the inner wall of the inner tube 204.

[0044] like Figure 3As shown, the controller 121 as a control unit (control unit) 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 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. An input / output device 122 such as a touch panel is connected to the controller 121.

[0045] 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, a process recipe recording the steps, conditions, etc. of the semiconductor device manufacturing method (substrate processing method) described later, etc. are stored in a readable manner in the storage device 121c. The process recipe is a combination of the processes (steps) in the semiconductor device manufacturing method (substrate processing method) described later by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc. are referred to as programs. In this specification, when the term "program" is used, there is a case where only a process recipe alone is included, a case where only a control program alone is included, or a case where a combination of a process recipe and a control program is included. RAM121b is configured as a storage area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0046] The I / O port 121d is connected to the above-mentioned MFC312, 322, 332, 512, 522, 532, air supply valve 235, exhaust valve 236, 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 boat elevator 115, etc.

[0047] 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 according to an 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 gas supply valve 235, the exhaust valve 236, the valves 314, 324, 334, 514, 524, 534, the opening and closing operation of the APC valve 243 and the pressure adjustment operation of the APC valve 243 by the pressure sensor 245, 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 boat 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer boat 217 by the wafer boat elevator 115, the storage operation of the wafer 200 in the wafer boat 217, etc. according to the contents of the read recipe.

[0048] The controller 121 can be configured 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 on a computer. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are also collectively referred to as recording media. In this specification, the recording medium sometimes includes only the storage device 121c monomer, sometimes includes only the external storage device 123 monomer, or sometimes includes both. It is also possible to provide the program to the computer using a communication unit such as the Internet or a dedicated line instead of using the external storage device 123.

[0049] The controller 121 is configured to enable the first exhaust pipe 231, the second exhaust pipe 232, and the gas supply unit to perform the following processes:

[0050] (a) While exhaust of the atmosphere in the processing container (processing chamber 201) is stopped, the first processing gas is supplied to the processing chamber ( Figure 5 (A));

[0051] (b) After (a), the atmosphere in the processing container is exhausted to the storage portion 234 of the first exhaust pipe 231 and the second exhaust pipe 232 with the exhaust valve 236 closed and the gas supply valve 235 opened. Figure 5 (B));

[0052] (c) After (b), the gas supply valve 235 is closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped, and the atmosphere in the processing container is exhausted by the first exhaust pipe 231 ( Figure 5 (C));

[0053] (d) After (c), the second process gas is supplied to the process chamber 200 while the gas supply valve 235 is closed and the exhaust of the atmosphere in the process chamber by the storage unit 234 is stopped. Figure 5 (D)); and

[0054] (e) (a) to (d) are performed to process the substrate (wafer 200 ) in the processing container.

[0055] Furthermore, the controller 121 may also perform the following processing (f), or may perform (g) after (f).

[0056] (f) After step (d), the atmosphere in the processing container is exhausted by the first exhaust pipe 231 while the gas supply valve 235 and the exhaust valve 236 are closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped.

[0057] (g) A step of exhausting the atmosphere in the storage section 234 toward the exhaust device (pump 246 (vacuum pump 246)) while stopping exhaust of the atmosphere in the processing container by the first exhaust pipe 231 and opening the exhaust valve 236.

[0058] Here, in (e), (a), (b), (c), (d), and (f) may be performed, or (a), (b), (c), (d), (f), and (g) may be performed. In addition, in (e), (a) to (d) may be performed a predetermined number of times.

[0059] In (g), the opening degree of the exhaust valve 236 may be controlled so that the exhaust amount from the storage portion 234 to the exhaust device (vacuum pump 246) becomes a predetermined exhaust amount.

[0060] (g) may be performed before (a) or in parallel with (a).

[0061] In (g), the reservoir 234 may be evacuated to a reduced pressure atmosphere. In other words, the reservoir 234 may be evacuated until the pressure therein is lower than the pressure therein.

[0062] (2) Substrate processing steps

[0063] As one of the steps in the manufacturing process of a semiconductor device, Figure 4 An example of a process for forming a Mo-containing film containing molybdenum (Mo) used as a control gate electrode of a 3D NAND on a wafer 200 is described. The process of forming the Mo-containing film is performed using the processing furnace 202 of the substrate processing apparatus 10. In the following description, the operation of each unit constituting the substrate processing apparatus 10 is controlled by the controller 121.

[0064] In the substrate processing step (semiconductor device manufacturing step) of this embodiment, the following steps are performed:

[0065] (A) supplying a gas containing a Group XV element to the wafer 200 to form a first layer containing a Group XV element on a surface of the wafer 200;

[0066] (B) a step of supplying a gas containing the Mo element to the wafer 200;

[0067] (C) a step of supplying a reducing gas as a reaction gas to the wafer 200; and

[0068] (D) a step of performing (B) and (C) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer to form a film containing the Mo element on the first layer,

[0069] Thus, a Mo-containing film as a metal-containing film is formed on the first layer of the wafer 200 .

[0070] When the term "wafer" is used in this specification, it may refer to "the wafer itself" or "a stack of a wafer and a predetermined layer, film, etc. formed on its surface". In this specification, when the term "surface of a wafer" is used, it may refer to "the surface of the wafer itself" or "the surface of a predetermined layer, film, etc. formed on the wafer". When the term "substrate" is used in this specification, it is synonymous with the term "wafer".

[0071] (Wafer loading)

[0072] When a plurality of wafers 200 are loaded into the wafer boat 217 (wafer loading), as shown in FIG. Figure 1 As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115, carried into the processing chamber 201 (boat loading), and stored in the processing container. In this state, the seal cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0073] (Pressure adjustment and temperature adjustment)

[0074] The vacuum pump 246 is used to perform vacuum exhaust so that the space in the processing chamber 201, i.e., 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 maintained in a state of always being in operation at least until the processing of the wafer 200 is completed. In addition, the heater 207 is used to heat the processing chamber 201 so that the temperature in the processing chamber 201 reaches the desired temperature. At this time, the amount of power supplied to the heater 207 is feedback controlled (temperature adjusted) based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 is desired. The heating of the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.

[0075] [First layer formation step]

[0076] [First process]

[0077] (Pretreatment step: supply of gas containing Group XV elements)

[0078] The valve 334 is opened to allow the gas containing the Group XV element to flow in the gas supply pipe 330. The gas containing the Group XV element is flow-regulated by the MFC 332, supplied from the gas supply hole 430a of the nozzle 430 to the processing chamber 201, and exhausted from the first exhaust pipe 231. At this time, the gas containing the Group XV element is supplied to the wafer 200. In addition, the valve 534 may be opened at this time to allow an inert gas such as Ar gas to flow in the gas supply pipe 530. The Ar gas flowing in the gas supply pipe 530 is flow-regulated by the MFC 532, supplied to the processing chamber 201 together with the gas containing the Group XV element, and exhausted from the first exhaust pipe 231. At this time, in order to prevent the gas containing the Group XV element from entering the nozzles 410 and 420, the valves 514 and 524 are opened to allow the Ar gas to flow into the gas supply pipes 510 and 520. Ar gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 320 and the nozzles 410 and 420 , and is exhausted from the first exhaust pipe 231 .

[0079] 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 supply flow rate of the gas containing the Group XV element controlled by MFC332 is, for example, set to a flow rate in the range of 0.01 to 5.0 slm. In order to suppress the gas containing the Group XV element from entering each nozzle, the supply flow rate of the Ar gas controlled by MFC512, 522, and 532 is set to a flow rate in the range of, for example, 0.1 to 5.0 slm. At this time, the temperature of the heater 207 is set to a temperature that makes the temperature of the wafer 200 a temperature in the range of, for example, 300 to 650° C. The temperature of the wafer 200 is preferably set to a temperature below the temperature of the metal film formation process described later. In addition, the expression of a numerical range such as "1 to 3990 Pa" in the present disclosure means that the lower limit and the upper limit are included in the range. Therefore, for example, "1 to 3990 Pa" means "above 1 Pa and below 3990 Pa". The same is true for other numerical ranges.

[0080] (Supply of at least one of dilution gas and reduction gas)

[0081] In addition, during the supply of the gas containing the fifteenth group element, there is a time to supply at least one of the dilution gas and the reducing gas. Here, the dilution gas can be used as a reducing gas in addition to the inert gas. Preferably, a gas having the property of suppressing the state change and decomposition of the material containing the fifteenth group element can be used. By supplying such a gas into the processing chamber 201, the processing chamber 201 becomes an atmosphere that suppresses the state change and decomposition of the gas containing the fifteenth group element. Regarding the supply of these gases, specifically, the valve 324 is opened to supply the reducing gas as the dilution gas to the gas supply pipe 320. The reducing gas is flow-adjusted by the MFC322, supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420, and exhausted from the first exhaust pipe 231. At this time, the wafer 200 is supplied with a gas containing the fifteenth group element and a reducing gas as a dilution gas. In addition, at this time, the valve 524 can also be opened at the same time to allow an inert gas such as Ar gas to flow in the gas supply pipe 520. The Ar gas flowing in the gas supply pipe 520 is flow-regulated by the MFC 522, supplied into the processing chamber 201 together with the reducing gas, and exhausted from the first exhaust pipe 231. In addition, when only an inert gas is supplied as a dilution gas, the valve 324 is closed and the inert gas is supplied from another inert gas supply system.

[0082] (Concentration adjustment of materials containing Group XV elements)

[0083] In addition, in order to adjust the concentration of the material containing the fifteenth group element supplied to the wafer 200 to a predetermined concentration, a dilution gas may also be supplied. The gas containing the fifteenth group element may be a gas composed of a simple substance containing the fifteenth group element material, or a gas containing the fifteenth group element material and a mixture of a dilution gas. According to each case, at least one of the flow rate of the gas containing the fifteenth group element, the flow rate of the reducing gas, and the flow rate of the dilution gas is adjusted to a predetermined concentration. Here, the flow rate of each gas is adjusted so that the concentration of the material containing the fifteenth group element (the gas containing the fifteenth group element) is, for example, in the range of 0.1 to 50%. By supplying a gas of such a concentration, a first layer containing the fifteenth group element can be formed. In addition, it is possible to suppress the situation where the concentration of the fifteenth group element in the metal film (Mo-containing film) formed on the first layer becomes high. In addition, if the concentration is less than 0.1%, it is difficult to form the first layer containing the fifteenth group element, the formation time of the first layer increases, and the manufacturing productivity may be reduced. In addition, if the concentration exceeds 50%, the concentration of the Group 15 element in the first layer increases, the concentration of the Group 15 element in the metal film (Mo-containing film) increases, and the characteristics of the metal film may deteriorate. In addition, by supplying a gas with a concentration exceeding 50%, the amount of decomposition products of the material containing the Group 15 element generated in the processing chamber 201 increases, and the ratio of the Group 15 element to other elements (such as hydrogen) in the first layer does not reach a predetermined ratio, and it may be difficult to obtain the effects described in the present disclosure.

[0084] At this time, the gas flowing in the processing chamber 201 is a gas containing at least a Group 15 element. Here, the Group 15 element is at least one of phosphorus (P) and arsenic (As). The gas containing the Group 15 element is a gas containing at least one of P and As. In addition, the gas containing the Group 15 element may preferably contain hydrogen (H). Examples of such gases containing P and H include alkyl phosphine gases such as trimethylphosphine ((CH3)3P) gas, triethylphosphine ((C2H5)3P) gas, tri-n-propylphosphine ((n-C3H7)3P) gas, triisopropylphosphine ((i-C3H7)3P) gas, tri-n-butylphosphine ((n-C4H9)3P) gas, triisobutylphosphine ((i-C4H9)3P) gas, tri-tert-butylphosphine ((t-C4H9)3P) gas, and tert-butylphosphine (t-C4H9PH2) gas, aminophosphine (NH2PH2) gas, tri(dimethylamino)phosphine ([(CH3)2 Aminophosphine gases such as bis(dimethylamino) phosphine (PH[N(CH3)2]2) gas, bis(dimethylamino) chlorophosphine ([(CH3)2N]2PCl) gas, phosphamide gases such as bis(dimethylamino) methylphosphine (CH3P[N(CH3)]2) gas, dimethylaminodimethylphosphine ((CH3)2PN(CH3)2) gas, diethylaminodiethylphosphine ((C2H5)2PN(C2H5)2) gas, phosphine-based gases such as phosphine (PH3) gas, diphosphine (P2H4) gas, trivinylphosphine ((CH2=CH)3P) gas, etc. In addition, the material containing the Group XV element is at least one of these materials, and the gas containing the Group XV element is sometimes a single gas containing the Group XV element material, and sometimes a mixed gas containing the Group XV element material and a diluent gas.

[0085] By supplying such a gas to the wafer 200, a first layer containing at least P is formed on the surface of the wafer 200. Preferably, the first layer is a layer containing P and H. It is further preferred that the first layer is a layer of a substance including molecules of a material containing a Group XV element and a state in which the molecules of the material containing a Group XV element are partially decomposed. For example, the first layer formed when PH3 is used as a material containing a Group XV element may contain P, H, and PHx. Here, X is an integer less than 3, and PHx is, for example, at least one of PH, PH2, and PH3. In addition, in order to form a first layer containing such a substance, the temperature in the processing chamber 201 is preferably set to a temperature at which a portion of the material containing a Group XV element can be decomposed. For example, when PH3 is used as a material containing a Group XV element, the temperature in the processing chamber 201 is set to a temperature in the range of 300°C to 650°C.

[0086] [Second step]

[0087] (Residual gas removal)

[0088] After a predetermined time, for example, 1 second to 600 seconds, has passed since the supply of the gas containing the Group XV element began, the valve 334 of the gas supply pipe 330 is closed to stop the supply of the gas containing the Group XV element. That is, the time for supplying the gas containing the Group XV element to the wafer 200 is set to, for example, a time in the range of 1 to 600 seconds. At this time, the APC valve 243 of the first exhaust pipe 231 remains open, and the vacuum pump 246 is used to vacuum exhaust the processing chamber 201, and the gas containing the Group XV element that remains in the processing chamber 201 and has not reacted or has participated in the formation of the first layer is discharged from the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted. By reducing the pressure in the processing chamber 201, the gas containing the Group XV element that remains in the gas supply pipe 330 and the nozzle 430 can be discharged. By exhausting the gas containing the XV element remaining in the gas supply pipe 330 and the nozzle 430, it is possible to suppress the situation in which the gas containing the XV element remaining in the gas supply pipe 330 and the nozzle 430 is supplied to the processing chamber 201 during the formation process of the metal-containing film. In addition, at this time, the valves 514, 524, and 534 can also be kept in an open state to maintain the supply of Ar gas to the processing chamber 201. In addition to the function of suppressing the gas from entering each nozzle, the Ar gas can also function as a purge gas. When the Ar gas is supplied as the purge gas, the effect of removing the gas containing the XV element remaining in the processing chamber 201 that has not reacted or participated in the formation of the first layer from the processing chamber 201 can be improved.

[0089] [Metal-Containing Film Formation Step]

[0090] [Third step]

[0091] (Supply of metal-containing gas)

[0092] Next, the valve 314 is opened, and the metal-containing gas as the raw material gas flows into the gas supply pipe 310. The metal-containing gas is flow-regulated by the MFC 312, supplied from the gas supply hole 410a of the nozzle 410 into the processing chamber 201, and exhausted from the first exhaust pipe 231. At this time, the metal-containing gas is supplied to the wafer 200. At this time, the valve 514 is opened at the same time, and an inert gas such as Ar gas is flowed in the gas supply pipe 510. The Ar gas flowing in the gas supply pipe 510 is flow-regulated by the MFC 512, supplied into the processing chamber 201 together with the metal-containing gas, and exhausted from the first exhaust pipe 231. At this time, in order to prevent the metal-containing gas from intruding into the nozzles 420 and 430, the valves 524 and 534 are opened, and the Ar gas is flowed in the gas supply pipes 520 and 530. The Ar gas is supplied into the processing chamber 201 via the gas supply pipes 320 and 330 and the nozzles 420 and 430, and exhausted from the first exhaust pipe 231.

[0093] 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, 500 Pa. The supply flow rate of the metal-containing gas controlled by the MFC 312 is, for example, 0.1 to 1.0 slm. The supply flow rates of the Ar gas controlled by the MFCs 512, 522, and 532 are respectively set to flow rates in the range of, for example, 0.1 to 5.0 slm. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is, for example, in the range of 300 to 650° C.

[0094] At this time, the main gas flowing in the processing chamber 201 (the gas supplied to the wafer 200) is a metal-containing gas. That is, the metal-containing gas is supplied to the wafer 200. Here, as the metal-containing gas, for example, a molybdenum (Mo)-containing gas containing molybdenum (Mo) as a metal element can be used. As the Mo-containing gas, for example, molybdenum trichloride (MoCl3) gas, molybdenum tetrachloride (MoCl4) gas, molybdenum pentachloride (MoCl5) gas, molybdenum hexachloride (MoCl6) gas, and molybdenum dioxide dichloride (MoO2Cl2) gas, molybdenum tetrachloride (MoOCl4) gas containing Mo and chlorine (Cl) can be used. By supplying the Mo-containing gas, a Mo-containing layer as a metal-containing layer is formed on the wafer 200 (first layer). In the case of using MoCl5, the Mo-containing layer can be a Mo layer containing Cl or an adsorption layer of MoCl5. In addition, when MoO2Cl2 (or MoOCl4) is used, it may be a Mo layer containing Cl and O, or it may be an adsorption layer of MoO2Cl2 (or MoOCl4), or it may contain both. In addition, it is preferred that the Mo layer is a layer containing P contained in the first layer. For example, when the first layer contains P, H, and PHx, the Mo-containing gas reacts with the molecules constituting the first layer, and the elements and molecules constituting the first layer are separated from the first layer. In the process of this separation, the elements and molecules constituting the first layer can enter the Mo layer.

[0095] [Fourth step]

[0096] (Residual gas removal)

[0097] After a predetermined time, for example, 1 to 60 seconds, has passed since the start of the supply of the metal-containing gas, the valve 314 of the gas supply pipe 310 is closed to stop the supply of the metal-containing gas. That is, the time for supplying the metal-containing gas to the wafer 200 is set to, for example, a time in the range of 1 to 60 seconds. At this time, the APC valve 243 of the first exhaust pipe 231 remains in an open state, and the vacuum pump 246 is used to vacuum exhaust the processing chamber 201, and the metal-containing gas remaining in the processing chamber 201 that has not reacted or participated in the formation of the metal-containing layer is removed from the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted. At this time, the valves 514, 524, and 534 can also be kept open to maintain the supply of Ar gas to the processing chamber 201. In addition to the function of inhibiting the gas from entering each nozzle, the Ar gas can also act as a purge gas. When Ar gas is supplied as a purge gas, the effect of removing the metal-containing gas remaining in the processing chamber 201 that has not reacted or participated in the formation of the metal-containing layer from the processing chamber 201 can be improved.

[0098] [Fifth step]

[0099] (Reducing gas supply)

[0100] After the residual gas in the processing chamber 201 is removed, the valve 324 is opened to allow the reducing gas to flow into the gas supply pipe 320. The reducing gas is flow-regulated by the MFC 322, supplied from the gas supply hole 420a of the nozzle 420 into the processing chamber 201, and exhausted from the first exhaust pipe 231. At this time, the reducing gas is supplied to the wafer 200. At this time, the valves 514, 524, and 534 are kept open to maintain the supply of Ar gas to the gas supply pipes 510, 520, and 530. The Ar gas flowing in the gas supply pipes 510, 520, and 530 is flow-regulated by the MFCs 512, 522, and 532, respectively. The Ar gas flowing in the gas supply pipe 520 is supplied to the processing chamber 201 through the gas supply pipe 320 and the nozzle 420 together with the reducing gas, and is exhausted from the first exhaust pipe 231. In addition, the Ar gas flowing in the gas supply pipe 530 is supplied to the processing chamber 201 via the gas supply pipe 330 and the nozzle 430, and is exhausted from the first exhaust pipe 231. In addition, the Ar gas flowing in the gas supply pipe 510 is supplied to the processing chamber 201 via the gas supply pipe 310 and the nozzle 410, and is exhausted from the first exhaust pipe 231 to prevent the reducing gas from entering the nozzle 410.

[0101] 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 133,000 Pa, for example, 5,000 Pa. The supply flow rate of the reducing gas controlled by the MFC 322 is, for example, in the range of 1 to 50 slm, preferably in the range of 15 to 40 slm. The supply flow rates of the Ar gas controlled by the MFCs 512, 522, and 532 are respectively set to flow rates in the range of, for example, 0.1 to 5.0 slm. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is, for example, in the range of 300 to 650° C.

[0102] At this time, the main gas flowing in the processing chamber 201 is a reducing gas as a reactive gas. That is, the reducing gas is supplied to the wafer 200 .

[0103] In addition, when the reducing gas is supplied in the above-mentioned amount, the desired reduction reaction can be obtained. That is, the deposition rate of the film on the wafer 200 can be increased, and a film with desired characteristics can be obtained. On the other hand, when the reducing gas is supplied in this way, the exhaust time of the reducing gas may sometimes be longer. In addition, depending on the type (characteristics) of the reducing gas, the problem of not being able to exhaust the gas at one time using the pump 246 may sometimes occur.

[0104] Here, as the reducing gas, for example, a gas composed of hydrogen (H) is used. Preferably, a gas composed of a single hydrogen substance is used. Specifically, hydrogen (H2) gas or deuterium (D2) gas can be used. The following is an example of using H2 gas as the reducing gas.

[0105] [Sixth step]

[0106] (Residual gas removal)

[0107] After a predetermined time, for example, 1 to 1200 seconds, has passed since the start of the supply of the reducing gas, the valve 324 of the gas supply pipe 320 is closed to stop the supply of the reducing gas. Then, by the same processing steps as the second step described above, the reducing gas and reaction byproducts that have not reacted or have participated in the formation of the metal-containing layer remaining in the processing chamber 201 are exhausted from the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted.

[0108] (Scheduled number of implementations)

[0109] The cycle of the third step to the sixth step is performed in sequence at least once (predetermined number of times (n times, n is an integer greater than 1)), thereby forming a Mo-containing film as a metal-containing film of predetermined thickness on the wafer 200. The above cycle is preferably repeated multiple times. In addition, the Mo-containing film is a film with molybdenum as a main component, and a layer containing Mo and P is formed on the wafer 200 side (first layer side) of the Mo-containing film. It is preferably configured so that the P concentration in the Mo-containing film decreases toward the surface of the Mo-containing film.

[0110] (Post-Purge and Atmospheric Pressure Restoration)

[0111] Ar gas is supplied to the processing chamber 201 from the gas supply pipes 510, 520, and 530, respectively, and exhausted from the first exhaust pipe 231. The Ar gas acts as a purge gas, whereby the processing chamber 201 is purged with an inert gas, and the gas and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Afterwards, 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 restoration).

[0112] (Wafer removal)

[0113] After that, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the outer tube 203 is opened. Then, the processed wafers 200 are carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After that, the processed wafers 200 are taken out of the wafer boat 217 (wafer taking out).

[0114] (3) Effects of this embodiment

[0115] According to the present embodiment, one or more of the following effects can be obtained.

[0116] (A) By forming the first layer between the surface of the wafer 200 and the Mo-containing film, the adhesion between the Mo-containing film and the wafer 200 can be improved. Thus, a metal film with good film properties can be formed without forming a barrier film on the surface of the wafer 200.

[0117] (B) By including the Group XV element in the first layer in the Mo-containing film, it is possible to improve adhesion with the film (underlayer) formed on the surface of the wafer 200. In other words, the bonding strength between the first layer and the surface of the wafer 200 and the bonding strength between the first layer and the Mo-containing film can be improved.

[0118] (C) By diffusing the Group XV element contained in the first layer into the Mo-containing film, the bonding force of the elements present in the Mo-containing film can be increased, that is, bonding between Mo elements and bonding between Mo elements and the Group XV element occurs.

[0119] (D) The reactivity of the first layer with the Mo-containing gas as the metal-containing gas can be improved, and the film-forming rate of the Mo-containing film can be improved. That is, the productivity (productivity) of the semiconductor device can be improved. For example, the case of using PH3 gas as the gas containing the fifteenth group element and using, for example, MoO2Cl2 as the Mo-containing gas is described. In this case, a layer containing PHx is formed as the first layer. The PHx and MoO2Cl2 are easy to react chemically, and are easier to react than the case where the first layer is not formed on the surface of the wafer 200, and a layer containing Mo is formed on the wafer 200 (on the first layer), and molecules containing P are separated from the first layer. Molecules containing P include, for example, tetrachloroammonium (POCl4). Due to such a reaction, the film-forming rate of the Mo-containing film can be increased. In addition, through this chemical reaction, the fifteenth group element enters the Mo-containing film (the fifteenth group element diffuses in the Mo-containing film). In addition, it can also be said that a part of the first layer (surface) is removed by the raw material gas (metal-containing gas). In addition, it can also be said that a part of the first layer (surface) is decomposed by the raw material gas.

[0120] (E) When forming the first layer, even when the temperature of the wafer 200 and the components around the wafer 200 (for example, at least one of the support and the processing container) reaches the decomposition temperature of the material containing the Group XV element, by supplying a diluent gas, it is possible to suppress excessive decomposition of the material containing the Group XV element. That is, by supplying a diluent gas, it is possible to form an atmosphere that suppresses the decomposition of the material containing the Group XV element. In addition, even if the material containing the Group XV element decomposes in the processing chamber 201, it is possible to use a diluent gas to suppress the excessive supply of decomposition products to the wafer 200. That is, the effect of flushing the decomposition products by using a diluent gas can be obtained. In addition, it is believed that the diluent gas can suppress the decomposition of the material containing the Group XV element by reducing the partial pressure of the gas containing the Group XV element. In addition, by reducing the partial pressure of the gas containing the Group XV element, it is possible to reduce the probability that the molecules of the gas containing the Group XV element collide with the components (for example, the support and the processing container) that are above the decomposition temperature. As a result, it is believed that the probability that the molecules of the gas containing the Group XV element receive heat energy from the components that are above the decomposition temperature and decompose can be reduced. In addition, the same effect can be obtained even at the total pressure, not limited to the partial pressure of the gas containing the Group 15 element. Figure 1In a substrate processing apparatus having a heating unit around a processing container, the temperature of components around the wafer 200 is sometimes higher than the set temperature of the wafer 200, and the material containing the Group XV element is easily decomposed in such an environment. Therefore, in such a structure of a substrate processing apparatus, a more significant effect can be obtained. In addition, it is preferred that the partial pressure of the gas containing the Group XV element in the processing chamber 201 is less than the partial pressure of the inert gas as a diluent gas. By setting such a partial pressure relationship, the decomposition of the gas containing the Group XV element can be suppressed.

[0121] (F) When forming the first layer, even when the temperature of the wafer 200 or the components around the wafer 200 (for example, at least one of the supports and the processing container) reaches the decomposition temperature of the material containing the Group XV element, excessive decomposition of the material containing the Group XV element can be suppressed by supplying a reducing gas. That is, by supplying a reducing gas, an atmosphere that suppresses the decomposition of the material containing the Group XV element can be formed. It is believed that the reducing gas itself has the same effect as the dilution gas and also has the function of suppressing the thermal decomposition of the material containing the Group XV element. In order to obtain such a mechanism in which the reducing gas directly suppresses the thermal decomposition of the material containing the Group XV element, it is preferred that the same element is contained in both the gas containing the Group XV element and the reducing gas. As such an element, for example, there is hydrogen (H). As a specific material, there are the materials described above. In addition, it is preferred that the partial pressure of the gas containing the Group XV element in the processing chamber 201 is smaller than the partial pressure of the reducing gas. By setting such a partial pressure relationship, the decomposition of the gas containing the Group XV element can be suppressed. In order to set such a partial pressure, for example, as Figure 4 As shown, the flow rate of the reducing gas may be made larger than the flow rate of the gas containing the Group XV element.

[0122] (G) By forming the metal film (Mo-containing film) in an atmosphere that suppresses decomposition of the first layer, at least one of the effects of (A), (B), (C), and (D) can be obtained.

[0123] (4) Exhaust process of reaction gas

[0124] To address the problem that occurs when the supply amount of the reducing gas as the reaction gas is large, the substrate processing step (semiconductor device manufacturing step) of the present embodiment may be performed as follows.

[0125] exist Figure 5 In the substrate processing step, the following processing is performed:

[0126] (a) Processing, in which the first processing gas (reducing gas) as the reaction gas RG is supplied into the processing container (processing chamber 201) while the exhaust of the atmosphere in the processing container (processing chamber 201) is stopped. Figure 5 (A));

[0127] (b) After (a), the atmosphere in the processing container is exhausted to the storage part 234 of the first exhaust pipe 231 and the second exhaust pipe 232 while the exhaust valve 236 is closed and the gas supply valve 235 is opened. Figure 5 (B));

[0128] (c) After (b), the atmosphere in the processing container is exhausted by the first exhaust pipe 231 while the gas supply valve 235 is closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped. Figure 5 (C));

[0129] (d) After (c), the second processing gas (raw material gas) is supplied into the processing container while the gas supply valve 235 is closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped ( Figure 5 (D));

[0130] (e) Processing: (a) to (d) are performed to process the substrate (wafer 200) in the processing container.

[0131] Furthermore, the following processing (f) and (g) may be performed.

[0132] (f) step, after step (d), the atmosphere in the processing container is exhausted by the first exhaust pipe 231 while the gas supply valve 235 and the exhaust valve 236 are closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped ( Figure 5 (E)).

[0133] (g) Step 200 stops exhausting the atmosphere in the processing container by the first exhaust pipe 231, and exhausts the atmosphere in the storage portion 234 to the vacuum exhaust device (vacuum pump 246) while the exhaust valve 236 is opened. Figure 5 (F)

[0134] Here, in the process of (a), the first process gas supplied to the process chamber 201 is, for example, a reducing gas, specifically, a high-pressure H2 gas. The supply of the first process gas is performed in the same manner as in the fifth step. In addition, in the process of (a), the gas supply valve 235 and the exhaust valve 236 of the storage portion 234 are both closed.

[0135] In the process of (b), the gas supply valve 235 of the storage part 234 is opened, and the exhaust valve 236 on the exhaust side is closed. Thus, part of the atmosphere in the processing container can be exhausted to the storage part 234.

[0136] In the process of (c), the gas supply valve 235 and the exhaust valve 236 of the storage part 234 are both closed. As a result, the atmosphere in the processing container is exhausted from the first exhaust pipe 231.

[0137] In the process of (d), both the gas supply valve 235 and the exhaust valve 236 of the storage part 234 are closed. The second process gas is, for example, a raw material gas.

[0138] exist Figure 5 In (E), the gas supply valve 235 and the exhaust valve 236 of the storage part 234 are closed, and the atmosphere in the processing container is exhausted by the first exhaust pipe 231. Figure 5 In (F), the atmosphere in the storage section 234 is exhausted by the vacuum exhaust device (vacuum pump 246) while the process of (a) is performed. After the exhaust of the storage section 234, the process returns to (b). Figure 5 (B)), the processes of (b), (c), (d), (f) and (g) may be repeated.

[0139] Alternatively, in (e), (a), (b), (c), (d), and (f) may be performed ( Figure 5 (A)~ Figure 5 (E)), and (a), (b), (c), (d), (f) and (g) can also be performed ( Figure 5 (A)~ Figure 5 (F)). Alternatively, in (e), (a) to (d) ( Figure 5 (A)~ Figure 5 (D)) is performed a predetermined number of times. That is, these processes may be performed cyclically.

[0140] In (g), the opening degree of the exhaust valve 236 may be controlled so that the exhaust amount from the storage portion 234 to the vacuum exhaust device (vacuum pump 246) becomes a predetermined exhaust amount.

[0141] (g) can be performed before (a) or in parallel with (a). (g) being performed in parallel with (a) means that (g) starts at the same time as (a) and (a) ends earlier than (g); (g) starts after (a) starts and (g) ends before (a) ends; and (g) starts at the same time as (a) and (g) ends at the same time as (a).

[0142] In (g), the inside of the storage section 234 may be exhausted to a reduced pressure atmosphere.

[0143] In addition, in the above, an example of performing (a) first is shown, but it is not limited to this. Figure 4 As shown, the raw material gas may be supplied first. That is, (d) may be performed first.

[0144] Each "process" can also be renamed as a "step".

[0145] The first processing gas is a gas that reacts with the second processing gas. When the second processing gas is a raw material gas, the first processing gas is, for example, a reducing gas. The reducing gas is a gas containing hydrogen elements, for example, at least one of H2 gas, D2 gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, germane (GeH4) gas, phosphine (PH3) gas, etc. can be used. In addition, a gas obtained by activating at least one of them can be used. H2 gas and D2 gas are gases composed of a single substance of hydrogen.

[0146] In addition, the case where a gas containing the Mo element is used as the raw material gas (metal element-containing gas) is described as an example, but the present disclosure is not limited to this. For example, sometimes it can also be applied to the treatment of a gas containing at least one of the ruthenium (Ru) element and the tungsten (W) element in the raw material gas. These raw materials are fixed and liquefied after being exhausted from the processing container and recovered.

[0147] (5) Effect of the reaction gas exhaust process

[0148] According to this process, in (b), the atmosphere in the processing container is exhausted to the storage part 234 of the first exhaust pipe 231 and the second exhaust pipe 232, so that the exhaust time of the first processing gas from the exhaust system can be shortened and the processing productivity can be improved. In (e), by performing (a) to (d) a predetermined number of times, the productivity of the film forming process on the wafer 200 can be improved.

[0149] In (f), the atmosphere in the processing container is exhausted by the first exhaust pipe 231 while the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped, thereby preventing the first processing gas and the second processing gas from mixing in the exhaust system.

[0150] In (g), while the exhaust of the atmosphere in the processing container by the first exhaust pipe 231 is stopped and the exhaust valve 236 is opened, the atmosphere in the storage section 234 is exhausted to the vacuum exhaust device (vacuum pump 246), thereby enabling the atmosphere in the storage section 234 to be exhausted in a short time.

[0151] In (g), the opening of the exhaust valve 236 is controlled so that the exhaust volume from the storage section 234 to the vacuum exhaust device (vacuum pump 246) becomes a predetermined exhaust volume, thereby reducing the load of the vacuum pump 246 and the harm removal section 247. In addition, even if the pressure in the storage section 234 becomes a rapidly low state and the temperature in the storage section 234 decreases, by controlling the exhaust flow rate in the storage section 234 using the exhaust valve 236 as described above, the liquefaction of the gas in the storage section 234 can be suppressed.

[0152] If (g) is performed before (a), for example, before supplying high-pressure H2 gas, the storage unit 234 is exhausted. In this case, the pressure in the processing container can be adjusted during (a). On the other hand, if (g) is performed in parallel with (a), the processing productivity is further improved.

[0153] In (g), if the storage part 234 is exhausted to a reduced pressure atmosphere, the pressure difference between the processing container and the storage part 234 increases. This can increase the exhaust amount from the processing container to the storage part 234 in the next (b).

[0154] (6) Procedure

[0155] The program of this embodiment is a program for controlling the above-mentioned substrate processing apparatus 10 by a computer, and the program causes the substrate processing apparatus to execute the following steps by a computer:

[0156] In step (a), a first processing gas ( Figure 5 (A));

[0157] Step (b): after step (a), the atmosphere in the processing container is exhausted to the storage part 234 of the first exhaust pipe 231 and the second exhaust pipe 232 while the exhaust valve 236 is closed and the gas supply valve 235 is opened. Figure 5 (B));

[0158] Step (c): after step (b), the atmosphere in the processing container is exhausted through the first exhaust pipe 231 while the gas supply valve 235 is closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped. Figure 5 (C));

[0159] Step (d): after step (b), the second processing gas ( Figure 5 (D)); and

[0160] In step (e), steps (a) to (d) are performed to process the substrate (wafer 200 ) in the processing container.

[0161] Furthermore, the following steps (f) and (g) may be performed.

[0162] Step (f): after step (d), the atmosphere in the processing container is exhausted by the first exhaust pipe 231 while the gas supply valve 235 and the exhaust valve 236 are closed and the exhaust of the atmosphere in the processing container by the storage unit 234 is stopped. Figure 5 (E));

[0163] In step (g), the atmosphere in the storage portion 234 is exhausted to the vacuum exhaust device (vacuum pump 246) while the exhaust of the atmosphere in the processing container by the first exhaust pipe 231 is stopped and the exhaust valve 236 is opened. Figure 5 (F)).

[0164] In (e), (a), (b), (c), (d), and (f) can be performed ( Figure 5 (A)~ Figure 5 (E)), and (a), (b), (c), (d), (f) and (g) can also be performed ( Figure 5 (A)~ Figure 5 (F)). In addition, in (e), (a) to (d) ( Figure 5 (A)~ Figure 5 (D)) is performed a predetermined number of times.

[0165] In (g), the opening degree of the exhaust valve 236 may be controlled so that the exhaust amount from the storage portion 234 to the vacuum exhaust device (vacuum pump 246) becomes a predetermined exhaust amount.

[0166] (g) may be performed before (a) or in parallel with (a).

[0167] In (g), the inside of the storage section 234 may be exhausted to a reduced pressure atmosphere.

[0168] The program may be recorded in a computer-readable recording medium. Alternatively, the program may be provided as a computer-readable recording medium recording the program.

[0169] In addition, in the above-mentioned embodiment, the case where MoO 2 Cl 2 gas is used as the metal-containing gas (Mo-containing gas) is described as an example, but the present disclosure is not limited to this.

[0170] In addition, in the above-mentioned embodiment, the case where the reducing gas used in the first step and the reducing gas used in the fifth step use the same type of gas is described as an example, but the present disclosure is not limited to this. The reducing gas used in the first step and the reducing gas used in the fifth step can use gases with different molecular structures. For example, H2 gas can be used in the first step, and D2 gas or activated H2 gas can be used in the fifth step. In addition, in the fifth step, at least one of PH3 gas, silane-based gas described later, and borane-based gas can be used. In addition, the reducing gas used in the first step can use a gas having at least one of the characteristics of suppressing the decomposition of the material containing the fifteenth group element and the characteristic of becoming a carrier of the material containing the fifteenth group element. In addition, the reducing gas used in the fifth step can use a gas having at least one of the characteristics of reducing the Mo-containing gas as the raw material gas and the characteristic of suppressing the decomposition of the first layer.

[0171] In addition, in the above embodiment, the case where a gas containing P and H is used as the gas containing the fifteenth group element is described as an example, but the present invention is not limited to this. For example, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, tetrasilane (Si4H 10 ) and other reducing gases such as silane-based gases, monoborane (BH3), and diborane (B2H6) and other borane-based gases. However, among these gases, it is difficult to obtain byproducts such as POCl4 that are easily detached when PH3 is used, so the characteristics of the Mo-containing film may be deteriorated. Therefore, as a gas containing a Group 15 element, a gas containing P is preferred. A gas containing P and H is further preferred.

[0172] In addition, in the above-mentioned embodiment, the case where a gas containing the Mo element is used as the raw material gas (metal element-containing gas) is described as an example, but the present disclosure is not limited to this. For example, it can sometimes be applied to the treatment of using a gas containing at least one of the ruthenium (Ru) element and the tungsten (W) element as the raw material gas.

[0173] In addition, in the above-mentioned embodiment, an example of film formation using a batch-type vertical device, i.e., a substrate processing device, which processes multiple substrates at a time, is described, but the present disclosure is not limited to this, and can also be appropriately applied to the case of film formation using a single-piece substrate processing device that processes one or more substrates at a time. In addition, in the above-mentioned manner, an example of film formation using a substrate processing device having a hot-wall type processing furnace is described. The present disclosure is not limited to the above-mentioned manner, and can also be appropriately applied to the case of film formation using a substrate processing device having a cold-wall type processing furnace. When these substrate processing devices are used, film formation can also be performed in the same order and processing conditions as in the above-mentioned embodiment.

[0174] The process (a program recording the processing steps, processing conditions, etc.) used in the formation of these various thin films is preferably prepared separately (prepared in plurality) according to the content of the substrate processing (film type, composition ratio, film quality, film thickness, processing steps, processing conditions, etc. of the formed thin film). Moreover, it is preferred that when the substrate processing is started, an appropriate process is appropriately selected from a plurality of process according to the content of the substrate processing. Specifically, it is preferred that a plurality of process separately prepared according to the content of the substrate processing is pre-stored (installed) in a storage device 121c possessed by the substrate processing device via an electrical communication line and a recording medium (external storage device 123) recording the process. Moreover, it is preferred that when the substrate processing is started, the CPU 121a possessed by the substrate processing device appropriately selects an appropriate process from a plurality of process stored in the storage device 121c according to the content of the substrate processing. By configuring in this way, thin films of various film types, composition ratios, film qualities, and film thicknesses can be formed universally and with good reproducibility using one substrate processing device. In addition, the operator's operational burden (the burden of inputting processing steps, processing conditions, etc.) can be reduced, operational errors can be avoided, and substrate processing can be started quickly.

[0175] In addition, the present disclosure can also be implemented by, for example, changing the process of an existing substrate processing device. When changing the process, the process of the present disclosure can be installed in the existing substrate processing device via an electrical communication line and a recording medium recording the process, and the input and output devices of the existing substrate processing device can be operated to change the process itself to the process of the present disclosure.

[0176] The above-mentioned methods can be used in combination as appropriate. The processing steps and processing conditions in this case can be, for example, the same as the processing steps and processing conditions in the above-mentioned methods.

[0177] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present disclosure.

Claims

1. A substrate processing method, using a substrate processing device, the substrate processing device comprising: a processing container for processing a substrate; a first exhaust pipe connected to the processing container and an exhaust device for exhausting the atmosphere in the processing container; a second exhaust pipe connected to the exhaust device and the processing container in parallel with the first exhaust pipe; a storage portion disposed in the second exhaust pipe; an air supply valve disposed on the air supply side of the storage portion in the second exhaust pipe; and an exhaust valve disposed on the exhaust side of the storage portion in the second exhaust pipe, characterized in that: The substrate processing method comprises the following steps: (a) step of supplying a first processing gas into the processing container while exhausting the atmosphere in the processing container is stopped; (b) step, after step (a), exhausting the atmosphere in the processing container toward the storage portion of the first exhaust pipe and the second exhaust pipe while the exhaust valve is closed and the gas supply valve is opened; (c) step, after step (b), exhausting the atmosphere in the processing container by using the first exhaust pipe while the gas supply valve is closed and exhaust of the atmosphere in the processing container by the storage unit is stopped; (d) a step of supplying a second process gas into the process container after (c) with the gas supply valve closed and exhaust of the atmosphere in the process container by the storage unit stopped; and (e) Step (a) to (d) are performed to process the substrate in the processing container.

2. The substrate processing method according to claim 1, characterized in that: The substrate processing method comprises: step (f), after step (d), exhausting the atmosphere in the processing container by using the first exhaust pipe in a state where the gas supply valve and the exhaust valve are closed and the exhaust of the atmosphere in the processing container by the storage unit is stopped; In (e), (a), (b), (c), (d), and (f) are performed.

3. The substrate processing method according to claim 2, characterized in that: The substrate processing method comprises, after step (f), a step (g) of exhausting the atmosphere in the storage section by using the exhaust device while stopping exhaust of the atmosphere in the processing container by the first exhaust pipe and opening the exhaust valve, In (e), (a), (b), (c), (d), (f), and (g) are performed.

4. The substrate processing method according to claim 3, characterized in that: In (g), the opening degree of the exhaust valve is controlled so that the exhaust amount from the storage portion to the exhaust device becomes a predetermined exhaust amount.

5. The substrate processing method according to claim 3, characterized in that: (g) is performed before (a).

6. The substrate processing method according to claim 4, characterized in that: (g) is performed before (a).

7. The substrate processing method according to claim 3, characterized in that: (g) is performed in parallel with (a).

8. The substrate processing method according to claim 4, characterized in that: (g) is performed in parallel with (a).

9. The substrate processing method according to claim 1, characterized in that: In (e), (a) to (d) are repeated a predetermined number of times.

10. The substrate processing method according to claim 3, characterized in that: In (g), the storage section is evacuated to a reduced pressure atmosphere.

11. The substrate processing method according to claim 4, characterized in that: In (g), the storage section is evacuated to a reduced pressure atmosphere.

12. A method for manufacturing a semiconductor device, using a substrate processing device, the substrate processing device comprising: a processing container for processing a substrate; a first exhaust pipe connected to the processing container and an exhaust device for exhausting the atmosphere in the processing container; a second exhaust pipe connected to the exhaust device and the processing container in parallel with the first exhaust pipe; a storage portion disposed in the second exhaust pipe; an air supply valve disposed on the air supply side of the storage portion in the second exhaust pipe; and an exhaust valve disposed on the exhaust side of the storage portion in the second exhaust pipe, characterized in that: The method for manufacturing a semiconductor device comprises the following steps: (a) step of supplying a first processing gas into the processing container while exhausting the atmosphere in the processing container is stopped; (b) step, after step (a), exhausting the atmosphere in the processing container toward the storage portion of the first exhaust pipe and the second exhaust pipe while the exhaust valve is closed and the gas supply valve is opened; (c) step, after step (b), exhausting the atmosphere in the processing container by using the first exhaust pipe while the gas supply valve is closed and exhaust of the atmosphere in the processing container by the storage unit is stopped; (d) a step of supplying a second process gas into the process container after (c) with the gas supply valve closed and exhaust of the atmosphere in the process container by the storage unit stopped; and (e) Step (a) to (d) are performed to process the substrate in the processing container.

13. A program for controlling a substrate processing apparatus by a computer, the substrate processing apparatus comprising: a processing container for processing a substrate; a first exhaust pipe connected to the processing container and an exhaust device for exhausting the atmosphere in the processing container; a second exhaust pipe connected to the exhaust device and the processing container in parallel with the first exhaust pipe; a storage portion disposed in the second exhaust pipe; an air supply valve disposed on the air supply side of the storage portion in the second exhaust pipe; and an exhaust valve disposed on the exhaust side of the storage portion in the second exhaust pipe, characterized in that: The program causes the substrate processing apparatus to execute, through a computer: (a) step of supplying a first processing gas into the processing container while exhausting the atmosphere in the processing container is stopped; (b) step, after (a), exhausting the atmosphere in the processing container toward the storage portion of the first exhaust pipe and the second exhaust pipe while the exhaust valve is closed and the gas supply valve is opened; (c) step, after step (b), exhausting the atmosphere in the processing container by using the first exhaust pipe while the gas supply valve is closed and the exhaust of the atmosphere in the processing container by the storage unit is stopped; (d) a step of supplying a second process gas into the process container after step (c) while the gas supply valve is closed and exhaust of the atmosphere in the process container by the storage unit is stopped; and (e) Step (a) to (d) are performed to process the substrate in the processing container.

14. A substrate processing device, characterized in that: The substrate processing device comprises: a processing vessel that processes a substrate; a first exhaust pipe connected to the processing container and an exhaust device for exhausting the atmosphere in the processing container; a second exhaust pipe connected to the exhaust device and the processing container in parallel with the first exhaust pipe; a storage portion disposed in the second exhaust pipe; an air supply valve disposed on an air supply side of the storage portion in the second exhaust pipe; an exhaust valve disposed on an exhaust side of the storage portion in the second exhaust pipe; A gas supply unit capable of supplying a first process gas and a second process gas to the process container; and The control unit is configured to enable the first exhaust pipe, the second exhaust pipe, and the gas supply unit to perform the following processing: (a) processing, supplying a first processing gas into the processing container while stopping exhaust of the atmosphere in the processing container; (b) after (a), exhausting the atmosphere in the processing container toward the storage portion of the first exhaust pipe and the second exhaust pipe while the exhaust valve is closed and the gas supply valve is opened; (c) after (b), in a state where the gas supply valve is closed and exhaust of the atmosphere in the processing container by the storage unit is stopped, exhausting the atmosphere in the processing container by using the first exhaust pipe; (d) a process of supplying a second process gas into the process container after (c) with the gas supply valve closed and exhaust of the atmosphere in the process container by the storage unit stopped; and (e) Processing: performing (a) to (d) to process the substrate in the processing container.

Images