JP6652652B2 - Semiconductor device manufacturing method and substrate processing apparatus - Google Patents

Description

  The present invention relates to a method for manufacturing a semiconductor device.

  As one step of a manufacturing process of a semiconductor device (device), a substrate process performed by supplying a processing gas to a substrate in a processing chamber, for example, a film formation process may be performed.

JP 2014-187104 A

  With high integration and high performance of LSI (Large-Scale Integration) logic and memory, a wiring process in a back-end process requires a metal film to be formed in a portion having a smaller opening than in the past. Further, since a low resistivity is required in the wiring process, a tungsten (W) -containing film is often used as the metal film, but since the adhesion between the Si-based insulating film and the W-containing film is low, A barrier metal such as a tantalum nitride film (TaN film) or a titanium nitride film (TiN film) is often inserted at the interface between the Si-based insulating film and the W-containing film. However, the TaN film and the TiN film have problems such as high resistivity and easy oxidation.

  An object of the present invention is to improve the adhesion between an insulating film and a W-containing film as a metal film when forming a metal film on an insulating film in a wiring step, and to maintain a low wiring resistance.

  According to one embodiment of the present invention, (A) a first reducing gas including a borane-based gas or a silane-based gas is supplied to a substrate having an insulating film formed on a surface thereof to reduce the insulating film. And (B) forming a metal nitride film containing a metal element directly on the reduced insulating film, wherein the first reducing gas is supplied to and exhausted from the substrate. A step of supplying and exhausting a metal-containing gas containing the metal element to the substrate, and a step of supplying and exhausting a nitriding gas to the substrate in order, one or more times; C) a step of forming a first metal layer directly on the metal nitride film, comprising: supplying and exhausting the first reducing gas to the substrate; Supplying and exhausting the metal-containing gas; and And (D) a step of forming a second metal layer directly on the first metal layer, wherein a second reduction of the substrate, which is different from the first reduction gas, is performed. Supplying a gas and the metal-containing gas at the same time.

  By irradiating a substrate on which the insulating film is formed with a reducing gas to reduce the insulating film before forming the W-containing film, it is possible to improve the adhesion between the insulating film and the W-containing film. Become. Further, since a W-containing film, which is a metal film, is formed without using a barrier metal film such as a TaN film or a TiN film having a high resistivity, a low wiring resistance can be maintained.

FIG. 1 is a diagram showing an example of a preferred flow for creating a sample. 2A and 2B are schematic cross-sectional views of the sample prepared according to the flow shown in FIG. 1, wherein FIG. 2A shows the application of a photoresist (PR) on an SiO film, FIG. 2B shows exposure and development, and FIG. Are masked with a resist, the W buried portion is opened by etching, (d) the resist is removed and washed, (e) the SiO film is reduced to form a barrier metal / wiring film, and (f) W is removed by CMP. 3 is a schematic cross-sectional view in each process in which the steps are performed in order. FIG. 3 is a schematic configuration diagram of a processing furnace of a substrate processing apparatus suitably used in an embodiment of the present invention, and is a diagram showing a processing furnace portion in a longitudinal sectional view. FIG. 4 is a schematic cross-sectional view taken along line AA of FIG. FIG. 5 is a block diagram illustrating a configuration of a controller included in the substrate processing apparatus illustrated in FIG. FIG. 6 is a diagram showing a suitable gas supply timing in the film forming process according to the embodiment of the present invention.

  When forming a W film for a contact plug in a logic or memory back-end process as one process of a semiconductor device, the following process can be considered. First, a SiO film, for example, is formed as an interlayer insulating film on a substrate. In order to form a W film as a wiring in the SiO film, a photoresist (PR) is applied on the SiO film, and exposure and development are performed. , W are masked with a resist except for the region where W is to be buried, and the W buried portion is opened by etching. After that, a barrier metal / wiring film forming process is performed through resist removal and cleaning. It is considered that a tungsten nitride film (WN film) is formed as a barrier metal and a W film is formed as a wiring film. However, since the adhesion between the Si-based insulating film and the W-containing film is low, a barrier metal such as a tantalum nitride film (TaN film) or a titanium nitride film (TiN film) has conventionally been used to form the Si-based insulating film and the W-containing film. In some cases.

  The present inventors have conducted intensive research and found that organic materials and the like adhere to the Si-based insulating film, which is an interlayer insulating film, because the adhesion between the Si-based insulating film and the W-containing film is low. It has been found that the adhesiveness of the film is reduced to form the containing film. Therefore, as shown in FIGS. 1 and 2, in a series of processes for forming a W film as a wiring in the above-described SiO film, a substrate on which a Si-based insulating film is formed before forming a W-containing film. On the other hand, a reducing gas such as a borane-based gas or a silane-based gas was irradiated. That is, a photoresist (PR) is applied on the SiO film (FIG. 2A), exposed and developed (FIG. 2B), a region other than a region where W is embedded is masked with a resist, and W is etched by etching. The buried portion is opened (FIG. 2C). Thereafter, after removing and washing the resist (FIG. 2D), the SiO film is reduced to form a barrier metal / wiring film forming step (FIG. 2E), and W is removed by CMP (FIG. 2E). 2 (f)), a sample was prepared. FIG. 2E is a diagram illustrating a cross section of the manufactured sample. Before the formation of the W-containing film, the substrate on which the Si-based insulating film is formed is irradiated with a reducing gas such as a borane-based gas or a silane-based gas, so that the substrate adheres to the surface of the Si-based insulating film. It has been devised to improve the adhesion between the Si-based insulating film and the W-containing film by removing the organic substances and the like and attaching boron (B) or silicon (Si) or the like. The details will be described below.

<One Embodiment of the Present Invention> Hereinafter, one embodiment of the present invention will be described with reference to FIGS. The substrate processing apparatus 10 is configured as an example of an apparatus used in a semiconductor device manufacturing process.

(1) Configuration of Substrate Processing Apparatus 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 has a cylindrical shape, and is vertically installed by being supported by a heater base (not shown) as a holding plate.

  Inside the heater 207, an outer tube 203 constituting a reaction vessel (processing vessel) concentrically with the heater 207 is provided. The outer tube 203 is made of a heat-resistant material such as quartz (SiO) or silicon carbide (SiC), and is formed in a cylindrical shape with an upper end closed and a lower end opened. Below the outer tube 203, a manifold (inlet flange) 209 is disposed concentrically with the outer tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), for example, and is formed in a cylindrical shape having upper and lower ends opened. An O-ring 220a as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. When the manifold 209 is supported by the heater base, the outer tube 203 is vertically installed.

  Inside the outer tube 203, an inner tube 204 constituting a reaction vessel is provided. The inner tube 204 is made of a heat-resistant material such as quartz (SiO) or silicon carbide (SiC), and is formed in a cylindrical shape having an upper end closed and a lower end opened. A processing container (reaction container) mainly includes the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing container (inside the inner tube 204).

  The processing chamber 201 is configured to be capable of housing wafers 200 as substrates in a state where the wafers 200 are arranged in multiple stages in the vertical direction in a horizontal posture by a boat 217 described later.

  In 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 tube 204. Gas supply pipes 310 and 330 as gas supply lines are connected to the nozzles 410 and 430, respectively. Gas supply pipes 320a and 320b as gas supply lines are connected to the nozzle 420. As described above, the substrate processing apparatus 10 is provided with the three nozzles 410, 420, and 430 and the four gas supply pipes 310, 320a, 320b, and 330. Is configured to be supplied. However, the processing furnace 202 of the present embodiment is not limited to the above-described embodiment.

  The gas supply pipes 310, 320a, 320b, and 330 are provided with mass flow controllers (MFCs) 312, 322a, 320b, and 332, respectively, which are flow controllers (flow controllers) in order from the upstream side. The gas supply pipes 310, 320, and 330 are provided with valves 314, 324a, 320b, and 334, respectively, which are on-off valves. Gas supply pipes 510, 520, and 530 for supplying inert gas are connected to the gas supply pipes 310, 320a, 320b, and 330 downstream of the valves 314, 324a, 320b, and 334, respectively. The gas supply pipes 510, 520, and 530 are provided with MFCs 512, 522, and 532 that are flow controllers (flow control units) and valves 514, 524, and 534 that are on-off valves, respectively, in order from the upstream side.

  Nozzles 410 and 430 are connected to the distal ends of the gas supply pipes 310 and 330, respectively. The nozzle 420 is connected and connected after the gas supply pipe 320a and the gas supply pipe 320b are connected. The nozzles 410, 420, and 430 are configured as L-shaped nozzles, and the horizontal portion is provided to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, and 430 are provided inside a channel-shaped (groove-shaped) preliminary chamber 201a that protrudes radially outward of the inner tube 204 and extends in the vertical direction. In the preliminary chamber 201 a, it is provided upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

  The nozzles 410, 420, and 430 are provided so as to extend from a lower region of the processing chamber 201 to an upper region of the processing chamber 201, and a plurality of gas supply holes 410 a, 420 a, and 430 a are provided at positions facing the wafer 200. Is provided. Thus, the processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, respectively. A plurality of the gas supply holes 410a, 420a, and 430a are provided from the lower portion to the upper portion of the inner tube 204, have the same opening area, and are provided at the same opening pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-described embodiments. For example, the opening area may be gradually increased from the lower part to the upper part of the inner tube 204. Thereby, the flow rate of the gas supplied from the gas supply holes 410a, 420a, and 430a can be made more uniform.

  A plurality of gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 are provided at positions from the lower part to the upper part of the boat 217 described later. Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410 a, 420 a, and 430 a of the nozzles 410, 420, and 430 is stored in the wafer 200 stored from the lower part to the upper part of the boat 217, that is, in the boat 217. The wafer 200 is supplied to the entire area of the wafer 200. The nozzles 410, 420, and 430 may be provided so as to extend from the lower region to the upper region of the processing chamber 201, but are preferably provided to extend near the ceiling of the boat 217.

From the gas supply pipe 310, a first reducing gas is supplied as a processing gas into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410. As the first reducing gas, for example, a borane-based gas that is a B-containing gas containing boron (B) or a silane-based gas that is a silicon-containing gas containing silicon (Si) is used. In this embodiment, an example in which diborane (B ₂ H ₆ ) is used as a borane-based gas will be described.

From the gas supply pipe 320a, a reaction gas is supplied as a processing gas into the processing chamber 201 via the MFC 322a, the valve 324a, and the nozzle 420. As the reaction gas, for example, ammonia (NH ₃ ), which is an N-containing gas containing nitrogen (N), is used as a nitriding gas.

A second reducing gas different from the first reducing gas is supplied from the gas supply pipe 320b into the processing chamber 201 via the MFC 322b, the valve 324b, and the nozzle 420. As the second reducing gas, for example, hydrogen (H ₂ ) which is an H-containing gas containing a hydrogen atom (H) is used.

From the gas supply pipe 330, as a processing gas, a fluorine-containing metal source gas containing a metal element and fluorine (F) (also referred to as a metal-containing fluoride gas) is supplied into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 430. Supplied to As a raw material, tungsten hexafluoride (WF ₆ ) containing tungsten (W) as a metal element is used.

From the gas supply pipes 510, 520, and 530, for example, a nitrogen (N ₂ ) gas is supplied as an inert gas through the MFC 512, 522, 532, the valves 514, 524, 534, and the nozzles 410, 420, 430, respectively. 201. Hereinafter, an example in which N ₂ gas is used as the inert gas will be described. As the inert gas, for example, an argon (Ar) gas, a helium (He) gas, a neon (Ne) gas may be used in addition to the N ₂ gas. And a rare gas such as xenon (Xe) gas.

  A processing gas supply system is mainly configured by gas supply pipes 310, 320a, 320b, 330, MFCs 312, 322a, 322b, 332, valves 314, 324a, 324b, 334, and nozzles 410, 420, 430. , 420 and 430 may be considered as the processing gas supply system. The processing gas supply system may be simply referred to as a gas supply system. When the first reducing gas flows from the gas supply pipe 310, a first reducing gas supply system mainly includes the gas supply pipe 310, the MFC 312, and the valve 314, and the nozzle 410 is connected to the first reducing gas supply system. May be included. When a borane-based gas is used as the first reducing gas, the first reducing gas supply system may be referred to as a borane-based gas. When a silane-based gas is used as the second reducing gas, the first reducing gas supply system may be used. The system may be referred to as a silane-based gas supply system. When the reaction gas flows from the gas supply pipe 320a, a reaction gas supply system mainly includes the gas supply pipe 320a, the MFC 322a, and the valve 324a. However, the nozzle 320 may be included in the reaction gas supply system. When a nitriding gas flows as a reaction gas, the reaction gas supply system may be referred to as a nitriding gas supply system. When the second reducing gas flows from the gas supply pipe 320b, a second reducing gas supply system is mainly configured by the gas supply pipe 320b, the MFC 322b, and the valve 324b. May be included. When an H-containing gas flows as the second reducing gas, the second reducing gas supply system may be referred to as an H-containing gas supply system. When the source gas flows from the gas supply pipe 330, a source gas supply system mainly includes the gas supply pipe 330, the MFC 332, and the valve 334. However, the nozzle 430 may be included in the source gas supply system. When a metal-containing source gas is used as the source gas, the source gas supply system may be referred to as a metal-containing source gas supply system. In addition, an inert gas supply system is mainly configured by the gas supply pipes 510, 520, 530, the MFCs 512, 522, 532, and the valves 514, 524, 534. The inert gas supply system may be referred to as a purge gas supply system, a dilution gas supply system, or a carrier gas supply system.

  The gas supply method according to the present embodiment is performed in the preparatory chamber 201 a in an annular vertically long space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200, that is, in the cylindrical space. The gas is conveyed via the nozzles 410, 420, 430 arranged in the. Then, gas is ejected into the inner tube 204 from a plurality of gas supply holes 410a, 420a, 430a provided at positions of the nozzles 410, 420, 430 facing the wafer. More specifically, the source gas or the like is ejected in a direction parallel to the surface of the wafer 200, that is, in a horizontal direction by the gas supply hole 410a of the nozzle 410, the gas supply hole 420a of the nozzle 420, and the gas supply hole 430a of the nozzle 430. ing.

  The exhaust hole (exhaust port) 204a is a through hole formed at a position facing the nozzles 410, 420, and 430 on the side wall of the inner tube 204, that is, at a position 180 degrees opposite to the preliminary chamber 201a. , Are slit-shaped through holes elongated in the vertical direction. Therefore, 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, that is, the remaining gas (residual gas) is discharged to the exhaust hole 204a. Through the inner tube 204 and the outer tube 203, and flows into an exhaust passage 206 formed by a gap formed between the inner tube 204 and the outer tube 203. Then, the gas flowing into the exhaust path 206 flows into the exhaust pipe 231 and is discharged out of the processing furnace 202.

  The exhaust hole 204a is provided at a position facing the plurality of wafers 200 (preferably, at a position facing the upper part to the lower part of the boat 217), and the gas supply holes 410a, 420a, and 430a are used to discharge the wafer 200 in the processing chamber 201. The gas supplied to the vicinity flows in the horizontal direction, that is, in the direction parallel to the surface of the wafer 200, and then flows into the exhaust passage 206 through the exhaust hole 204a. That is, the gas remaining in the processing chamber 201 is exhausted in parallel with the main surface of the wafer 200 through the exhaust hole 204a. In addition, the exhaust hole 204a is not limited to the case where it is configured as a slit-shaped through hole, and may be configured with a plurality of holes.

  An exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is provided in the manifold 209. The exhaust pipe 231 has a pressure sensor 245 as a pressure detector (pressure detecting unit) for detecting the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump as a vacuum exhaust device, in order from the upstream side. 246 are connected. The APC valve 243 can open and close the valve while the vacuum pump 246 is operating, thereby performing evacuation of the processing chamber 201 and stopping the evacuation. Further, the APC valve 243 operates with the vacuum pump 246 operating. The pressure in the processing chamber 201 can be adjusted by adjusting the opening degree. An exhaust system, that is, an exhaust line is mainly configured by the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. Note that the vacuum pump 246 may be included in the exhaust system.

  Below the manifold 209, a seal cap 219 is provided as a furnace port lid capable of hermetically closing the lower end opening of the manifold 209. The seal cap 219 is configured to contact the lower end of the manifold 209 from below in the vertical direction. The seal cap 219 is made of a metal such as SUS, for example, and is formed in a disk shape. On the upper surface of the seal cap 219, an O-ring 220b is provided as a seal member that contacts the lower end of the manifold 209. On the opposite side of the processing chamber 201 in the seal cap 219, a rotation mechanism 267 for rotating a boat 217 that stores the wafer 200 is installed. The rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafer 200. The seal cap 219 is configured to be vertically moved up and down by a boat elevator 115 serving as a lifting / lowering mechanism installed vertically outside the outer tube 203. The boat elevator 115 is configured to be able to carry the boat 217 into and out of the processing chamber 201 by moving the seal cap 219 up and down. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217 and the wafers 200 stored in the boat 217 into and out of the processing chamber 201.

  The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers in a horizontal posture and in a vertical direction with the centers aligned with each other, that is, to support the wafers 200 in multiple stages. It is configured to be arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. Under the boat 217, a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages (not shown) in a horizontal posture. This configuration makes it difficult for heat from the heater 207 to be transmitted to the seal cap 219 side. However, the present embodiment is not limited to the above-described embodiment. For example, instead of providing the heat insulating plate 218 at the lower part of the boat 217, a heat insulating tube configured as a cylindrical member made of a heat resistant material such as quartz or SiC may be provided.

  As shown in FIG. 2, a temperature sensor 263 as a temperature detector is installed in the inner tube 204, and the amount of electricity supplied to the heater 207 is adjusted based on temperature information detected by the temperature sensor 263. The inside of the processing chamber 201 is configured to have a desired temperature distribution. The temperature sensor 263 is formed in an L shape similarly to the nozzles 410, 420, and 430, and is provided along the inner wall of the inner tube 204.

  As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. Have been. 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 configured as, for example, a touch panel or the like is connected to the controller 121.

  The storage device 121c includes, for example, a flash memory, an HDD (Hard Disk Drive), and the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe describing a procedure and conditions of a semiconductor device manufacturing method described later, and the like are stored in a readable manner. The process recipe is combined so that the controller 121 can execute each step (each step) in a semiconductor device manufacturing method described later and obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, and the like are collectively referred to simply as a program. In this specification, the term “program” may include only a process recipe alone, may include only a control program, or may include a combination of a process recipe and a control program. The RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily stored.

  The I / O port 121d is connected to the MFC 312, 322a, 322b, 332, 512, 522, 532, the valve 314, 324a, 324b, 334, 514, 524, 534, the pressure sensor 245, the APC valve 243, the vacuum pump 246, The heater 207, the temperature sensor 263, the rotation mechanism 267, the boat elevator 115, and the like are connected.

  The CPU 121a is configured to read and execute a control program from the storage device 121c and read a recipe or the like from the storage device 121c in response to an operation command input from the input / output device 122 or the like. The CPU 121a adjusts the flow rates of various gases by the MFCs 312, 322a, 322b, 332, 512, 522, and 532, and opens and closes the valves 314, 324a, 324b, 334, 514, 524, and 534 in accordance with the contents of the read recipe. Operation, opening / closing operation of the APC valve 243, pressure adjustment operation based on the pressure sensor 245 by the APC valve 243, temperature adjustment operation of the heater 207 based on the temperature sensor 263, start and stop of the vacuum pump 246, rotation of the boat 217 by the rotation mechanism 267 And a rotation speed adjusting operation, a raising / lowering operation of the boat 217 by the boat elevator 115, an operation of storing the wafer 200 in the boat 217, and the like.

  The controller 121 is stored in an external storage device (for example, a magnetic tape, a magnetic disk such as a flexible disk and a hard disk, an optical disk such as a CD and a DVD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory and a memory card). The above-described program can be configured by installing the program in a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively simply referred to as a recording medium. In this specification, the recording medium may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both. The provision of the program to the computer may be performed using communication means such as the Internet or a dedicated line without using the external storage device 123.

(2) Substrate Processing Step (Film Forming Step) An example of the present embodiment will be described with reference to FIG. 6 as one step of a semiconductor device (device) manufacturing process. Each step described below is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operation of each unit constituting the substrate processing apparatus 10 is controlled by the controller 121.

In the substrate processing step (semiconductor device manufacturing step) according to the present embodiment, (A) a step of supplying the B ₂ H ₆ gas to the wafer 200 having the SiO film formed on the surface to reduce the SiO film; (B) a step of forming a WN film containing a W element directly on the reduced SiO film, the step of supplying and exhausting a B ₂ H ₆ gas to the wafer 200; On the other hand, a step of supplying and exhausting a WF ₆ gas containing a W element, a step of supplying and exhausting an NH ₃ gas to and from the wafer 200 are sequentially performed at least once, and (C) on the WN film. Forming a first W layer directly, supplying and exhausting a B ₂ H ₆ gas to the wafer 200, and supplying and exhausting a WF ₆ gas to the wafer 200 And (c) sequentially performing one or more times of: A step of forming a second W layer directly on the core layer, a step of simultaneously supplying H ₂ gas and WF ₆ gas to the wafer 200;

  In this specification, the term “wafer” means “wafer itself” or “laminate (assembly) of a wafer and predetermined layers and films formed on the surface thereof”. (That is, a wafer including predetermined layers and films formed on the surface). In this specification, the term “surface of the wafer” is used to mean “the surface (exposed surface) of the wafer itself” or “the surface of a predetermined layer or film formed on the wafer. That is, it may mean "the outermost surface of the wafer as a laminate". Note that the use of the word “substrate” in this specification is synonymous with the use of the word “wafer”.

(Wafer Loading) A plurality of wafers 200 (exposed) on which a silicon oxide film (SiO film) as an insulating film is formed (exposed) on the outermost surface are loaded (boat loaded) into the processing chamber 201. Specifically, when a plurality of wafers 200 are loaded on the boat 217 (wafer charging), the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 as shown in FIG. And is carried into the processing chamber 201. In this state, the seal cap 219 closes the lower end opening of the reaction tube 203 via the O-ring 220.

(Pressure Adjustment and Temperature Adjustment) The inside of the processing chamber 201 is evacuated by the vacuum pump 246 to a desired pressure (degree of vacuum). 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 based on the measured pressure information (pressure adjustment). The vacuum pump 246 keeps operating at least until the processing on the wafer 200 is completed. Further, the inside of the processing chamber 201 is heated by the heater 207 so as to reach a desired temperature. At this time, the amount of power to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment). The heating of the inside of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed.

[B ₂ H ₆ Preflow Step] Subsequently, a step of reducing the SiO film formed on the wafer 200 is performed.

The valve 314 is opened, and B ₂ H ₆ gas, which is the first reducing gas, flows into the gas supply pipe 310. The flow rate of the B ₂ H ₆ gas is adjusted by the MFC 312, supplied to the processing chamber 201 from the gas supply hole 410 a of the nozzle 410, and exhausted from the exhaust pipe 231. At this time, the B ₂ H ₆ gas is supplied to the wafer 200 having the insulating film formed on the surface. At this time, the valve 514 is opened at the same time, and an inert gas such as N ₂ gas flows into the gas supply pipe 510. The flow rate of the N ₂ gas flowing through the gas supply pipe 510 is adjusted by the MFC 512, supplied to the processing chamber 201 together with the B ₂ H ₆ gas, and exhausted from the exhaust pipe 231. At this time, in order to prevent the B2H6 gas from entering the nozzle 420 and 430, opening the valve 524 and 534 to flow the _{N 2} gas into the gas supply pipe 520. The N ₂ gas is supplied into the processing chamber 201 via the gas supply pipes 320a, 320b, 330 and the nozzles 420, 430, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted to set the pressure in the processing chamber 201 to a pressure within a range of, for example, 1 to 3990 Pa. The supply flow rate of B ₂ H ₆ controlled by the MFC 312 is, for example, a flow rate within a range of 0.01 to 20 slm. The supply flow rate of the N ₂ gas controlled by the MFCs 512, 522, and 532 is, for example, a flow rate within a range of 0.1 to 30 slm. The time for supplying the B ₂ H ₆ gas to the wafer 200 is, for example, a time within a range of 0.01 to 60 seconds. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 falls within a range of, for example, 100 to 350 ° C. By supplying the B ₂ H ₆ gas, the SiO film formed on the wafer 200 is reduced. By removing organic substances present on the surface of the SiO film formed on the wafer 200 and attaching B, the adhesion between the SiO film and the WN film to be formed next can be improved.

After the insulating film is reduced, the valve 314 is closed, and the supply of the B ₂ H ₆ gas is stopped. At this time, a film including the reduced SiO film is exposed on the outermost surface of the wafer 200. That is, the surface of the wafer 200 is reduced. At this time, the B ₂ H ₆ gas may be used without plasma excitation without using plasma. By performing preflow using non-plasma, the SiO film can be reduced without causing plasma damage to the SiO film.

[Residual Gas Removal Step] After the supply of the B ₂ H ₆ gas is stopped, the inside of the processing chamber 201 is evacuated by the vacuum pump 246 while the APC valve 243 of the exhaust pipe 231 is kept open. The unreacted B ₂ H ₆ gas that has contributed to the reduction of the SiO film is removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of the N ₂ gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, and can enhance the effect of eliminating the B ₂ H ₆ gas remaining in the processing chamber 201 and remaining after contributing to the reduction of the SiO film from the processing chamber 201.

[Step of Forming Tungsten Nitride Film (WN Film)] Subsequently, a step of forming a WN film, which is a metal nitride film, on the wafer 200 on which the reduced SiO film is exposed is performed. That is, the WN film is formed directly on the SiO film. The WN film functions as a barrier metal film.

(B ₂ H ₆ gas supply step 11) The valve 314 is opened, and the B ₂ H ₆ gas, which is a B-containing gas, flows as the first reducing gas into the gas supply pipe 310. The flow rate of the B ₂ H ₆ gas is adjusted by the MFC 312, supplied to the processing chamber 201 from the gas supply hole 410 a of the nozzle 410, and exhausted from the exhaust pipe 231. At this time, the B ₂ H ₆ gas is supplied to the wafer 200. At this time, the valve 514 is opened at the same time, and N ₂ gas flows into the gas supply pipe 510. The flow rate of the N ₂ gas flowing through the gas supply pipe 510 is adjusted by the MFC 512. The N ₂ gas is supplied into the processing chamber 201 together with the B ₂ H ₆ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent the B ₂ H ₆ gas from entering the nozzles 420 and 430, the valves 524 and 534 are opened, and the N ₂ gas flows into the gas supply pipes 520 and 530. The N ₂ gas is supplied into the processing chamber 201 via the gas supply pipes 320a, 320b, 330 and the nozzles 420, 430, and is exhausted from the exhaust pipe 231.

When flowing the B ₂ H ₆ gas, the APC valve 243 is adjusted to set the pressure in the processing chamber 201 to a pressure within a range of, for example, 10 to 3990 Pa. The supply flow rate of the B ₂ H ₆ gas controlled by the MFC 312 is, for example, a flow rate within a range of 0.01 to 20 slm. The supply flow rate of the N ₂ gas controlled by the MFCs 512, 522, and 532 is, for example, a flow rate in a range of 0.0.01 to 30 slm. The time for supplying the B ₂ H ₆ gas to the wafer 200 is, for example, a time within a range of 0.01 to 60 seconds. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 falls within a range of, for example, 100 to 350 ° C. The gases flowing into the processing chamber 201 are only the B ₂ H ₆ gas and the N ₂ gas, and the outermost surface of the wafer 200 is reduced by the supply of the B ₂ H ₆ gas.

(Residual Gas Removal Step 12) After supplying the supply of the B ₂ H ₆ gas for a predetermined time, the valve 314 is closed to stop the supply of the B ₂ H ₆ gas. At this time, while the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246 and the B ₂ H ₆ gas remaining in the processing chamber 201 remains unreacted or contributes to reduction. Is removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of the N ₂ gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, and can enhance the effect of removing the unreacted or remaining B ₂ H ₆ gas remaining in the processing chamber 201 from the processing chamber 201.

(WF ₆ Gas Supply Step 13) The valve 334 is opened, and the WF ₆ gas, which is a raw material gas, flows into the gas supply pipe 330. The flow rate of the WF ₆ gas is adjusted by the MFC 332, supplied to the processing chamber 201 from the gas supply hole 430 a of the nozzle 430, and exhausted from the exhaust pipe 231. At this time, the WF ₆ gas is supplied to the wafer 200. At this time, the valve 534 is opened at the same time, and an inert gas such as N ₂ gas flows into the gas supply pipe 530. The flow rate of the N ₂ gas flowing through the gas supply pipe 530 is adjusted by the MFC 532, supplied to the processing chamber 201 together with the WF ₆ gas, and exhausted from the exhaust pipe 231. At this time, in order to prevent the WF ₆ gas from entering the nozzles 410 and 420, the valves 514 and 524 are opened, and the N ₂ gas flows through the gas supply pipes 510 and 520. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 310, 320a, 320b and the nozzles 410, 420, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted to set the pressure in the processing chamber 201 to a pressure within a range of, for example, 0.1 to 6650 Pa. The supply flow rate of the WF ₆ gas controlled by the MFC 332 is, for example, a flow rate in a range of 0.01 to 10 slm. The supply flow rate of the N ₂ gas controlled by the MFCs 512, 522, and 532 is, for example, a flow rate within a range of 0.1 to 30 slm. The time for supplying the WF ₆ gas to the wafer 200 is, for example, a time within a range of 0.01 to 600 seconds. At this time, the temperature of the heater 207 is set to a temperature at which the temperature of the wafer 200 becomes, for example, the same as that in step 11. At this time, the gases flowing into the processing chamber 201 are only the WF ₆ gas and the N ₂ gas. By supplying the WF ₆ gas, a W-containing layer having a thickness of, for example, less than one atomic layer to several atomic layers is formed on the wafer 200.

(Residual Gas Removal Step 14) After the W-containing layer and the like are formed, the valve 334 is closed, and the supply of the WF ₆ gas is stopped. Then, the WF ₆ gas remaining in the processing chamber 201 and remaining unreacted or having contributed to the formation of the W-containing layer is removed (removed) from the processing chamber 201 by the same processing procedure as in step 12.

(NH ₃ gas supply step 15) After removing the residual gas in the processing chamber 201, the valve 324a is opened, and NH ₃ gas, which is an N-containing gas, is supplied as a reaction gas into the gas supply pipe 320a. The flow rate of the NH ₃ gas is adjusted by the MFC 322 a, supplied to the processing chamber 201 through the gas supply hole 420 a of the nozzle 420, and exhausted from the exhaust pipe 231. At this time, the NH ₃ gas is supplied to the wafer 200. At this time, the valve 524 is simultaneously opened, and the N ₂ gas flows into the gas supply pipe 520. The flow rate of the N ₂ gas flowing through the gas supply pipe 520 is adjusted by the MFC 522. The N ₂ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent the NH ₃ gas from entering the nozzles 410 and 430, the valves 514 and 534 are opened, and the N ₂ gas flows through the gas supply pipes 510 and 530. The N ₂ gas is supplied into 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.

When flowing the NH ₃ gas, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 0.1 to 6650 Pa. The supply flow rate of the NH ₃ gas controlled by the MFC 322a is, for example, a flow rate within a range of 0.1 to 20 slm. The supply flow rate of the N ₂ gas controlled by the MFCs 512, 522, and 532 is, for example, a flow rate within a range of 0.1 to 30 slm. The time for supplying the NH ₃ gas to the wafer 200 is, for example, a time within a range of 0.01 to 30 seconds. At this time, the temperature of the heater 207 is set to the same temperature as in step 11.

At this time, the gas flowing into the processing chamber 201 is only the NH ₃ gas and the N ₂ gas. The NH ₃ gas undergoes a substitution reaction with at least a part of the W-containing layer formed on the wafer 200 in Step 13. At the time of the substitution reaction, W contained in the W-containing layer and N contained in the NH ₃ gas are combined to form a WN layer containing W and N on the wafer 200.

(Residual Gas Removal Step 16) After the formation of the WN layer, the valve 324a is closed, and the supply of the NH ₃ gas is stopped. Then, according to the same processing procedure as in step 12, the NH ₃ gas or reaction by-product remaining in the processing chamber 201 and remaining after the reaction has contributed to the formation of the WN layer is eliminated (removed) from the processing chamber 201.

(Execution of a predetermined number of times) A cycle of sequentially performing the above steps 11 to 16 is performed at least once (a predetermined number of times (n times), so that a barrier metal having a predetermined thickness (for example, 0.1 to 3 nm) is formed on the wafer 200. A WN film, which is a metal nitride film, is preferably formed by repeating the above-described cycle a plurality of times, in which case the B ₂ H ₆ gas and the WF ₆ gas are mixed with each other. It is supplied to the wafer 200 alternately (in a time-sharing manner) so as not to be performed.

[Tungsten (W) Nucleation Layer Forming Step (Nucation W Deposition)] Subsequently, a step of forming a W nucleation layer, which is a metal nucleation layer, on the wafer 200 on which the WN film is formed is executed. That is, the W nucleus layer is formed directly on the WN layer.

(B ₂ H ₆ gas supply step 21) B ₂ H ₆ gas is flown into the processing chamber 201 under the same processing procedure and processing conditions as those in step 11. The gases flowing into the processing chamber 201 are only the B ₂ H ₆ gas and the N ₂ gas, and the outermost surface of the wafer 200 is reduced by the supply of the B ₂ H ₆ gas.

(Residual Gas Removal Step 22) After supplying the B ₂ H ₆ gas for a predetermined time, the valve 324a is closed, and the supply of the B ₂ H ₆ gas is stopped. Then, the B ₂ H ₆ gas remaining in the processing chamber 201 and remaining unreacted or contributing to the reduction is eliminated (removed) from the processing chamber 201 in the same processing procedure as in step 12.

(WF ₆ Gas Supply Step 23) The WF ₆ gas is flown into the processing chamber 201 under the same processing procedure and processing conditions as those in Step 13. At this time, the gases flowing into the processing chamber 201 are only the WF ₆ gas and the N ₂ gas. By supplying the WF ₆ gas, a W-containing layer having a thickness of, for example, less than one atomic layer to several atomic layers is formed on the wafer 200.

(Residual Gas Removal Step 24) After the W-containing layer and the like are formed, the valve 334 is closed, and the supply of the WF ₆ gas is stopped. Then, the WF ₆ gas remaining in the processing chamber 201 and remaining after it has contributed to the formation of the W-containing layer is removed from the processing chamber 201 by the same processing procedure as in step S14.

(Execution of a predetermined number of times) A cycle of sequentially performing the above-described steps 21 to 24 is performed at least once (a predetermined number of times (n times), so that a W nucleus having a predetermined thickness (for example, 0.5 to 2 nm) is formed on the wafer 200. Forming a W-containing layer as a layer, the above-described cycle is preferably repeated a plurality of times, and thus, in the case of forming a W nucleus layer, the B ₂ H ₆ gas and the WF ₆ gas are not mixed with each other ( It is alternately supplied to the wafer 200 (in a time-division manner) to the wafer 200. The W nucleus layer may be referred to as a first metal layer or a first W layer.

[W layer formation step (W deposition)] Subsequently, a step of forming a W layer which is a metal layer with the W nucleus layer as a nucleus is performed. That is, the W layer is formed directly on the W core layer.

The valves 324b and 330 are opened, and H ₂ gas and WF ₆ gas flow into the gas supply pipes 320b and 330, respectively. The H ₂ gas flowing in the gas supply pipe 320b and the WF ₆ gas flowing in the gas supply pipe 330 are flow-adjusted by the MFCs 322b and 330, respectively, and are supplied from the gas supply holes 420a and 430a of the nozzles 420 and 430 to the processing chamber 201, respectively. And exhausted from the exhaust pipe 231. At this time, the H ₂ gas and the WF ₆ gas are supplied to the wafer 200. That is, the surface of the wafer 200 is exposed to the H ₂ gas and the WF ₆ gas. At this time, the valves 514 and 524 are simultaneously opened, and the N ₂ gas flows into the carrier gas supply pipes 510 and 520, respectively. The flow rates of the N ₂ gas flowing through the carrier gas supply pipes 510 and 520 are adjusted by the MFCs 512 and 522, respectively, supplied to the processing chamber 201 together with the H ₂ gas or the WF ₆ gas, and exhausted from the exhaust pipe 231. You. At this time, in order to prevent the H ₂ gas and the WF ₆ gas from entering the nozzle 410, the valve 514 is opened, and the N ₂ gas flows through the carrier gas supply pipe 510. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipe 310 and the nozzle 410, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is appropriately adjusted, and the pressure in the processing chamber 201 is set to, for example, a pressure in the range of 10 to 3990 Pa. The supply flow rate of the H ₂ gas controlled by the MFC 322b is, for example, a flow rate in a range of 100 to 20,000 sccm, and the supply flow rate of the WF ₆ gas controlled by the MFC 330 is, for example, a flow rate in a range of 10 to 1,000 sccm. The supply flow rate of the N ₂ gas controlled by the MFCs 512, 522, and 532 is, for example, a flow rate within a range of 10 to 10000 sccm. The time for supplying the H ₂ gas and the WF ₆ gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within a range of 1 to 1000 seconds. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 falls within a range of, for example, 100 to 600 ° C. The gas flowing into the processing chamber 201 is only the H ₂ gas and the WF ₆ gas, and the supply of the WF ₆ gas causes the W nucleus layer formed on the wafer 200 to have a thickness of, for example, 10 to 30 nm. Is formed. Note that the W layer may be referred to as a second metal layer or a second W layer. The W core layer and the W layer have substantially the same composition.

[Removal of Residual Gas] After the formation of the W layer, the valves 324b and 330 are closed, and the supply of the H ₂ gas and the WF ₆ gas is stopped. At this time, while the APC valve 243 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the WF ₆ gas remaining in the processing chamber 201 remains unreacted or contributes to W layer formation. Is removed from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open, and the supply of the N ₂ gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, and can enhance the effect of removing the WF ₆ gas remaining in the processing chamber 201 after unreacted or contributing to W layer formation from the processing chamber 201.

(After-Purge and Return to Atmospheric Pressure) N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 510, 520, and 530, and exhausted from the exhaust pipe 231. The N ₂ gas acts as a purge gas, whereby the inside of the processing chamber 201 is purged with an inert gas, and gases and by-products remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (after-purging). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (replacement with an inert gas), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

Then, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafer 200 is unloaded (boat unloaded) from the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported by the boat 217. Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharging).

(3) Effects of this embodiment According to this embodiment, one or more effects described below can be obtained. (A) Before a WN film as a W-containing film is formed on a substrate on which an insulating film is formed, a reducing gas such as a borane-based gas or a silane-based gas is irradiated to reduce the surface of the insulating film. Thus, the adhesion between the insulating film and the WN film can be improved. (B) Before the WN film as the W-containing film is formed on the substrate on which the insulating film is formed, the substrate is irradiated with a reducing gas such as a borane-based gas or a silane-based gas, so that the substrate adheres to the surface of the insulating film. By removing the organic substances and the like and attaching B or S), the adhesion between the insulating film and the WN film can be improved. (C) Since the WN film can be directly formed as a barrier metal film on the insulating film formed on the substrate, the wiring resistance is lower than in the case where a TaN film or a TiN film is used as a barrier metal film. Can be maintained (achieved). (D) When forming a W film as a metal wiring, after forming the W nucleus layer, the W nucleus layer is used as a nucleus to form the W layer, so that a W film having good film characteristics can be formed.

In the above-described embodiment, an example in which the B ₂ H ₆ gas is continuously supplied in the B ₂ H ₆ preflow step (that is, an example in which one cycle of the B ₂ H ₆ preflow is performed) has been described. The present invention is not limited to this. For example, the B ₂ H ₆ pre-flow step and the subsequent residual gas removing step may be alternately repeated a plurality of times.

Further, in the above-described embodiment, the example in which the H ₂ gas and the WF ₆ gas are continuously supplied in the W layer forming process has been described. The present invention is not limited to this. For example, the step of supplying the H ₂ gas and the WF ₆ gas and the subsequent step of removing the residual gas may be alternately repeated a plurality of times. That is, the H ₂ gas and the WF ₆ gas may be alternately supplied to the wafer 200 so as not to mix with each other (by time division).

  In the above-described embodiment, an example in which the SiO film is formed on the substrate as the insulating film has been described. However, the present invention is not limited to this. For example, a silicon nitride film (SiN film), a silicon oxynitride film (SiON film) It is also applicable to a substrate on which a silicon oxycarbonitride film (SiOCN film) and a polysilicon film (Poly-Si film) are formed.

Further, in the above-described embodiment, an example in which B ₂ H ₆ is used as the first reducing gas for reducing the insulating film has been described. However, the present invention is not limited thereto, and monoborane (BH ₃ ), triethylborane ((CH ₃ CH ₂ ) ₃ B, it may be used borane-based gas TEB) or the like. Alternatively, a silane-based gas such as monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), or trisilane (Si ₃ H ₈ ) may be used.

In the above-described embodiment, an example in which NH ₃ is used as the nitriding gas has been described. However, the present invention is not limited to this. For example, nitrogen (N ₂ ), nitrous oxide (N ₂ O), and diazene (N ₂ H ₂ ) gas, hydrazine _(N 2 _{H 4) gas,} N 3 _{H 8} gas, monomethyl hydrazine _{(CH 6 N} 2), dimethylhydrazine _{(C 2 H 8 N 2)} , monomethylamine _{((CH 3) NH 2)} , dimethylamine ((CH ₃ ) ₂ NH), trimethylamine ((CH ₃ ) ₃ N), monoethylamine (CH ₃ CH ₂ NH ₂ ), diethylamine ((C ₂ H ₅ ) ₂ NH), triethylamine ((C ₂ H ₅ ) _{3 N)} can also be used like.

Further, in the above-described embodiment, an example was described in which H ₂ gas was used as the H-containing gas as the second reducing gas. However, instead of H ₂ gas, deuterium (H-containing gas containing no other elements) was used. D ₂ ) It is also possible to use a gas or the like.

  In the above-described embodiment, an example in which W is used as the metal element has been described. However, the present invention is not limited to this, and titanium (Ti), tantalum (Ta), cobalt (Co), yttrium (Y), ruthenium (Ru), It is also possible to use aluminum (Al), molybdenum (Mo), niobium (Nb), manganese (Mn), nickel (Ni), or the like.

Further, in the above-described embodiment, an example in which a W film is formed using WF ₆ as the metal film has been described. However, the present invention is not limited to this, and a Ti film formed using titanium tetrafluoride (TiF ₄ ), Ta film formed by using a tantalum fluoride (TaF _5), Co film formed by using a two-cobalt fluoride (CoF _2), Y film formed by using a three-yttrium fluoride (YF _3), trifluoroethylene Ru film formed using ruthenium (RuF ₃ ), Al film formed using aluminum trifluoride (AlF ₃ ), Mo film formed using molybdenum pentafluoride (MoF ₅ ), niobium trifluoride ( It is also possible to use an Nb film formed using NbF ₃ ), a Mn film formed using manganese difluoride (MnF ₂ ), a Ni film formed using nickel difluoride (NiF ₂ ), or the like. Ah .

  In the above-described embodiment, the substrate processing apparatus is a batch-type vertical apparatus that processes a plurality of substrates at a time, and a nozzle for supplying a processing gas is provided upright in one reaction tube. Although an example in which a film is formed using a processing furnace having a structure in which an exhaust port is provided in the lower part of the above is described, the present invention is also applicable to a case where film formation is performed using a processing furnace having another structure. Further, the processing gas may not be supplied from a nozzle provided upright in the inner tube, but may be supplied from a gas supply port opened in a side wall of the inner tube. At this time, the exhaust port opened to the outer tube may be opened according to the height at which the plurality of substrates stacked and accommodated in the processing chamber exists. Further, the shape of the exhaust port may be a hole shape or a slit shape.

  Even when these substrate processing apparatuses are used, film formation can be performed under the same sequence and processing conditions as in the above-described embodiment.

  The process recipes (programs describing processing procedures and processing conditions) used for forming these various thin films include the contents of the substrate processing (film type, composition ratio, film quality, film thickness, processing procedure, processing It is preferable to individually prepare (prepare a plurality of them) according to conditions and the like. When starting the substrate processing, it is preferable to appropriately select an appropriate process recipe from a plurality of process recipes according to the content of the substrate processing. Specifically, the substrate processing apparatus is provided with a plurality of process recipes individually prepared according to the contents of the substrate processing via an electric communication line or a recording medium (external storage device 123) on which the process recipe is recorded. It is preferable to store (install) in the storage device 121c in advance. When starting the substrate processing, the CPU 121a included in the substrate processing apparatus appropriately selects an appropriate process recipe from a plurality of process recipes stored in the storage device 121c according to the content of the substrate processing. Is preferred. With this configuration, a single substrate processing apparatus can form thin films having various film types, composition ratios, film qualities, and film thicknesses in a general-purpose manner and with good reproducibility. In addition, it is possible to reduce an operator's operation load (input of a processing procedure, processing conditions, and the like), and to quickly start substrate processing while avoiding an operation error.

  The present invention can also be realized by, for example, changing a process recipe of an existing substrate processing apparatus. When the process recipe is changed, the process recipe according to the present invention is installed in an existing substrate processing apparatus via an electric communication line or a recording medium on which the process recipe is recorded, or the input / output of the existing substrate processing apparatus is performed. It is also possible to operate the apparatus and change the process recipe itself to the process recipe according to the present invention.

10 substrate processing apparatus 121 controller 200 wafer (substrate) 201 processing chamber

Claims (18)

(A) a step of supplying a first reducing gas composed of a borane-based gas or a silane-based gas to a substrate having an insulating film formed on a surface thereof to reduce the insulating film;
(B) forming a metal nitride film containing a metal element directly on the reduced insulating film, wherein the first reducing gas is supplied to and exhausted from the substrate; A step of supplying and exhausting a metal-containing gas containing the metal element to the substrate, and a step of supplying and exhausting a nitriding gas to the substrate one or more times in order,
(C) a step of forming a first metal layer directly on the metal nitride film, the step of supplying and exhausting the first reducing gas to the substrate; Performing the steps of supplying and exhausting the metal-containing gas one or more times in sequence,
(D) forming a second metal layer directly on the first metal layer, wherein a second reducing gas different from the first reducing gas and the metal are formed on the substrate; Simultaneously supplying the contained gas;
A method for manufacturing a semiconductor device having:
The said metal nitride film is a barrier metal film, is a metal nitride film other than a titanium nitride film and a tantalum nitride film, and has a resistivity lower than the resistivity of the titanium nitride film and the resistivity of the tantalum nitride film. 2. The method for manufacturing a semiconductor device according to item 1.
The metal element is tungsten, cobalt, nickel, molybdenum, aluminum, copper, zinc, a method of manufacturing a semiconductor device according to claim 1 or 2 selected from ruthenium.
The borane-based gas or a silane gas, monoboranes, diborane, triethylborane, monosilane, disilane, a method of manufacturing a semiconductor device according to any one of claims 1 to 3 selected from trisilane.
The second reducing gas manufacturing method of a semiconductor device according to any one of claims 1 to 4 is hydrogen.
Wherein in the step (A), a method of manufacturing a semiconductor device according to any one of claims 1 to 5 for supplying the first reducing gas in non-plasma to the substrate.
The insulating layer, a method of manufacturing a semiconductor device according to any one of claims 1 to 6 having a lower adhesion than the titanium nitride film or a tantalum nitride film with respect to the metal nitride layer.
The method according to claim 7, wherein the insulating film is selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon oxycarbonitride film, and a polysilicon film.
Wherein the first metal layer a second metal layer have the same composition, any one of the first of claims 1 to 8 metal film is formed by a metal layer and said second metal layer 13. The method for manufacturing a semiconductor device according to the above item .
A processing chamber for processing the substrate on which the insulating film is formed,
  A first reducing gas supply system that supplies a first reducing gas containing a borane-based gas or a silane-based gas to the processing chamber;
  A second reducing gas supply system that supplies a second reducing gas different from the first reducing gas into the processing chamber;
  A nitriding gas supply system for supplying a nitriding gas into the processing chamber;
  A source gas supply system for supplying a metal-containing gas into the processing chamber,
  An exhaust system for exhausting an atmosphere in the processing chamber;
(A) a process of supplying the first reducing gas to the substrate to reduce the insulating film;
(B) a process of forming a metal nitride film containing a metal element directly on the reduced insulating film, the process comprising supplying the first reducing gas to the substrate and exhausting the substrate; For the substrate, a process of supplying and exhausting the metal-containing gas, and for the substrate, a process of supplying and exhausting the nitriding gas, sequentially performing one or more times,
(C) a process of forming a first metal layer directly on the metal nitride film, the process comprising supplying the first reducing gas to the substrate and exhausting the substrate; A process of supplying and exhausting the metal-containing gas one or more times in sequence,
(D) a process of forming a second metal layer directly on the first metal layer, the process of simultaneously supplying the second reducing gas and the metal-containing gas to the substrate; A control unit configured to control the first reducing gas supply system, the second reducing gas supply system, the nitriding gas supply system, the source gas supply system, and the exhaust system so as to execute ,
A substrate processing apparatus.
The said metal nitride film is a barrier metal film, is a metal nitride film other than a titanium nitride film and a tantalum nitride film, and has a resistivity lower than the resistivity of the titanium nitride film and the resistivity of the tantalum nitride film. The substrate processing apparatus according to claim 10.
The substrate processing apparatus according to claim 10, wherein the metal element is selected from tungsten, cobalt, nickel, molybdenum, aluminum, copper, zinc, and ruthenium.
The substrate processing apparatus according to claim 10, wherein the borane-based gas or the silane-based gas is selected from monoborane, diborane, triethylborane, monosilane, disilane, and trisilane.
14. The substrate processing apparatus according to claim 10, wherein the second reducing gas is hydrogen.
15. The method according to claim 10, wherein in the step (A), the first reducing gas supply system is configured to supply the first reducing gas to the substrate in a non-plasma manner. 16. Substrate processing equipment.
The substrate processing apparatus according to claim 10, wherein the insulating film has lower adhesion to the metal nitride film than a titanium nitride film or a tantalum nitride film.
17. The substrate processing apparatus according to claim 10, wherein the insulating film is selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon oxycarbonitride film, and a polysilicon film.
18. The metal film according to claim 10, wherein the first metal layer and the second metal layer have the same composition, and a metal film is formed by the first metal layer and the second metal layer. A substrate processing apparatus according to any one of the preceding claims.