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

Abstract

The present invention relates to a substrate processing method, a recording medium, a substrate processing apparatus, and a semiconductor device manufacturing method. A technique for suppressing an increase in resistance of a film containing a metal element is provided. There are provided: (a) a process of supplying a gas containing a metal element to a substrate housed in a processing container; (b) a process of supplying a reducing gas to the substrate; (c) a process of forming a film containing a metal element on the substrate by performing (a) and (b) a prescribed number of times; (d) a process of supplying a modifying gas to the film after (c), and forming a layer containing an element contained in the modifying gas on a surface of the film; and (e) a process of, after (d), making an atmosphere in the processing container and a transfer chamber adjacent to the processing container a rare gas atmosphere, and carrying the substrate out of the processing container into the transfer chamber.

Description

Technical Field

[0001] This disclosure relates to substrate processing methods, recording media, substrate processing apparatus, and methods for manufacturing semiconductor devices. Background Technology

[0002] For word lines in NAND flash memory and DRAM with a three-dimensional structure, a low-resistance tungsten (W) film can be used, for example. In addition, sometimes a titanium nitride (TiN) film is used as a barrier film between the W film and the insulating film (see, for example, Patent Document 1 and Patent Document 2).

[0003] Existing technical documents

[0004] Patent documents

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

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

[0007] The problem that the invention aims to solve

[0008] However, with the increasing complexity of three-dimensional NAND flash memory, etching has become difficult, thus making the thin-film fabrication of word lines a challenge.

[0009] To address this issue, sometimes films containing molybdenum (Mo) are used instead of TiN and W films to achieve thinning and low resistance. However, in the manufacturing process, at least one of nitrogen (N) and oxygen (O) is mixed into the Mo film or adsorbed onto the surface of the Mo film, resulting in increased resistance of the Mo film.

[0010] The purpose of this disclosure is to provide a technique for suppressing the increase in resistance of films containing metallic elements.

[0011] Methods for solving problems

[0012] According to one aspect of this disclosure, the following technology is provided, which has:

[0013] (a) A process of supplying a gas containing a metal element to a substrate contained in a processing container;

[0014] (b) The process of supplying reducing gas to the aforementioned substrate;

[0015] (c) A process of forming a film containing a metal element on the aforementioned substrate by performing (a) and (b) a specified number of times;

[0016] (d) Following (c), the step of supplying a modified gas to the aforementioned membrane to form a layer containing the elements contained in the aforementioned modified gas on the surface of the aforementioned membrane; and

[0017] (e) After (d), the process of moving the substrate from the aforementioned processing container to the aforementioned transfer chamber by filling the aforementioned processing container and the transfer chamber adjacent to the aforementioned processing container with a rare gas atmosphere.

[0018] The effects of the invention

[0019] According to this disclosure, it is possible to suppress the increase in resistance of films containing metallic elements. Attached Figure Description

[0020] [ Figure 1 This is a schematic configuration diagram of a substrate processing apparatus suitable for use in embodiments of this disclosure.

[0021] [ Figure 2 This is a longitudinal cross-sectional view of a processing furnace in a substrate processing apparatus according to one embodiment of the present disclosure.

[0022] [ Figure 3 ]for Figure 2 A rough cross-sectional view of line AA in the diagram.

[0023] [ Figure 4 [This is a schematic configuration diagram of the controller of the substrate processing apparatus in one embodiment of this disclosure, and a block diagram showing the control system of the controller.]

[0024] [ Figure 5 [A diagram illustrating a substrate processing step in one embodiment of this disclosure.]

[0025] [ Figure 6 ] Figure 6 (A) is a diagram showing the state before the formation of a Si capping layer on the Mo-containing film. Figure 6 (B) is a diagram showing the state after a Si capping layer is formed on a Mo-containing film.

[0026] Explanation of reference numerals in the attached figures

[0027] 10. Substrate processing apparatus; 124. Transfer chamber; 200. Wafer (an example of a substrate); 201. Processing chamber (an example of a processing container). Detailed Implementation

[0028] <One implementation of this disclosure>

[0029] Hereinafter, one embodiment of the present disclosure will be described with reference to the accompanying drawings. It should be noted that the drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to the actual situation. Furthermore, the dimensional relationships and ratios of the elements may not necessarily be consistent among multiple drawings.

[0030] [Composition of the substrate processing device]

[0031] First of all, Figure 1 The substrate processing apparatus 10 implementing the present disclosure will be described below. The substrate processing apparatus 10 includes a housing 111, and a front maintenance opening 103 is provided at the lower part of the front wall 111a of the housing 111 as an opening for maintenance. The front maintenance opening 103 is opened and closed by a front maintenance door 104.

[0032] On the front wall 111a of the housing 111, a cassette loading and unloading outlet 112 is provided to connect the inside and outside of the housing 111. The cassette loading and unloading outlet 112 is opened and closed by a front gate 113. A loading port (transfer container transfer platform) 114 is provided on the front side of the cassette loading and unloading outlet 112. The loading port 114 is configured to align the placed cassette 110.

[0033] The crystal cell 110 is a sealed substrate transfer container, which is moved into or out of the loading port 114 by an in-process transfer device (not shown).

[0034] A rotating crystal box rack (transfer container storage rack) 105 is provided at the upper part of the approximately central part in the front-back direction inside the housing 111. The rotating crystal box rack 105 is configured to store multiple crystal boxes 110.

[0035] The rotating crystal box rack 105 includes: a vertically erected and intermittently rotating support column 116; and multiple rack plates (transfer container racks) 117 radially supported on the support column 116 at various positions in the upper, middle and lower layers, the rack plates 117 being configured to store the crystal boxes 110 in a state where each rack holds multiple crystal boxes 110.

[0036] Below the rotating crystal box holder 105, there is a crystal box opener (conveying container cover opening and closing mechanism) 121, which has the structure of holding the crystal box 110 and being able to open and close the cover of the crystal box 110.

[0037] A crystal box conveying mechanism (container conveying mechanism) 118 is provided between the loading port 114 and the rotary crystal box rack 105 and the crystal box opener 121. The crystal box conveying mechanism 118 is configured to hold the crystal box 110 and be able to lift and lower it, move forward and backward in the horizontal direction, and convey the crystal box 110 between the loading port 114, the rotary crystal box rack 105 and the crystal box opener 121.

[0038] A sub-shell 119 is provided at the lower part of the approximately central portion in the front-rear direction within the shell 111, extending all the way to the rear end. On the front wall 119a of the sub-shell 119, a pair of wafer loading and unloading outlets (substrate loading and unloading outlets) 120 are provided side by side in two layers. The wafer loading and unloading outlets 120 are used to load and unload wafers 200 relative to the sub-shell 119. A cassette opener 121 is provided on the upper and lower wafer loading and unloading outlets 120 respectively.

[0039] The cell opener 121 includes: a mounting stage 122 for placing the cell 110; and an opening / closing mechanism 123 for opening and closing the cover of the cell 110. The cell opener 121 is configured such that the opening / closing mechanism 123 opens and closes the cover of the cell 110 placed on the mounting stage 122, thereby opening and closing the wafer inlet / outlet of the cell 110.

[0040] The sub-housing 119, together with the space containing the cassette transfer mechanism 118 and the rotating cassette holder 105 (cassette transfer space), forms an airtight transfer chamber 124. In the front region of the transfer chamber 124, a wafer transfer mechanism (substrate transfer mechanism) 125 is provided. The wafer transfer mechanism 125 has a wafer carrier plate 125c that can hold the required number of wafers 200 (5 in the figure). The wafer carrier plate 125c can move linearly in the horizontal direction, rotate in the horizontal direction, and move up and down. The wafer transfer mechanism 125 is configured to load and unload wafers 200 from the wafer boat (substrate holder) 217. When transferring wafers 200 from the cassette 110 to the wafer boat 217, the cassette 110 and the wafer loading / unloading outlet 120 are sealed together, and the gas atmosphere inside the cassette 110 and the transfer chamber 124 is the same.

[0041] In the rear region of the transfer chamber 124, a standby section 126 is formed to house the crystal boat 217 and keep it in standby mode. A vertical processing furnace 202 is provided above the standby section 126. The processing furnace 202 forms a processing chamber 201 inside, and the lower end of the processing chamber 201 becomes a furnace opening, which is opened and closed by a sealing cover 219.

[0042] Between the right end of the housing 111 and the right end of the standby section 126 of the sub-housing 119, a crystal boat lift (substrate holder lifting mechanism) 115 for lifting the crystal boat 217 is provided. A sealing cover 219, which serves as a cover, is horizontally mounted on the arm 128 connected to the lifting platform of the crystal boat lift 115. The sealing cover 219 vertically supports the crystal boat 217 and can airtightly seal the furnace gate 147 when the crystal boat 217 is loaded into the processing chamber 201.

[0043] The crystal boat 217 is configured to hold multiple (e.g., about 50 to 125) wafers 200 in a multi-layered manner with their centers aligned and in a horizontal orientation.

[0044] An exhaust pipe 131 is provided on the back wall 119b of the sub-housing 119 for venting the atmosphere from the transfer chamber 124. From upstream, the exhaust pipe 131 is sequentially connected to a pressure sensor 145 (a pressure detector, or pressure sensing unit) for detecting the pressure within the transfer chamber 124, an APC (Auto Pressure Controller) valve 143, and a vacuum pump 146 (a vacuum venting device). The APC valve 143 can perform vacuum venting and stop vacuum venting within the transfer chamber 124 by opening and closing the valve while the vacuum pump 146 is operating. Furthermore, the pressure within the transfer chamber 124 can be adjusted by regulating the valve opening while the vacuum pump 146 is operating. The exhaust pipe 131, the APC valve 143, and the pressure sensor 145 constitute the venting system for the transfer chamber 124 and the crystal cell 110 sealed to the transfer chamber 124. Including the vacuum pump 146 in the venting system is also an option.

[0045] Additionally, on the back wall 119b of the sub-casing 119, a gas supply pipe 150 for supplying inactive gases other than rare gases and a gas supply pipe 151 for supplying rare gases are respectively connected. On the gas supply pipe 150, starting from the upstream side, an MFC 152 serving as a flow controller (flow control unit) and a valve 154 serving as an on / off valve are sequentially provided. On the gas supply pipe 151, starting from the upstream side, an MFC 153 serving as a flow controller (flow control unit) and a valve 155 serving as an on / off valve are sequentially provided.

[0046] An inactive gas other than a rare gas is supplied from the gas supply pipe 150 to the transfer chamber 124 via the MFC 152 and the valve 154. For example, nitrogen (N2) gas can be used as an inactive gas other than a rare gas. When the inactive gas flows into the transfer chamber 124 from the gas supply pipe 150, the inactive gas supply system for the transfer chamber 124 and the cell 110 sealed to the transfer chamber 124 is mainly composed of the gas supply pipe 150, the MFC 152, and the valve 154.

[0047] Rare gas is supplied to the transfer chamber 124 through the gas supply pipe 151, MFC 153, and valve 155. Examples of rare gases that can be used include helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe). When rare gas flows into the transfer chamber 124 from the gas supply pipe 151, the rare gas supply system for the transfer chamber 124 and the cell 110 sealed to the transfer chamber 124 mainly consists of the gas supply pipe 151, MFC 153, and valve 155.

[0048] Furthermore, a temperature sensor 163, serving as a temperature detector, is installed within the transfer chamber 124. The system is configured to adjust the electrical current supplied to the heater 107 based on the temperature information detected by the temperature sensor 163, thereby achieving the desired temperature distribution within the transfer chamber 124. The heater 107 constitutes the main heating system for the transfer chamber 124.

[0049] Next, in Figure 2 and Figure 3 The configuration surrounding the processing chamber 201 will be described below. The processing chamber 201 includes a processing furnace 202, which is equipped with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 is cylindrical in shape and is vertically mounted by means of a heater base (not shown) supported by a retaining plate.

[0050] Inside the heater 207, an outer tube 203 constituting a reaction vessel (processing vessel) is arranged concentrically with the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape that is closed at the top and open at the bottom. Below the outer tube 203, a manifold (inlet 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 that is open at both the top and bottom. An O-ring 220a, serving as a sealing component, is provided between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported on the heater base, thereby allowing the outer tube 203 to be installed vertically.

[0051] 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 (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape that is closed at the top and open at the bottom. The processing vessel (reaction vessel) is composed of at least the outer tube 203 and the manifold 209. The inner tube 204 can be included in the processing vessel. A processing chamber 201 is formed in the hollow part of the processing vessel (inside the inner tube 204).

[0052] The processing chamber 201 is configured to house the wafer 200, which serves as a substrate, in a state in which multiple layers are arranged in a horizontal orientation along the vertical direction using the crystal boat 217 described later.

[0053] Inside the processing chamber 201, nozzles 410, 420, and 430 are provided so as to penetrate the side wall of the manifold 209 and the inner pipe 204. Gas supply pipes 310, 320, and 330 are respectively connected to the nozzles 410, 420, and 430. However, the processing furnace 202 of this embodiment is not limited to the above-described form.

[0054] Mass flow controllers (MFCs) 312, 322, and 332, serving as flow controllers (flow control units), are sequentially installed on gas supply pipes 310, 320, and 330, starting from the upstream side. Additionally, valves 314, 324, and 334, serving as on / off valves, are installed on gas supply pipes 310, 320, and 330, respectively. Downstream of valves 314, 324, and 334 in gas supply pipes 310, 320, and 330, gas supply pipes 510, 520, and 530, supplying inert gases other than rare gases, and gas supply pipes 511, 521, and 531, supplying rare gases, are respectively connected.

[0055] On gas supply pipes 510, 520, and 530, starting from the upstream side, MFCs 512, 522, and 532, serving as flow controllers (flow control units), and valves 514, 524, and 534, serving as on / off valves, are respectively installed. Additionally, on gas supply pipes 511, 521, and 531, starting from the upstream side, MFCs 513, 523, and 533, serving as flow controllers (flow control units), and valves 515, 525, and 535, serving as on / off valves, are respectively installed.

[0056] Nozzles 410, 420, and 430 are respectively connected to the front ends of gas supply pipes 310, 320, and 330. Nozzles 410, 420, and 430 are configured in the form of L-shaped nozzles, with their horizontal portions extending through the side wall of manifold 209 and inner tube 204. The vertical portions of nozzles 410, 420, and 430 are disposed inside a channel-shaped (groove-shaped) preparation chamber 201a, and are disposed upward along the inner wall of inner tube 204 (above the arrangement direction of wafers 200) within the preparation chamber 201a. The preparation chamber 201a is formed to protrude radially outward from inner tube 204 and extend vertically.

[0057] Nozzles 410, 420, and 430 are arranged to extend from the lower region to the upper region of the processing chamber 201, and multiple gas supply holes 410a, 420a, and 430a are respectively provided at positions opposite to the wafer 200. Thus, processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420a, and 430. Multiple gas supply holes 410a, 420a, and 430a are provided from the lower to the upper part of the inner tube 204, each having the same opening area and the same opening spacing. However, the gas supply holes 410a, 420a, and 430a are not limited to the above configuration. For example, the opening area can gradually increase from the lower part to the upper part of the inner tube 204. This allows for a more uniform flow rate of gas supplied from the gas supply holes 410a, 420a, and 430a.

[0058] Gas supply holes 410a, 420a, and 430a of nozzles 410, 420, and 430 are provided at a height position from the lower part to the upper part of the crystal boat 217 (described later). Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430 of nozzles 410, 420, and 430a is supplied to the entire area of ​​the wafer 200 housed in the crystal boat 217 from the lower part to the upper part. Nozzles 410, 420, and 430 can be provided in such a way that they extend from the lower region to the upper region of the processing chamber 201, but are preferably provided in a way that they extend to near the top of the crystal boat 217.

[0059] A gas containing a metal element is supplied as a processing gas into the processing chamber 201 through the gas supply pipe 310 via MFC 312, valve 314, and nozzle 410. For example, a gas containing molybdenum (Mo), a gas containing ruthenium (Ru), or a gas containing tungsten (W) can be used as the gas containing the metal element.

[0060] When the gas containing metal elements flows into the gas supply pipe 310, the gas supply system for the processing chamber 201 mainly consists of the gas supply pipe 310, MFC 312, and valve 314. However, it is also possible to include the nozzle 410 in the gas supply system for the metal elements.

[0061] A reducing gas is supplied as a processing gas into the processing chamber 201 via the gas supply pipe 320 through the MFC 322, valve 324, and nozzle 420. For example, hydrogen (H2) gas, deuterium (D2) gas, or a gas containing activated hydrogen can be used as the reducing gas.

[0062] When reducing gas flows into the gas supply pipe 320, the reducing gas supply system for the processing chamber 201 is mainly composed of the gas supply pipe 320, MFC 322, and valve 324. It is also possible to include the nozzle 420 in the reducing gas supply system.

[0063] Modified gas is supplied as a treatment gas from gas supply pipe 330 through MFC 332, valve 334, and nozzle 430 into treatment chamber 201. As the modified gas, for example, one gas selected from the following: silicon hydride gas, chlorosilane gas, oxygen-containing gas, nitrogen-containing gas, boron-containing gas, fluorine-containing gas, phosphorus-containing gas, etc., or a mixture of gases containing at least one or more gases can be used.

[0064] When modified gas flows into the gas supply pipe 330, the modified gas supply system for the processing chamber 201 is mainly composed of the gas supply pipe 330, MFC 332, and valve 334. It is also possible to include the nozzle 430 in the modified gas supply system.

[0065] Non-reactive gases other than rare gases are supplied to the processing chamber 201 from gas supply pipes 510, 520, and 530 via MFCs 512, 522, and 532, valves 514, 524, and 534, and nozzles 410, 420, and 430, respectively. For example, nitrogen (N2) gas can be used as one of these non-reactive gases.

[0066] When inactive gas flows into the gas supply pipes 510, 520, and 530, the inactive gas supply system for the processing chamber 201 is mainly composed of gas supply pipes 510, 520, and 530, MFCs 512, 522, and 532, valves 514, 524, and 534, and gas supply pipes 310, 320, and 330. It is also possible to include nozzles 410, 420, and 430 in the inactive gas supply system.

[0067] Rare gases are supplied to the processing chamber 201 from gas supply pipes 511, 521, and 531 via MFCs 513, 523, and 533, valves 515, 525, and 535, and nozzles 410, 420, and 430, respectively. Examples of rare gases that can be used include helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).

[0068] When rare gas flows into the processing chamber 201 from gas supply pipes 511, 521, and 531, the rare gas supply system mainly consists of gas supply pipes 511, 521, 531, MFCs 513, 523, and 533, valves 515, 525, and 535, and gas supply pipes 310, 320, and 330. It is also possible to include nozzles 410, 420, and 430 within the rare gas supply system.

[0069] In the gas supply method of this embodiment, gas is transported via nozzles 410, 420, and 430 disposed within a preparation chamber 201a (which is located within an annular longitudinal space defined by the inner wall of the inner tube 204 and the ends of multiple wafers 200). Furthermore, gas is ejected into the inner tube 204 from multiple gas supply holes 410a, 420a, and 430a located opposite the wafers on the nozzles 410, 420, and 430. More specifically, processing gas is ejected in a direction parallel to the surface of the wafer 200 through the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420a, and 430a.

[0070] The exhaust port (vent) 204a is a through-hole formed on the side wall of the inner tube 204 opposite to the nozzles 410 and 420. For example, it is a narrow slit-like through-hole that is elongated in the vertical direction. Gas supplied from the gas supply holes 410a and 420a of the nozzles 410 and 420 into the processing chamber 201 and flowing over the surface of the wafer 200 flows through the exhaust port 204a into the exhaust passage 206, which is formed by the gap between the inner tube 204 and the outer tube 203. Furthermore, the gas flowing into the exhaust passage 206 flows into the exhaust pipe 231 and is discharged out of the processing furnace 202.

[0071] The exhaust port 204a is located opposite to the plurality of wafers 200. Gas supplied from the gas supply ports 410a and 420a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally and then flows into the exhaust passage 206 through the exhaust port 204a. The exhaust port 204a is not limited to being configured as a slit-shaped through hole, but may also be composed of multiple holes.

[0072] An exhaust pipe 231 for venting the atmosphere inside the processing chamber 201 is provided on the manifold 209. From upstream, the exhaust pipe 231 is sequentially connected to a pressure sensor 245 (a pressure detector, or pressure sensing unit) for detecting the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 (a vacuum venting device). The APC valve 243 can perform vacuum venting and stop vacuum venting in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by regulating the valve opening while the vacuum pump 246 is operating. The exhaust system for the processing chamber 201 is mainly composed of the exhaust port 204a, exhaust path 206, exhaust pipe 231, APC valve 243, and pressure sensor 245. Including the vacuum pump 246 in the exhaust system is a viable option.

[0073] Below the manifold 209, a sealing cover 219, serving as a furnace opening cover, is provided to airtightly seal the lower opening of the manifold 209. The sealing cover 219 is configured to abut against the lower end of the manifold 209 from a vertical downward direction. The sealing cover 219 is made of a metal such as SUS and is formed in a disc shape. An O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209 on the upper surface of the sealing cover 219. On the side of the sealing cover 219 opposite to the processing chamber 201, a rotation mechanism 267 is provided to rotate a crystal boat 217 containing the wafer 200. The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217.

[0074] The sealing cover 219 is configured to move vertically upwards and downwards via a crystal boat lift 115, which is vertically mounted outside the outer tube 203 and serves as a lifting mechanism. The crystal boat lift 115 is configured to move the crystal boat 217 into and out of the processing chamber 201 by raising and lowering the sealing cover 219. The crystal boat lift 115 is configured as a transport device for transporting the crystal boat 217 and the wafers 200 contained within the crystal boat 217 to and from the processing chamber 201. The transport system mainly consists of the crystal boat lift 115 and the wafer transfer mechanism 125.

[0075] The crystal boat 217, serving as a substrate support, is configured such that multiple (e.g., 25 to 200) wafers 200 are arranged horizontally and aligned at intervals in the vertical direction. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. At the lower part of the crystal boat 217, a heat insulation plate 218, made of a heat-resistant material such as quartz or SiC, is supported horizontally and in multiple layers (not shown). With this configuration, heat from the heater 207 is not easily conducted to the sealing cover 219 side. However, this embodiment is not limited to the above-described configuration. For example, the heat insulation plate 218 may not be provided at the lower part of the crystal boat 217, but instead a heat insulation cylinder made of a cylindrical member made of a heat-resistant material such as quartz or SiC may be provided.

[0076] like Figure 3 As shown, a temperature sensor 263, serving as a temperature detector, is installed inside the inner tube 204. The configuration is such that the electrical current supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving the desired temperature distribution within the processing chamber 201. The temperature sensor 263, like the nozzles 410, 420, and 430, is L-shaped and arranged along the inner wall of the inner tube 204. The heater 207 constitutes the main heating system within the processing chamber 201.

[0077] like Figure 4 As shown, the controller 121, which serves as the control unit (control mechanism), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured 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.

[0078] Storage device 121c is configured such as flash memory or HDD (Hard Disk Drive). Within storage device 121c, control programs that control the operation of the substrate processing apparatus and process flow describing the steps and conditions of the semiconductor device manufacturing method (described later) are stored in a readable manner. The process flow is a combination of steps in the semiconductor device manufacturing method (described later) that enable the controller 121 to execute and obtain a predetermined result, and functions as a program. Hereinafter, the process flow, control programs, etc., will also be referred to collectively as a program. In this specification, the term "program" is used in cases where only the process flow is included, cases where only the control program is included, or cases where a combination of the process flow and the control program is included. RAM 121b is configured as a storage area (working area) for temporarily holding programs, data, etc., read by CPU 121a.

[0079] I / O port 121d is connected to the aforementioned MFCs 152, 153, 312, 322, 332, 512, 513, 522, 523, 532, 533, valves 154, 155, 314, 324, 334, 514, 515, 524, 525, 534, 535, pressure sensors 145, 245, APC valves 143, 243, vacuum pumps 146, 246, heaters 107, 207, temperature sensors 163, 263, rotating mechanism 267, crystal boat lift 115, wafer transfer mechanism 125, etc.

[0080] CPU 121a is configured to read and execute control programs from storage device 121c, and to read process data from storage device 121c based on input commands from input / output device 122. CPU 121a is configured to control the following actions according to the read process data: various gas flow regulation actions performed using MFCs 152, 153, 312, 322, 332, 512, 513, 522, 523, 532, and 533; opening and closing actions of valves 154, 155, 314, 324, 334, 514, 515, 524, 525, 534, and 535; opening and closing actions of APC valves 143 and 243; and actions based on pressure sensor 145. The pressure regulation operation of 245 using APC valves 143 and 243, the temperature regulation operation of heaters 107 and 207 based on temperature sensors 163 and 263, the start and stop of vacuum pumps 146 and 246, the rotation and rotation speed regulation operation of crystal boat 217 using rotating mechanism 267, the lifting operation of crystal boat 217 using crystal boat elevator 115, and the transfer operation of wafer 200 between crystal cell 110 and crystal boat 217 using wafer transfer mechanism 125, etc.

[0081] The controller 121 can be configured to install the aforementioned program stored in an external storage device (e.g., magnetic tape, floppy disk, hard disk, CD, DVD, MO, USB memory, memory card, etc.) 123 onto a computer. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium. Hereinafter, they will also be referred to collectively as a recording medium. In this specification, the recording medium includes cases containing only the storage device 121c, cases containing only the external storage device 123, or cases containing both. The program can also be provided to the computer without using the external storage device 123, but using communication means such as the Internet or dedicated lines.

[0082] [Substrate processing process]

[0083] As a step in the manufacturing process of semiconductor devices (equipment), using Figure 5 , Figure 6 (A) and Figure 6 (B) describes an example of a process for forming a Mo-containing film on wafer 200, for example, as a control gate electrode for a 3D NAND flash memory. Here, as... Figure 6 As shown in (A), on a wafer 200 with a Mo-containing film formed on its surface, as Figure 6 As shown in (B), a silicon (Si) capping film is formed. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121.

[0084] In the substrate processing step (semiconductor device manufacturing step) based on this embodiment, the following are included:

[0085] (a) A process of supplying a gas containing a metal element to a wafer 200 housed in a processing chamber 201;

[0086] (b) The process of supplying reducing gas to wafer 200;

[0087] (c) A process of forming a film containing metal elements on wafer 200 by performing (a) and (b) a specified number of times;

[0088] (d) Following (c), the process of supplying a modifying gas to a membrane containing a metal element, and forming a layer containing the element contained in the modifying gas on the surface of the membrane; and

[0089] (e) After (d), the process of moving the wafer 200 from the processing chamber 201 to the transfer chamber 124 by filling the processing chamber 201 and the transfer chamber 124 with a rare gas atmosphere.

[0090] In this specification, the term "wafer" is used to refer to "the wafer itself" or "a laminate of a wafer and a specified layer or film formed on its surface." The term "surface of the wafer" is used to refer to "the surface of the wafer itself" or "the surface of a specified layer, film, etc., formed on the wafer." The term "substrate" is used in the same way as "wafer."

[0091] [Chip loading]

[0092] Valves 154, 314, 324, and 334 are opened to allow nitrogen (N2) gas, which is an inactive gas other than rare gases, to flow into gas supply pipes 150, 310, 320, and 330. The N2 gas flow rate is regulated by MFCs 152, 512, 522, and 532 and supplied to the processing chamber 201, the transfer chamber 124, and the crystal cell 110 sealed to the transfer chamber 124.

[0093] In a state where the processing chamber 201, the transfer chamber 124, and the crystal cassette 110 which is sealed with the transfer chamber 124 are in an N2 gas atmosphere, multiple wafers 200 are transferred from the crystal cassette 110 (wafer filling (step S10)) to the crystal boat 217.

[0094] Then, as Figure 2 As shown, the crystal boat 217, which supports multiple wafers 200, is lifted by the crystal boat lift 115 and moved into the processing chamber 201 (crystal boat loading (step S11)), and housed in the processing container. In this state, the sealing cap 219 closes the lower opening of the outer tube 203 by means of the O-ring 220.

[0095] Then, the APC valve 143 of the exhaust pipe 131 located in the transfer chamber 124 is opened, and the vacuum pump 146 is used to perform vacuum exhaust in the transfer chamber 124 and the crystal box 110 sealed with the transfer chamber 124, thereby removing the N2 gas remaining in the transfer chamber 124 and the crystal box 110. Next, the APC valve 143 is closed, and the valve 155 is opened simultaneously, allowing Ar gas, which is a rare gas, to flow into the gas supply pipe 151, replacing the atmosphere in the transfer chamber 124 and the crystal box 110 with an Ar gas atmosphere (atmosphere replacement (step S12)). It should be noted that the atmosphere replacement in the transfer chamber 124 and the crystal box 110 does not necessarily need to be performed immediately after step S11, but only before the unloading of the crystal boat in step S22 described later.

[0096] [Pressure and temperature regulation (step S13)]

[0097] Vacuum pump 246 is used to exhaust vacuum from the processing chamber 201, the space where wafer 200 is located, to achieve the desired pressure (vacuum level). At this time, the pressure within the processing chamber 201 is measured by pressure sensor 245, and based on this measured pressure information, APC valve 243 is subjected to feedback control (pressure regulation). Vacuum pump 246 remains operational at least until the processing of wafer 200 is complete.

[0098] Additionally, heating is performed using heater 207 to achieve a desired temperature within the processing chamber 201. During this process, the power supply to heater 207 is controlled feedback (temperature regulation) based on temperature information detected by temperature sensor 263 to achieve a desired temperature distribution within the processing chamber 201. Hereinafter, the temperature of heater 207 is set to a temperature within the range of, for example, 300°C to 650°C for the wafer 200. Furthermore, the heating within the processing chamber 201 performed using heater 207 continues at least until the processing of the wafer 200 is completed, i.e., until step S20, during which the temperature within the processing chamber 201 remains constant.

[0099] [Gas containing metallic elements (step S14)]

[0100] Valve 314 is opened, allowing a metal-containing gas, serving as the raw material gas, to flow into the gas supply pipe 310. The flow rate of the metal-containing gas is regulated by MFC 312, supplying it into the processing chamber 201 from the gas supply port 410a of nozzle 410 and exhausting it from the exhaust pipe 231. At this time, the metal-containing gas is supplied to the wafer 200.

[0101] At the same time, valve 515 is opened, allowing Ar gas, a rare gas, to flow into gas supply pipe 511. The flow rate of the Ar gas flowing into gas supply pipe 511 is regulated by MFC 513, and it is supplied into processing chamber 201 together with the gas containing metal elements, and is exhausted from exhaust pipe 231. Ar gas acts as a carrier gas, which can promote the supply of gas containing metal elements into processing chamber 201.

[0102] At this time, in order to prevent the gas containing metal elements from entering the nozzles 420 and 430, valves 525 and 535 are opened to allow Ar gas to flow into the gas supply pipes 521 and 531. The Ar gas is supplied to the processing chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430, and is exhausted from the exhaust pipe 231.

[0103] At this time, the APC valve 243 is adjusted to bring the pressure in the processing chamber 201 to, for example, a range of 1 to 3990 Pa. The supply flow rate of the metal-containing gas controlled by MFC 312 is, for example, a range of 0.1 to 1.0 slm, preferably 0.1 to 0.5 slm. The supply flow rate of Ar gas controlled by MFCs 513, 523, and 533 is each set to, for example, a range of 0.1 to 20 slm. It should be noted that the expression of numerical ranges such as "1 to 3990 Pa" in this disclosure means that the lower and upper limits are included within the range. Therefore, for example, "1 to 3990 Pa" means "above 1 Pa and below 3990 Pa". The same applies to other numerical ranges.

[0104] At this time, the gas flowing into the processing chamber 201 consists only of a gas containing a metal element and Ar gas as a rare gas. Mo-containing gas can be used as the gas containing the metal element. Examples of Mo-containing gases include molybdenum pentachloride (MoCl5), molybdenum dichloride dioxide (MoO2Cl2), and molybdenum oxide tetrachloride (MoOCl4). By supplying the gas containing the metal element, a layer containing the metal element is formed on the wafer 200. Here, when MoO2Cl2 gas is used as the gas containing the metal element, the layer containing the metal element is a Mo-containing layer. The Mo-containing layer can be a Mo layer containing Cl and O, an adsorption layer of MoO2Cl2, or both. Furthermore, the Mo-containing layer is a film with Mo as the main component, and may also contain elements such as Cl, O, and H in addition to Mo.

[0105] [Residual gas removal (step S15)]

[0106] After a predetermined time, for example, 0.01 to 10 seconds, elapsed from the start of supplying 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, for example, within the range of 0.01 to 10 seconds. At this time, with the APC valve 243 of the exhaust pipe 231 open, the vacuum pump 246 is used to perform vacuum exhaust in the processing chamber 201, removing any unreacted gas or metal-containing gas that may contribute to the formation of the metal-containing layer remaining in the processing chamber 201. That is, the processing chamber 201 is purged (first purging step).

[0107] At this time, valves 515, 525, and 535 remain open, maintaining the supply of Ar gas into the processing chamber 201. The Ar gas acts as a purging gas, which can improve the effect of removing unreacted gases or gases containing metal elements that contribute to the formation of a layer containing metal elements from the processing chamber 201.

[0108] [Reducing gas supply (step S16)]

[0109] After removing the residual gas from the processing chamber 201, valve 324 is opened, allowing reducing gas to flow into the gas supply pipe 320. The reducing gas flow rate is regulated by MFC 322, supplying it into the processing chamber 201 from the gas supply port 420a of nozzle 420 and exhausting it from exhaust pipe 231. At this time, reducing gas is supplied to wafer 200.

[0110] At this time, valve 525 is simultaneously opened, allowing Ar gas, which is a rare gas, to flow into gas supply pipe 521. The flow rate of the Ar gas flowing into gas supply pipe 521 is regulated by MFC 523, and it is supplied to processing chamber 201 together with reducing gas, and exhausted from exhaust pipe 231. Ar gas acts as a carrier gas, which can promote the supply of reducing gas into processing chamber 201.

[0111] At this time, in order to prevent the gas containing metal elements from entering the nozzles 410 and 430, valves 515 and 535 are opened to allow Ar gas to flow into the gas supply pipes 511 and 531. The Ar gas is supplied to the processing chamber 201 through the gas supply pipes 310 and 330 and the nozzles 410 and 430, and is exhausted from the exhaust pipe 231.

[0112] At this time, adjust APC valve 243 to bring the pressure inside processing chamber 201 to, for example, a range of 1 to 39900 Pa. The supply flow rate of reducing gas controlled by MFC 322 is, for example, a range of 1 to 50 slm, preferably 15 to 30 slm. The supply flow rate of Ar gas controlled by MFCs 513, 523, and 533 is set to, for example, a range of 0.1 to 30 slm. The time for supplying reducing gas to wafer 200 is set to, for example, a range of 0.01 to 120 seconds.

[0113] At this point, the gas flowing into the processing chamber 201 consists only of a reducing gas and Ar gas as a rare gas. Here, the reducing gas can be, for example, hydrogen (H2) gas, deuterium (D2) gas, or a gas containing activated hydrogen. When H2 gas is used as the reducing gas, the H2 gas undergoes a displacement reaction with at least a portion of the Mo-containing layer formed on the wafer 200 in step S14. That is, O and chlorine (Cl) in the Mo-containing layer react with H2, detach from the Mo layer, and are discharged from the processing chamber 201 as reaction byproducts such as water vapor (H2O), hydrogen chloride (HCl), and chlorine (Cl2). Thus, a layer containing Mo and substantially free of Cl and O (Mo layer) is formed on the wafer 200.

[0114] [Residual gas removal (step S17)]

[0115] After the layer containing the metal element is formed, valve 324 is closed to stop the supply of reducing gas. Then, using the same processing steps as step S15 (first purging step) described above, Ar gas is used as the purging gas to remove unreacted or reactive reducing gases and reaction byproducts remaining in the processing chamber 201 that contribute to the formation of the layer containing the metal element. That is, the processing chamber 201 is purged (second purging step).

[0116] [Perform the prescribed number of times (step S18)]

[0117] The above steps S14 to S17 are performed sequentially at least once (a predetermined number of times (n times)) to form a film containing metal elements with a predetermined thickness (e.g., 0.5 to 20.0 nm) on the wafer 200. It is preferable to repeat the above cycle multiple times. Alternatively, each of steps S14 to S17 may be performed at least once.

[0118] [Modified gas supply (step S19)]

[0119] After removing the residual gas from the processing chamber 201, valve 334 is opened, allowing modified gas to flow into the gas supply pipe 330. The modified gas flow rate is regulated by MFC 332, supplying it into the processing chamber 201 from the gas supply port 430a of nozzle 430 and exhausting it from exhaust pipe 231. At this time, modified gas is supplied to wafer 200.

[0120] At the same time, valve 535 is opened, allowing Ar gas, which is a rare gas, to flow into gas supply pipe 531. The flow rate of the Ar gas flowing into gas supply pipe 531 is regulated by MFC 533, and it is supplied to processing chamber 201 together with reducing gas, and exhausted from exhaust pipe 231. Ar gas acts as a carrier gas, which can promote the supply of modified gas into processing chamber 201.

[0121] At this time, in order to prevent the gas containing metal elements from entering the nozzles 410 and 420, valves 515 and 525 are opened to allow Ar gas to flow into the gas supply pipes 511 and 521. The Ar gas is supplied to the processing chamber 201 through the gas supply pipes 310 and 320 and the nozzles 410 and 420, and is exhausted from the exhaust pipe 231.

[0122] At this time, adjust APC valve 243 to bring the pressure in processing chamber 201 to a range of, for example, 1 to 3990 Pa. The supply flow rate of the modified gas, controlled by MFC 332, is set to a range of, for example, 0.1 to 30 slm, preferably 0.1 to 10 slm. The supply flow rates of Ar gas, controlled by MFCs 513, 523, and 533, are each set to a range of, for example, 0.1 to 30 slm. The time for supplying the modified gas to wafer 200 is set to a time range of, for example, 1 to 1200 seconds.

[0123] At this time, the gas flowing into the processing chamber 201 consists only of the modified gas and Ar gas as a rare gas. Here, the modified gas can be one of the following: silicon hydride gas, chlorosilane gas, oxygen-containing gas, nitrogen-containing gas, boron-containing gas, fluorine-containing gas, phosphorus-containing gas, or a mixture containing at least one gas.

[0124] By supplying a modifying gas, a layer containing the elements contained in the modifying gas can be formed on the surface of the film on the wafer 200. In other words, the surface of the film can be modified. When using silicon hydride gas as the modifying gas, a layer containing silicon (Si) (capping layer) can be formed on the surface of the Mo-containing film formed on the wafer 200 in step S14. It should be noted that as the silicon hydride gas, one gas selected from silane (SiH4), disilane (Si2H6), and trisilane (Si3H8), or a mixture of at least one gas, can be used.

[0125] like Figure 6 As shown in (A), when the Mo-containing film is not covered by a Si capping layer, the Mo-containing film may sometimes be nitrided due to nitrogen (N) in the atmospheric atmosphere, resulting in increased resistivity. In contrast, in this embodiment, as... Figure 6 As shown in (B), a Si capping layer is formed on the Mo-containing film, which can suppress the nitriding of the Mo-containing film due to nitrogen in the atmospheric atmosphere and reduce the effects of nitrogen.

[0126] [Residual gas removal (step S20)]

[0127] After the capping layer is formed, valve 334 is closed to stop the supply of modified gas. Then, using the same processing steps as step S15 (first purging step) described above, Ar gas is used as the purging gas to remove unreacted or modified gas and reaction byproducts remaining in the processing chamber 201 that contribute to the formation of the capping layer. That is, the processing chamber 201 is purged (post-purging step).

[0128] [Atmospheric pressure recovery (step S21)]

[0129] After the atmosphere in the processing chamber 201 is replaced with Ar gas, the pressure in the processing chamber 201 returns to atmospheric pressure.

[0130] [Chip removal]

[0131] Then, the sealing cover 219 is lowered using the crystal boat lift 115, and the lower end of the outer tube 203 is opened. The processed wafer 200, supported by the crystal boat 217, is then moved from the lower end of the outer tube 203 into the transfer chamber 124 (crystal boat unloading (step S22)). The processed wafer 200 is then transferred from the crystal boat 217 to the wafer cassette 110 (wafer removal (step S23)). It should be noted that the removal of the wafer 200 is preferably performed while maintaining the temperature set within the processing chamber 201 from the time of film deposition. By maintaining the temperature set within the processing chamber 201 from the time of film deposition, the time required for temperature adjustment of the processing chamber 201 can be shortened.

[0132] In step S12, the transfer chamber 124 and the die cell 110 are filled with an Ar gas atmosphere, and in step S20, the processing chamber 201 is also filled with an Ar gas atmosphere. Therefore, the transfer of the processed wafer 200 from the processing chamber 201 to the die cell 110 is carried out in the transfer chamber 124 under an Ar gas atmosphere. By maintaining such an atmosphere, it is possible to suppress the nitriding of the Mo-containing film caused by nitrogen in the atmospheric atmosphere on the Mo-containing film while maintaining the temperature in the processing chamber 201 from the time of substrate processing (i.e., a high-temperature state).

[0133] In this embodiment, a Si capping layer is formed on the Mo-containing film, which can suppress the adsorption (nitriding) of nitrogen in the atmospheric atmosphere on the surface of the Mo-containing film and reduce the influence of nitrogen. By removing the wafer under an Ar gas atmosphere as described above, the wafer 200 does not come into contact with nitrogen during wafer removal, thereby further suppressing the nitriding of the Mo-containing film.

[0134] [Effects of this implementation method]

[0135] As described above, a modification treatment is performed to form a layer containing the elements contained in the modifying gas on the surface of a film containing metal elements (which is formed on wafer 200). This process suppresses oxygen adsorption on the surface of the film on wafer 200 and nitrogen adsorption on the surface of the film on wafer 200. It should be noted that oxygen adsorption is also called oxidation. In addition, nitrogen adsorption is also called nitriding.

[0136] Furthermore, not only the film on the wafer 200 can be modified, but also the film on the inner wall of the processing chamber 201 can be modified. Therefore, even when nitrogen gas enters the processing chamber 201 during wafer 200 loading, nitrogen adsorption on the film on the inner wall of the processing chamber 201 can be suppressed. If nitrogen is adsorbed on the film on the inner wall of the processing chamber 201, it may detach during film formation and potentially enter the film formed on the wafer 200. Therefore, by modifying the film on the inner wall of the processing chamber 201, this situation can be suppressed.

[0137] In the semiconductor device manufacturing method of this embodiment, it is preferable to perform the process while maintaining the temperature setting in the processing chamber 201 in (c) and (d).

[0138] Thus, by maintaining the temperature set during film formation during the transfer process, the time required for temperature conditioning within the processing chamber 201 can be shortened. As a result, manufacturing output can be increased. Furthermore, thermal stress caused by temperature drops in parts of the processing chamber 201 and transfer chamber 124 can be suppressed, thus reducing the likelihood of film peeling due to thermal stress.

[0139] Additionally, it is preferable to have: (f) a process prior to (a) of transferring the wafer 200 from the transfer chamber 124 to the processing chamber 201 with an atmosphere of inactive gas other than rare gas in the processing chamber 201 and the transfer chamber 124; and (g) a process between (f) and (e) of changing the atmosphere of inactive gas other than rare gas in the processing chamber 201 and the transfer chamber 124 to a rare gas atmosphere.

[0140] Thus, by using inexpensive, inactive gases before film formation and only using expensive rare gases after film formation, the amount of expensive rare gases used can be suppressed.

[0141] Additionally, in step (d), a silicon hydride gas or a chlorosilane-based gas can be used as the modifying gas to form a silicon (Si) layer on the surface of the membrane. As the silicon hydride gas, one gas selected from silane (SiH4), disilane (Si2H6), and trisilane (Si3H8), or a mixture containing at least one of these gases, can be used. As the chlorosilane-based gas, hexachlorodisilane (HCDS) can be used.

[0142] By using the aforementioned gas as a modifying gas to form a silicon (Si) layer on the surface of a film containing metal elements, it is possible to suppress the nitriding of the film caused by nitrogen present outside the processing chamber 201.

[0143] Additionally, in (d), an oxygen-containing (O) gas can be used as the modifying gas to form an oxide layer on the surface of the membrane. The oxygen-containing gas can be one of the following: oxygen (O2), water vapor (H2O), nitric oxide (NO), nitrous oxide (N2O), ozone (O3), a mixture of hydrogen (H2) and oxygen (O2), or a mixture containing at least one of these gases.

[0144] By using the aforementioned gas as a modifying gas to pre-oxidize the surface of the membrane containing metal elements, or by pre-filling the sites on the membrane surface that can bond with nitrogen with oxygen, it is possible to suppress the adsorption (nitriding) of nitrogen present outside the processing chamber 201 on the surface of the membrane.

[0145] Additionally, in (d), a nitrogen-containing gas can be used as the modifying gas to form a nitrided layer on the surface of the membrane. The nitrogen-containing gas can be one of ammonia (NH3), hydrazine (N2H4), diazepine (N2H2), nitrogen (N2), or a mixture containing at least one of these gases.

[0146] Alternatively, the aforementioned gas can be used as the modifying gas instead of natural nitriding to form a fully modified layer (nitrided layer) on the membrane surface. It should be noted that a fully modified layer refers to a state where other elements do not readily bind to the membrane surface. In the case of Mo films, this means forming a MoN layer on the surface. By forming such a layer, the uniformity of each wafer 200 during subsequent removal of the nitrided layer can be improved. The composition of the modified layer formed on each wafer 200 can be homogenized. By homogenizing the composition of the modified layer for each wafer 200, the removal rate of modification due to compositional differences can be suppressed. Furthermore, by forming such a nitrided layer, the adsorption of atmospheric oxygen onto the membrane surface can be suppressed. That is, by filling the oxygen-binding sites on the membrane surface with nitrogen, the adsorption of oxygen to the membrane surface can be suppressed.

[0147] Additionally, in step (d), a boron-containing (B) gas can be used as a modifying gas to form a boron-containing layer on the surface of the membrane. The boron-containing gas can be one of diborane (B₂H₆) gas, boron trichloride (BCl₃) gas, or a mixture containing at least one of these gases.

[0148] By using the aforementioned gas as a modifying gas to form a boron-containing layer on the surface of a membrane containing metal elements, the adsorption of nitrogen and oxygen present outside the processing chamber 201 can be suppressed.

[0149] Additionally, in step (d), a fluorine-containing (F) gas can be used as a modifying gas to form a fluorine-containing layer on the surface of the membrane. The fluorine-containing gas can be one of the following: tungsten hexafluoride (WF6) gas, fluorine (F2) gas, nitrogen trifluoride (NF3) gas, chlorine trifluoride (ClF3) gas, hydrogen fluoride (HF) gas, or a mixture containing at least one of these gases.

[0150] By using the aforementioned gas as a modifying gas to fluorinate the surface of a membrane containing metal elements, it is possible to suppress the oxidation and nitriding of the membrane caused by oxygen and nitrogen present outside the processing chamber 201.

[0151] Additionally, in step (d), a phosphorus-containing (P) gas can be used as a modifying gas to form a phosphorus-containing (P) layer on the surface of the membrane. The phosphorus-containing gas can be phosphine (PH3) gas or a mixture containing phosphine (PH3) gas.

[0152] By using the aforementioned gas as a modifying gas to form a phosphorus (P) layer on the surface of a membrane containing metal elements, the adsorption and reaction of nitrogen and oxygen present outside the processing chamber 201 can be suppressed.

[0153] Furthermore, in (d), compared to (a) to (c), the temperature setting within the processing chamber 201 can be maintained or decreased. Maintaining the temperature setting within the processing chamber 201 improves manufacturing productivity, but oxidation and nitriding may also occur in the membrane during the membrane modification process. Therefore, in the membrane modification process, it is preferable to form at least one of a Si-containing layer, an oxygen-containing layer, a nitrogen-containing layer, and a phosphorus-containing layer on the surface of the membrane.

[0154] Furthermore, rare gases are preferably used as the carrier gas and purge gas supplied in (a) to (d). This helps to suppress nitriding of the film during film formation and modification.

[0155] <Other Implementation Methods>

[0156] The embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the embodiments described above, and various modifications can be made without departing from its spirit.

[0157] For example, the above embodiment describes a batch substrate processing apparatus that processes multiple substrates at a time as a vertical device for film formation. However, this disclosure is not limited to this, and it can also be appropriately applied when a monolithic substrate processing apparatus that processes one or more substrates at a time is used for film formation.

[0158] Furthermore, the substrate processing apparatus of the embodiments described in this disclosure is applicable not only to semiconductor manufacturing apparatuses for manufacturing semiconductors, but also to apparatuses for processing glass substrates, such as LCD devices. The substrate processing includes, for example, CVD, PVD, forming oxide films, forming nitride films, forming metal-containing films, annealing, oxidation, nitriding, and diffusion processes. It is also applicable to various substrate processing apparatuses such as exposure apparatuses, coating apparatuses, drying apparatuses, and heating apparatuses.

Claims

1. A substrate processing method, which has the following characteristics: (a) A process of supplying a gas containing a metal element to a substrate contained in a processing container; (b) The process of supplying reducing gas to the substrate; (c) A process of forming a film containing a metal element on the substrate by performing (a) and (b) a specified number of times; (d) After (c), a process of supplying a modified gas to the membrane to form a layer containing the elements contained in the modified gas on the surface of the membrane; (e) After (d), the process of moving the substrate from the processing container to the transfer chamber by filling the processing container and the transfer chamber adjacent to the processing container with a rare gas atmosphere; (f) The process of forming an atmosphere of inactive gases other than rare gases in the processing container and transfer chamber, prior to (a), of transferring the substrate from the transfer chamber into the processing container; and (g) Between (f) and (e), a process of replacing the atmosphere of inactive gases other than rare gases in the transfer chamber with a rare gas atmosphere.

2. The method of claim 1, wherein, (e) The process is carried out while maintaining the temperature settings within the processing container described in (c) and (d).

3. The method of claim 1, wherein, In (d), a silicon-containing layer is formed on the surface of the membrane using either a silicon-containing gas or a chlorosilane-based gas as the modifying gas.

4. The method of claim 1, wherein, In (d), an oxygen-containing gas is used as the modified gas to form an oxide layer on the surface of the membrane.

5. The method of claim 1, wherein, In (d), a nitrogen-containing gas is used as the modifying gas to form a nitrided layer on the surface of the membrane.

6. The method of claim 1, wherein, In (d), a boron-containing gas is used as the modified gas to form a boron-containing layer on the surface of the membrane.

7. The method of claim 1, wherein, In (d), a fluorine-containing gas is used as the modifying gas to form a fluorine-containing layer on the surface of the membrane.

8. The method of claim 1, wherein, In (d), a phosphorus-containing gas is used as the modified gas to form a phosphorus-containing layer on the surface of the membrane.

9. The method of claim 1, wherein, In (d), compared to (a) to (c), the temperature setting inside the processing container is maintained or the temperature setting inside the processing container is reduced.

10. The method of claim 1, wherein, Rare gases are used as the carrier gas and purge gas supplied in (a) to (d).

11. A computer-readable recording medium containing a program that enables a substrate processing apparatus to perform the following steps using a computer: (a) The step of supplying a gas containing a metal element to a substrate contained within a processing container; (b) The step of supplying reducing gas to the substrate; (c) The step of forming a film containing a metal element on the substrate by performing (a) and (b) a specified number of times; (d) After (c), the step of supplying a modified gas to the membrane to form a layer containing the elements contained in the modified gas on the surface of the membrane; (e) After (d), the substrate is moved from the processing container to the transfer chamber by filling the processing container and the transfer chamber with a rare gas atmosphere. (f) The step of forming an atmosphere of inactive gases other than rare gases in the processing container and the transfer chamber, prior to (a) the step of transferring the substrate from the transfer chamber to the processing container; and (g) Between (f) and (e), the step of replacing the atmosphere of inactive gases other than rare gases in the transfer chamber with a rare gas atmosphere.

12. A substrate processing apparatus, comprising: Handling containers; A transfer chamber adjacent to the processing container; The conveying system is used to convey substrates; A gas supply system containing metal elements supplies a gas containing metal elements into the processing container; A reducing gas supply system that supplies reducing gas into the processing container; A modified gas supply system that supplies modified gas into the processing container; A rare gas supply system that supplies rare gas into the processing container and the transfer chamber; An exhaust system that vents air from the processing container and the transfer chamber; and The control unit is configured to control the conveying system, the metal-containing gas supply system, the reducing gas supply system, the modified gas supply system, the rare gas supply system, and the exhaust system in a manner that allows for the execution of each step of claim 1.

13. A method for manufacturing a semiconductor device, comprising: (a) A process of supplying a gas containing a metal element to a substrate contained in a processing container; (b) The process of supplying reducing gas to the substrate; (c) A process of forming a film containing a metal element on the substrate by performing (a) and (b) a specified number of times; (d) After (c), a process of supplying a modified gas to the membrane to form a layer containing the elements contained in the modified gas on the surface of the membrane; (e) After (d), the process of moving the substrate from the processing container to the transfer chamber by filling the processing container and the transfer chamber adjacent to the processing container with a rare gas atmosphere; (f) The process of forming an atmosphere of inactive gases other than rare gases in the processing container and transfer chamber, prior to (a), of transferring the substrate from the transfer chamber into the processing container; and (g) Between (f) and (e), a process of replacing the atmosphere of inactive gases other than rare gases in the transfer chamber with a rare gas atmosphere.

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