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

Abstract

The present invention makes it possible to improve film characteristics of a metal-based film.　The present invention comprises: (a) a step for supplying, to a substrate, a gas which contains a group 15 element, to form a first layer containing the group 15 element on the surface of the substrate; (b) a step for supplying, to the substrate, a gas which contains elemental Mo; (c) a step for supplying a reducing gas to the substrate; and (d) a step for carrying out (b) and (c) a prescribed number of times in an atmosphere in which decomposition of the first layer is suppressed, to form, on the first layer, a film which contains elemental Mo.

Description

Technical Field

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

Background Art

[0002] For example, a low-resistance tungsten (W) film is used as a word line of a NAND-type flash memory or DRAM having a three-dimensional structure. Further, for example, a titanium nitride (TiN) film may be used as a barrier film between this W film and an insulating film (see, for example, Patent Document 1 and Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, as the NAND-type flash memory having a three-dimensional structure becomes higher in layer, etching has become difficult, and thus thinning of the word line has become an issue. In order to solve this problem, a method for forming a metal-based film having good film characteristics without forming a barrier film as described above has been demanded.

[0005] An object of the present disclosure is to provide a technique capable of improving the film characteristics of a metal-based film.

Means for Solving the Problems

[0006] According to one aspect of the present disclosure, (a) supplying a gas containing a Group 15 element to a substrate to form a first layer containing a Group 15 element on a surface of the substrate; (b) supplying a gas containing Mo to the substrate; (c) supplying a reducing gas to the substrate; (d) performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer to form a film containing Mo element on the first layer; The present invention provides a technique having the following features: Effect of the Invention

[0007] According to one aspect of the present disclosure, it is possible to improve the film characteristics of a metal film formed on a substrate. [Brief description of the drawings]

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

[0009] The following will be described with reference to FIGS. 1 to 4. Note that the drawings used in the following description are all schematic, and the dimensional relationships and ratios of the respective elements shown in the drawings do not necessarily match the actual ones. Also, the dimensional relationships and ratios of the respective elements do not necessarily match even between multiple drawings.

[0010] (1) Configuration of Substrate Processing Apparatus The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as heating means (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.

[0011] Inside the heater 207, an outer tube 203 that forms a reaction tube (reaction vessel, processing vessel) concentrically with the heater 207 is disposed. The outer tube 203 is made of a heat-resistant material such as quartz (SiO 2 ), silicon carbide (SiC), etc., and is formed in a cylindrical shape with the upper end closed and the lower end open. 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) and is formed in a cylindrical shape with the upper end and the lower end open. An O-ring 220a as a seal member is provided between the upper end portion of the manifold 209 and the outer tube 203. Since the manifold 209 is supported by the heater base, the outer tube 203 is in a vertically installed state.

[0012] Inside the outer tube 203, an inner tube 204 that forms a reaction vessel is disposed. The inner tube 204 is made of a heat-resistant material such as quartz or SiC, and is formed in a cylindrical shape with the upper end closed and the lower end open. The processing vessel (reaction vessel) is mainly constituted by the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion (inside the inner tube 204) of the processing vessel.

[0013] The processing chamber 201 is configured to be able to accommodate the wafer 200 as a substrate in a state where it is arranged in multiple stages in the vertical direction in a horizontal posture by the boat 217 as a support tool.

[0014] 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, 320, and 330 are respectively connected to the nozzles 410, 420, and 430. However, the processing furnace 202 of the present embodiment is not limited to the above-described form.

[0015] Mass flow controllers (flow control units) MFCs 312, 322, and 332 are respectively provided in the gas supply pipes 310, 320, and 330 in order from the upstream side. Also, valves 314, 324, and 334 which are on-off valves are respectively provided in the gas supply pipes 310, 320, and 330. Gas supply pipes 510, 520, and 530 for supplying inert gas are respectively connected to the downstream sides of the valves 314, 324, and 334 of the gas supply pipes 310, 320, and 330. MFCs 512, 522, and 532 which are flow controllers (flow control units) and valves 514, 524, and 534 which are on-off valves are respectively provided in the gas supply pipes 510, 520, and 530 in order from the upstream side.

[0016] Nozzles 410, 420, and 430 are respectively connected to the tip ends of the gas supply pipes 310, 320, and 330. The nozzles 410, 420, and 430 are configured as L-shaped nozzles, and their horizontal portions are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, and 430 are provided inside the preliminary chamber 201a having a channel shape (groove shape) formed so as to protrude radially outward from the inner tube 204 and extend in the vertical direction, and are provided upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner tube 204 in the preliminary chamber 201a.

[0017] The nozzles 410, 420, and 430 are provided to extend from the lower region to the upper region of the processing chamber 201, and a plurality of gas supply holes 410a, 420a, and 430a are respectively provided at positions facing the wafer 200. Thereby, 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 these gas supply holes 410a, 420a, and 430a are provided over the lower to upper portions of the inner tube 204, each having the same opening area and further provided at the same opening pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-described form. For example, the opening area may be gradually increased from the lower portion to the upper portion of the inner tube 204. Thereby, it becomes possible to make the flow rate of the gas supplied from the gas supply holes 410a, 420a, and 430a more uniform.

[0018] A plurality of gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 are provided at a plurality of positions at the height from the lower portion to the upper portion of the boat 217 described later. Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 is supplied to the entire area of the wafer 200 accommodated from the lower portion to the upper portion of the boat 217. The nozzles 410, 420, and 430 only need to be provided to extend from the lower region to the upper region of the processing chamber 201, but it is preferable that they are provided to extend up to near the ceiling of the boat 217.

[0019] From the gas supply pipe 310, a raw material gas (metal-containing gas) containing a metal element is supplied into the processing chamber 201 as a processing gas via the MFC 312, the valve 314, and the nozzle 410.

[0020] From the gas supply pipe 320, a reducing gas is supplied into the processing chamber 201 as a processing gas via the MFC 322, the valve 324, and the nozzle 420.

[0021] From the gas supply pipe 330, a gas containing a Group 15 element different from the reducing gas is supplied into the processing chamber 201 as a processing gas via the MFC 332, the valve 334, and the nozzle 430.

[0022] From the gas supply pipes 510, 520, and 530, an inert gas, for example, argon (Ar) gas, is supplied into the processing chamber 201 via the MFCs 512, 522, 532, the valves 514, 524, 534, and the nozzles 410, 420, 430, respectively. Hereinafter, an example using Ar gas as the inert gas will be described. However, as the inert gas, in addition to Ar gas, for example, noble gases such as helium (He) gas, neon (Ne) gas, and xenon (Xe) gas may be used.

[0023] When mainly flowing the source gas from the gas supply pipe 310, mainly, the source gas supply system is constituted by the gas supply pipe 310, the MFC 312, and the valve 314. However, the nozzle 410 may also be considered to be included in the source gas supply system. The source gas supply system may also be referred to as a metal-containing gas supply system. When flowing the reducing gas from the gas supply pipe 320, mainly, the reducing gas supply system is constituted by the gas supply pipe 320, the MFC 322, and the valve 324. However, the nozzle 420 may also be considered to be included in the reducing gas supply system. When flowing the gas containing a Group 15 element from the gas supply pipe 330, mainly, the gas supply system for the gas containing a Group 15 element is constituted by the gas supply pipe 330, the MFC 332, and the valve 334. However, the nozzle 430 may also be considered to be included in the gas supply system for the gas containing a Group 15 element. Also, the metal-containing gas supply system, the reducing gas supply system, and the gas supply system for the gas containing a Group 15 element may be referred to as a processing gas supply system. Also, the nozzles 410, 420, 430 may be considered to be included in the processing gas supply system. Also, mainly, the inert gas supply system is constituted by the gas supply pipes 510, 520, 530, the MFCs 512, 522, 532, and the valves 514, 524, 534.

[0024] The gas supply method in this embodiment conveys gas via nozzles 410, 420, and 430 disposed in a preliminary chamber 201a within an annular vertically elongated space defined by the inner wall of the inner tube 204 and the ends of a plurality of wafers 200. Then, the gas is jetted into the inner tube 204 from a plurality of gas supply holes 410a, 420a, and 430a provided at positions of the nozzles 410, 420, and 430 facing the wafers. More specifically, raw material gas and the like are jetted in a direction parallel to the surface of the wafer 200 through 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.

[0025] The exhaust hole (exhaust port) 204a is a through-hole formed in the side wall of the inner tube 204 at a position facing the nozzles 410, 420, and 430. For example, it is a slit-shaped through-hole elongated in the vertical direction. The gas supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 and flowing on the surface of the wafer 200 flows into a gap (within the exhaust path 206) formed between the inner tube 204 and the outer tube 203 through the exhaust hole 204a. Then, the gas flowing into the exhaust path 206 flows into the exhaust pipe 231 and is discharged outside the processing furnace 202.

[0026] The exhaust hole 204a is provided at a position facing a plurality of wafers 200. The gas supplied from the gas supply holes 410a, 420a, and 430a near the wafer 200 in the processing chamber 201 flows horizontally and then flows into the exhaust path 206 through the exhaust hole 204a. The exhaust hole 204a is not limited to being configured as a slit-shaped through-hole and may be composed of a plurality of holes.

[0027] The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. Connected to the exhaust pipe 231, in order from the upstream side, are a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum exhaust device. The APC valve 243 can perform vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operating, and further, can adjust the pressure in the processing chamber 201 by adjusting the valve opening degree in a state where the vacuum pump 246 is operating. Mainly, the exhaust system is constituted by the exhaust hole 204a, the exhaust passage 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The vacuum pump 246 may be considered to be included in the exhaust system.

[0028] Below the manifold 209, a seal cap 219 is provided as a furnace lid that can airtightly close the lower end opening of the manifold 209. The seal cap 219 is configured to abut against the lower end of the manifold 209 from the lower side 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. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. On the opposite side of the seal cap 219 from the processing chamber 201, a rotation mechanism 267 for rotating a boat 217 that houses 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 wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically moved up and down by a boat elevator 115 as an elevating mechanism vertically installed 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, transfer system) that transfers the boat 217 and the wafer 200 housed in the boat 217 into and out of the processing chamber 201.

[0029] The boat 217 is configured to arrange a plurality of wafers 200, for example, 25 to 200 wafers, in a horizontal posture and at intervals in the vertical direction with their centers aligned with each other. The boat 217 is made of a heat-resistant material such as quartz or SiC, for example. A dummy substrate 218 made of a heat-resistant material such as quartz or SiC is horizontally supported in multiple stages at the lower part of the boat 217. With this configuration, the heat from the heater 207 is less likely to be transmitted to the seal cap 219 side. However, the present embodiment is not limited to the above-described form. For example, instead of providing the dummy substrate 218 at the lower part of the boat 217, a heat-insulating cylinder configured as a cylindrical member made of a heat-resistant material such as quartz or SiC may be provided.

[0030] As shown in FIG. 2, a temperature sensor 263 as a temperature detector is installed in the inner tube 204, and the energization amount to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is configured in an L shape similar to the nozzles 410, 420, and 430 and is provided along the inner wall of the inner tube 204.

[0031] As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121.

[0032] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe describing the procedures and conditions of a semiconductor device manufacturing method (substrate processing method) to be described later, etc. are stored in a readable manner. The process recipe is a combination that causes the controller 121 to execute each step (each process) in the semiconductor device manufacturing method (substrate processing method) to be described later and can obtain a predetermined result, and functions as a program. Hereinafter, this process recipe, control program, etc. are collectively referred to simply as a program. When the term "program" is used in this specification, it may include only the process recipe alone, only the control program alone, or a combination of the process recipe and the control program. The RAM 121b is configured as a memory area (work area) that temporarily holds programs, data, etc. read by the CPU 121a.

[0033] The I / O port 121d is connected to the aforementioned MFCs 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, etc.

[0034] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe, etc. from the storage device 121c in response to an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 512, 522, 532, the opening / closing operation of the valves 314, 324, 334, 514, 524, 534, the opening / closing operation of the APC valve 243 and the pressure adjustment operation based on the pressure sensor 245 by the APC valve 243, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the start and stop of the vacuum pump 246, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting operation of the boat 217 by the boat elevator 115, the operation of accommodating the wafer 200 in the boat 217, etc. in accordance with the content of the read recipe.

[0035] The controller 121 can be configured by installing the aforementioned program stored in an external storage device (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory or a memory card) 123 into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. In this specification, the recording medium may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer without using the external storage device 123 by using communication means such as the Internet or a dedicated line.

[0036] (2) Substrate Processing Step As an example of a step in the manufacturing process of a semiconductor device (device), an example of a step of forming a Mo-containing film containing molybdenum (Mo) used as a control gate electrode of, for example, 3D NAND on a wafer 200 will be described with reference to FIG. 4. The step of forming the Mo-containing film is executed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operations of each part constituting the substrate processing apparatus 10 are controlled by the controller 121.

[0037] In the substrate processing step (manufacturing step of a semiconductor device) according to the present embodiment, (a) A step of supplying a gas containing a Group 15 element to the wafer 200 to form a first layer containing a Group 15 element on the surface of the wafer 200; (b) A step of supplying a gas containing Mo element to the wafer 200; (c) A step of supplying a reducing gas to the wafer 200; (d) Performing (b) and (c) a predetermined number of times in an atmosphere that suppresses the decomposition of the first layer to form a film containing Mo element on the first layer, and forming a Mo-containing film as a metal-containing film on the first layer of the wafer 200.

[0038] In this specification, when the term "wafer" is used, it may mean "the wafer itself" or "a laminate of the wafer and a predetermined layer or film formed on its surface". In this specification, when the term "surface of the wafer" is used, it may mean "the surface of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer". In this specification, when the term "substrate" is used, it is synonymous with the case when the term "wafer" is used.

[0039] (Wafer Loading) When a plurality of wafers 200 are loaded (wafer charge) onto a boat 217, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by a boat elevator 115 and carried into (boat load) the processing chamber 201 and accommodated in a processing container. In this state, the seal cap 219 closes the lower end opening of the outer tube 203 via an O-ring 220.

[0040] (Pressure adjustment and temperature adjustment) The inside of the processing chamber 201, that is, the space where the wafers 200 are present, is evacuated by a vacuum pump 246 so as to reach a desired pressure (degree of vacuum). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and based on the measured pressure information, the APC valve 243 is feedback-controlled (pressure adjustment). The vacuum pump 246 is maintained in an always-operating state until at least the processing on the wafers 200 is completed. Also, the inside of the processing chamber 201 is heated by a heater 207 so as to reach a desired temperature. At this time, based on the temperature information detected by a temperature sensor 263, the amount of power supplied to the heater 207 is feedback-controlled 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 until at least the processing on the wafers 200 is completed.

[0041] [Formation process of the first layer] [First process] (Pre treatment process; Gas supply containing group 15 elements) Open valve 334 and flow a gas containing a Group 15 element into gas supply pipe 330. The gas containing a Group 15 element is flow rate adjusted by MFC 332, supplied into processing chamber 201 from gas supply hole 430a of nozzle 430, and exhausted from exhaust pipe 231. At this time, the gas containing a Group 15 element is supplied to wafer 200. Note that at this time, valve 534 may be opened and an inert gas such as Ar gas may be flowed into gas supply pipe 530. The Ar gas flowing through gas supply pipe 530 is flow rate adjusted by MFC 532, supplied into processing chamber 201 together with the gas containing a Group 15 element, and exhausted from exhaust pipe 231. At this time, in order to prevent the gas containing a Group 15 element from entering nozzles 410 and 420, valves 512 and 524 are opened and Ar gas is flowed into gas supply pipes 510 and 520. The Ar gas is supplied into processing chamber 201 via gas supply pipes 310 and 320 and nozzles 410 and 420, and exhausted from exhaust pipe 231.

[0042] At this time, adjust APC valve 243 so that the pressure in processing chamber 201 is, for example, a pressure within the range of 1 to 3990 Pa, for example, 1000 Pa. The supply flow rate of the gas containing a Group 15 element controlled by MFC 332 is, for example, a flow rate within the range of 0.01 to 5.0 slm. The supply flow rates of Ar gas controlled by MFCs 512, 522, and 532 are, for example, each within the range of 0.1 to 5.0 slm in order to suppress the entry of the gas containing a Group 15 element into each nozzle. At this time, set the temperature of heater 207 to a temperature such that the temperature of wafer 200 is, for example, within the range of 300 to 650 °C. The temperature of wafer 200 is preferably set to a temperature equal to or lower than the temperature of the metal-containing film forming step described later. Note that the notation of a numerical range such as "1 to 3990 Pa" in the present disclosure means that the lower limit value and the upper limit value are included in that range. Thus, for example, "1 to 3990 Pa" means "1 Pa or more and 3990 Pa or less". The same applies to other numerical ranges.

[0043] (Supply of at least one of a dilution gas and a reducing gas) Also, while supplying a gas containing a Group 15 element, it has a timing of supplying at least one of a dilution gas and a reducing gas. Here, as the dilution gas, in addition to an inert gas, a reducing gas can be used. Preferably, a gas having characteristics of suppressing a change in state or decomposition of the Group 15 element-containing material can be used. By supplying such a gas into the processing chamber 201, the inside of the processing chamber 201 is made into an atmosphere that suppresses a change in state or decomposition of the gas containing a Group 15 element. Specifically, for the supply of these gases, the valve 324 is opened, and a reducing gas, which is a dilution gas, is supplied to the gas supply pipe 320. The reducing gas is adjusted in flow rate by the MFC 322, supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420, and exhausted from the exhaust pipe 231. At this time, a gas containing a Group 15 element and a reducing gas as a dilution gas are supplied to the wafer 200. Incidentally, at the same time, the valve 524 may be opened to flow an inert gas such as Ar gas through the gas supply pipe 520. The Ar gas flowing through the gas supply pipe 520 is adjusted in flow rate by the MFC 522, supplied into the processing chamber 201 together with the reducing gas, and exhausted from the exhaust pipe 231. Further, when only an inert gas is supplied as the dilution gas, the valve 324 may be closed and the inert gas may be supplied from another inert gas supply system.

[0044] (Concentration adjustment of Group 15 element-containing material) In addition, a dilution gas may be supplied to adjust the concentration of the Group 15 element-containing material supplied to the wafer 200 to a predetermined concentration. The gas containing a Group 15 element may be a gas composed of a single substance of the Group 15 element-containing material or a gas in which the gas of the Group 15 element-containing material and the dilution gas are mixed. Depending on each case, at least one or more of the flow rate of the gas containing a Group 15 element, the flow rate of the reducing gas, and the flow rate of the dilution gas are adjusted so as to reach a predetermined concentration. Here, the concentration of the Group 15 element-containing material (gas containing a Group 15 element) is adjusted such that the flow rate of each gas is, for example, in the range of 0.1 to 50%. By supplying a gas having such a concentration, a first layer containing a Group 15 element can be formed. In addition, it is possible to suppress an increase in the concentration of the Group 15 element in the metal film (Mo-containing film) formed on the first layer. Note that if the concentration is less than 0.1%, it is difficult to form the first layer containing a Group 15 element, the formation time of the first layer increases, and the manufacturing throughput may decrease. Further, if the concentration exceeds 50%, the concentration of the Group 15 element in the first layer increases, the concentration of the Group 15 element in the metal film (Mo-containing film) increases, and the characteristics of the metal film may deteriorate. In addition, by supplying a gas having a concentration exceeding 50%, the amount of decomposition products of the Group 15 element-containing material generated in the processing chamber 201 increases, and the ratio of the Group 15 element and other elements (for example, hydrogen) in the first layer does not reach a predetermined ratio, and it may be difficult to obtain the effects described in the present disclosure.

[0045] At this time, the gas flowing in the processing chamber 201 is at least a gas containing a Group 15 element. Here, the Group 15 element is at least one of phosphorus (P) and arsenic (As). The gas containing a Group 15 element is a gas containing at least one of P and As. Further, preferably, the gas containing a Group 15 element may contain hydrogen (H). Examples of such a gas containing P and H include trimethylphosphine ((CH 3 ) 3 P) gas, triethylphosphine ((C 2 H 5 ) 3 P) gas, tri-n-propylphosphine ((n-C 3 H 7) 3 P) gas, triisopropylphosphine ((i-C 3 H 7 ) 3 P) gas, trinormalbutylphosphine ((n-C 4 H 9 ) 3 P) gas, triisobutylphosphine ((i-C 4 H 9 ) 3 P) gas, tritertiarybutylphosphine ((t-C 4 H 9 ) 3 P) gas, tertiarybutylphosphine (t-C 4 H 9 PH 2 ) gases such as alkylphosphine gases and aminophosphine (NH 2 PH 2 ) gas, tris(dimethylamino)phosphine ([(CH 3 ) 2 N)] 3 P) gas, bis(dimethylamino)phosphine (PH[N(CH 3 ) 2 2 ) gas, bis(dimethylamino)chlorophosphine ([(CH 3 ) 2 N] 2 PCl) gases such as aminophosphine gases and bis(dimethylamino)methylphosphine (CH 3 P[N(CH 3 ) 2 2 ) gas, dimethylaminodimethylphosphine ((CH 3 ) 2 PN(CH 3 ) 2 ) gas, diethylaminodiethylphosphine ((C 2 H 5 ) 2 PN(C 2 H 5 ) 2 ) gases such as phosphinasamide gases and phosphine (PH 3 ) gas, diphosphine (P 2 H 4 ​​)Phosphine-based gases such as gas, and trivinylphosphine ((CH 2 =CH) 3 P) gas, etc. can be used. The Group 15 element-containing material is at least one or more of these materials, and the Group 15 element-containing gas may be a single gas of the Group 15 element-containing material or a mixed gas of the Group 15 element-containing material and a diluent gas.

[0046] By supplying such a gas to the wafer 200, a first layer containing at least P is formed on the surface of the wafer 200. Preferably, the first layer is a layer containing P and H. More preferably, the first layer is a layer containing molecules of the Group 15 element-containing material and substances in a state where the molecules of the Group 15 element-containing material are partially decomposed. For example, when PH 3 is used as the Group 15 element-containing material, the first layer formed may contain P, H, and PHx. Here, X is an integer of 3 or less, and PHx is, for example, at least one or more of PH, PH 2 , PH 3 . In order to form the first layer containing such substances, the temperature in the processing chamber 201 is preferably a temperature at which a part of the Group 15 element-containing material can be decomposed. For example, when PH 3 is used as the Group 15 element-containing material, the temperature in the processing chamber 201 is in the range of 300°C to 650°C.

[0047] [Second step] (Residual gas removal) After a predetermined time has elapsed since the start of the supply of the group 15 element-containing gas, for example, after 1 to 600 seconds, the valve 334 of the gas supply pipe 330 is closed to stop the supply of the group 15 element-containing gas. That is, the time for supplying the group 15 element-containing gas to the wafer 200 is, for example, within the range of 1 to 600 seconds. At this time, the APC valve 243 of the exhaust pipe 231 remains open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to remove the unreacted gas or the group 15 element-containing gas remaining in the processing chamber 201 after contributing to the formation of the first layer from the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted. By reducing the pressure in the processing chamber 201, the group 15 element-containing gas remaining in the gas supply pipe 330 and the nozzle 430 can be exhausted. By exhausting the group 15 element-containing gas remaining in the gas supply pipe 330 and the nozzle 430, it is possible to suppress the supply of the group 15 element-containing gas remaining in the gas supply pipe 330 and the nozzle 430 into the processing chamber 201 during the formation process of the metal-containing film. At this time, the valves 514, 524, and 534 may remain open to maintain the supply of Ar gas into the processing chamber 201. The Ar gas acts as a gas entry suppression gas to each nozzle and can also act as a purge gas. When supplying Ar gas as a purge gas, the effect of removing the unreacted gas or the group 15 element-containing gas remaining in the processing chamber 201 after contributing to the formation of the first layer from the processing chamber 201 can be enhanced.

[0048] [Metal-containing film formation process] [Third step] (Metal-containing gas supply) Next, open valve 314 and flow the metal-containing gas, which is the source gas, into gas supply pipe 310. The metal-containing gas is adjusted in flow rate by MFC 312, supplied into processing chamber 201 from gas supply hole 410a of nozzle 410, and exhausted from exhaust pipe 231. At this time, the metal-containing gas is supplied to wafer 200. At the same time, open valve 514 and flow an inert gas such as Ar gas into gas supply pipe 510. The Ar gas flowing through gas supply pipe 510 is adjusted in flow rate by MFC 512, supplied into processing chamber 201 together with the metal-containing gas, and exhausted from exhaust pipe 231. At this time, open valves 524 and 534 to flow Ar gas into gas supply pipes 520 and 530 in order to prevent the metal-containing gas from entering nozzles 420 and 430. The Ar gas is supplied into processing chamber 201 through gas supply pipes 320 and 330 and nozzles 420 and 430, and exhausted from exhaust pipe 231.

[0049] At this time, adjust APC valve 243 so that the pressure in processing chamber 201 is, for example, a pressure within the range of 1 to 3990 Pa, for example, 500 Pa. The supply flow rate of the metal-containing gas controlled by MFC 312 is, for example, 0.1 to 1.0 slm. The supply flow rates of the Ar gas controlled by MFCs 512, 522, and 532 are each, for example, within the range of 0.1 to 5.0 slm. At this time, set the temperature of heater 207 so that the temperature of wafer 200 is, for example, within the range of 300 to 650 °C.

[0050] At this time, the main gas flowing in processing chamber 201 (the gas supplied to wafer 200) is the metal-containing gas. That is, the metal-containing gas is supplied to wafer 200. Here, as the metal-containing gas, for example, a molybdenum (Mo)-containing gas containing molybdenum (Mo) as a metal element can be used. As the Mo-containing gas, for example, molybdenum pentachloride (MoCl 5 ) gas containing Mo and chlorine (Cl), for example, molybdenum dichloride dioxide (MoO 2 Cl 2 ) gas containing Mo, oxygen (O), and Cl, molybdenum oxychloride (MoOCl 4) can be used. By supplying the Mo-containing gas, a Mo-containing layer as a metal-containing layer is formed on the wafer 200 (first layer). The Mo-containing layer may be a Mo layer containing Cl when using MoCl 5 , or may be an adsorption layer of MoCl 5 . Also, when using MoO 2 Cl 2 (or MoOCl 4 ), it may be a Mo layer containing Cl or O, or may be an adsorption layer of MoO 2 Cl 2 (or MoOCl 4 ), or may contain both of them. Preferably, the Mo layer is a layer containing P contained in the first layer. For example, when the first layer contains P, H, and PHx, the Mo-containing gas reacts with the molecules constituting the first layer, and the elements and molecules constituting the first layer desorb from the first layer. In the process of this desorption, the elements and molecules constituting the first layer can be incorporated into the Mo layer.

[0051] [Fourth step] (Residual gas removal) After a predetermined time has elapsed since the start of the supply of the metal-containing gas, for example, after 1 to 60 seconds, 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 1 to 60 seconds. At this time, the APC valve 243 of the exhaust pipe 231 remains open, and the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to remove the unreacted or metal-containing gas remaining in the processing chamber 201 after contributing to the formation of the metal-containing layer from the inside of the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted. At this time, the valves 514, 524, and 534 may remain open to maintain the supply of Ar gas into the processing chamber 201. The Ar gas acts as a gas for suppressing the entry of gas into each nozzle and can also act as a purge gas. When supplying Ar gas as a purge gas, the effect of removing the unreacted or metal-containing gas remaining in the processing chamber 201 after contributing to the formation of the metal-containing layer from the inside of the processing chamber 201 can be enhanced.

[0052] [Step 5] (Reduction gas supply) After removing the residual gas in the processing chamber 201, open valve 324 and flow the reduction gas into gas supply pipe 320. The reduction gas is adjusted in flow rate by MFC 322, supplied into the processing chamber 201 from the gas supply hole 420a of nozzle 420, and exhausted from exhaust pipe 231. At this time, the reduction gas is supplied to the wafer 200. At this time, valves 514, 524, and 534 are kept open to maintain the supply of Ar gas into gas supply pipes 510, 520, and 530. The Ar gas flowing through gas supply pipes 510, 520, and 530 is adjusted in flow rate by MFCs 512, 522, and 532 respectively. The Ar gas flowing through gas supply pipe 520 is supplied into the processing chamber 201 together with the reduction gas through gas supply pipe 320 and nozzle 420, and exhausted from exhaust pipe 231. Also, the Ar gas flowing through gas supply pipe 530 is supplied into the processing chamber 201 through gas supply pipe 330 and nozzle 430, and exhausted from exhaust pipe 231. Also, the Ar gas flowing through gas supply pipe 510 is supplied into the processing chamber 201 through gas supply pipe 310 and nozzle 410, and exhausted from exhaust pipe 231 to prevent the reduction gas from entering nozzle 410.

[0053] At this time, adjust APC valve 243 so that the pressure in the processing chamber 201 is, for example, a pressure within the range of 1 to 13300 Pa, for example, 5000 Pa. The supply flow rate of the reduction gas controlled by MFC 322 is, for example, a flow rate within the range of 1 to 50 slm, preferably 15 to 40 slm. The supply flow rates of the Ar gas controlled by MFCs 512, 522, and 532 are, for example, flow rates within the range of 0.1 to 5.0 slm respectively. At this time, set the temperature of heater 207 to a temperature such that the temperature of the wafer 200 is, for example, within the range of 300 to 650 °C.

[0054] At this time, the main gas flowing in the processing chamber 201 is the reduction gas. That is, the reduction gas is supplied to the wafer 200.

[0055] Here, as the reducing gas, for example, a gas composed of hydrogen (H) is used. Preferably, it is a gas composed of pure hydrogen. Specifically, hydrogen (H 2 ) gas and deuterium (D 2 ) can be used. Hereinafter, the case where H 2 gas is used as the reducing gas will be described as an example.

[0056] [Sixth step] (Residual gas removal) After a predetermined time has elapsed since the start of the supply of the reducing gas, for example, after 1 to 1200 seconds, the valve 324 of the gas supply pipe 320 is closed to stop the supply of the reducing gas. Then, in the same processing procedure as the above-described second step, unreacted gas or reducing gas and reaction by-products remaining in the processing chamber 201 after contributing to the formation of the metal-containing layer are removed from the processing chamber 201. That is, the atmosphere in the processing chamber 201 is exhausted.

[0057] (Performed a predetermined number of times) By performing the cycle of sequentially performing the above-described third step to sixth step at least once or more (a predetermined number of times (n times)), a Mo-containing film as a metal-containing film having a predetermined thickness is formed on the wafer 200. The above cycle is preferably repeated a plurality of times. The Mo-containing film is a film mainly composed of molybdenum. On the wafer 200 side (the first layer side) of the Mo-containing film, a layer containing Mo and P is formed. Preferably, the P concentration in the Mo-containing film is configured to decrease toward the surface of the Mo-containing film.

[0058] (After purge and return to atmospheric pressure) Ar 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 Ar gas acts as a purge gas, whereby the inside of the processing chamber 201 is purged with an inert gas, and the gas and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (return to atmospheric pressure).

[0059] (Wafer unloading) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the outer tube 203 is opened. Then, the processed wafer 200 is unloaded (boat unloading) from the lower end of the outer tube 203 to the outside of the outer tube 203 while being supported by the boat 217. Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge).

[0060] (3) Effects according to this embodiment According to this embodiment, one or more of the following effects can be obtained. (a) By forming the first layer between the surface of the wafer 200 and the Mo-containing film, the adhesion between the Mo-containing film and the wafer 200 can be improved. Thereby, a metal-based film with good film characteristics can be formed without forming a barrier film on the surface of the wafer 200.

[0061] (b) By including the group 15 element contained in the first layer in the Mo-containing film, the adhesion to the film (underlying film) formed on the surface of the wafer 200 can be improved. That is, the bonding force between the first layer and the surface of the wafer 200 and the bonding force between the first layer and the Mo-containing film can be increased.

[0062] (c) By diffusing the group 15 element contained in the first layer into the Mo-containing film, the bonding force of the elements present in the Mo-containing film can be improved. That is, bonds are formed between Mo elements and between Mo elements and group 15 elements.

[0063] (d) The reactivity between the first layer and the Mo-containing gas as the metal-containing gas can be increased, and the film formation rate of the Mo-containing film can be improved. That is, the productivity (throughput) of the semiconductor device can be improved. For example, as the gas containing a group 15 element, PH 3 gas is used, and as the Mo-containing gas, for example, MoO 2 Cl 2A case where it is used will be described. In this case, as the first layer, a layer containing PHx is formed. This PHx easily undergoes a chemical reaction with 2 Cl 2 and reacts more easily compared to the case where the first layer is not formed on the surface of the wafer 200. A layer containing Mo is formed on the wafer 200 (on the first layer), and a molecule containing P desorbs from the first layer. The molecule containing P is, for example, phosphorus oxychloride (POCl 4 ). Since such a reaction occurs, the film formation rate of the Mo-containing film can be improved. Note that due to this chemical reaction, a Group 15 element is incorporated into the Mo-containing film (diffuses into the Mo-containing film). Note that it can also be said that a part (surface) of the first layer is partially removed by the source gas (metal-containing gas). It can also be said that a part (surface) of the first layer is partially decomposed by the source gas.

[0064] (e) When forming the first layer, even if the temperature of the wafer 200 and the members around the wafer 200 (for example, at least one or more of a support tool and a processing container) is at the decomposition temperature of the group 15 element-containing material, by supplying a dilution gas, excessive decomposition of the group 15 element-containing material can be suppressed. That is, by supplying a dilution gas, an atmosphere for suppressing the decomposition of the group 15 element-containing material can be formed. Further, even if the group 15 element-containing material decomposes in the processing chamber 201, the dilution gas can suppress the decomposition products from being excessively supplied to the wafer 200. That is, the effect of flushing away the decomposition products by the dilution gas can be obtained. Note that it is considered that the dilution gas can suppress the decomposition of the group 15 element-containing material by reducing the partial pressure of the gas containing the group 15 element. Further, by reducing the partial pressure of the gas containing the group 15 element, the probability that the molecules of the gas containing the group 15 element collide with the members (for example, a support tool and a processing container) whose temperature is equal to or higher than the decomposition temperature can be reduced. Thereby, it is considered that the probability that the molecules of the gas containing the group 15 element receive thermal energy from the members whose temperature is equal to or higher than the decomposition temperature and decompose can be reduced. Note that not only the partial pressure of the group 15 element-containing gas but also the total pressure has the same effect. In a substrate processing apparatus having a heating unit around the processing container as shown in FIG. 1, the temperature of the members existing around the wafer 200 may be higher than the set temperature of the wafer 200, and in such an environment, decomposition of such a group 15 element-containing material is likely to occur. Therefore, in such a configuration of the substrate processing apparatus, a more remarkable effect can be obtained. Preferably, the partial pressure of the gas containing the group 15 element in the processing chamber 201 is made smaller than the partial pressure of the inert gas as the dilution gas. By setting such a partial pressure relationship, it becomes possible to suppress the decomposition of the gas containing the group 15 element.

[0065] (f) When forming the first layer, even if the temperature of the wafer 200 and the members around the wafer 200 (for example, at least one or more of a support tool and a processing container) is at the decomposition temperature of the group 15 element-containing material, by supplying a reducing gas, excessive decomposition of the group 15 element-containing material can be suppressed. That is, by supplying a reducing gas, an atmosphere for suppressing the decomposition of the group 15 element-containing material can be obtained. It is considered that the reducing gas itself has the same effect as the diluting gas and also has an action of suppressing the thermal decomposition of the group 15 element-containing material. In order to obtain such a mechanism in which the reducing gas directly suppresses the thermal decomposition of the group 15 element-containing material, preferably, the same element is contained in both the gas containing the group 15 element and the reducing gas. Such an element is, for example, hydrogen (H). Specific materials are as described above. Preferably, the partial pressure of the gas containing the group 15 element in the processing chamber 201 is made smaller than the partial pressure of the reducing gas. By setting such a partial pressure relationship, it becomes possible to suppress the decomposition of the gas containing the group 15 element. To set such a partial pressure, for example, as shown in FIG. 4, the flow rate of the reducing gas may be made larger than the flow rate of the gas containing the group 15 element.

[0066] (g) By forming a metal film (Mo-containing film) in an atmosphere for suppressing the decomposition of the first layer, at least one or more of the effects of (a), (b), (c), and (d) can be obtained. The atmosphere for suppressing the decomposition of the first layer will be described in detail in a modified example.

[0067] (4) Other embodiments Next, a modified example of the substrate processing step in the above-described embodiment will be described in detail. In the following modified examples, only the points different from the above-described embodiment will be described in detail.

[0068] (Modified Example 1) In this modification, as shown in FIG. 5, the supply flow rate of the reducing gas in the reducing gas supply step, which is the fifth step described above, is set to be higher than the supply flow rate of the reducing gas as a dilution gas supplied during the supply of the gas containing a group 15 element, which is the first step. In this manner, by increasing the supply flow rate of the reducing gas in the fifth step, the amount of reduction of the Mo-containing gas molecules adsorbed on the wafer 200 can be increased, and decomposition of the first layer can be suppressed. In the metal-containing film formation step including the fifth step, the temperature of the wafer 200 is set so as to promote the reaction between the Mo-containing gas adsorbed on the wafer 200 and the reducing gas. At such a temperature, the reactivity of the Mo-containing gas and the reducing gas can be increased, but the first layer may decompose. When the first layer decomposes, the Mo-containing film can be formed while removing the first layer, so that the impurities (e.g., P) in the Mo-containing film can be reduced, but the adhesion between the Mo-containing film and the wafer 200 may decrease. In the Mo-containing film formation step as in modification 1, the flow rate of the reducing gas can be increased to suppress the decomposition of the first layer. Here, the decomposition of the first layer is, for example, thermal decomposition. The decomposition reaction is 3 For example, 2PH 3 →2P+3H 2 This reaction can be suppressed by increasing the flow rate of the reducing gas in the fifth step. The flow rate of the reducing gas in the fifth step is preferably set to be higher than the flow rate of the Mo-containing gas in the third step. Furthermore, by suppressing the decomposition of the first layer, it is possible to suppress the elements (e.g., P) contained in the first layer from being excessively incorporated into the Mo-containing film. If impurities are excessively incorporated into the Mo-containing film, the electrical properties (e.g., resistivity) of the Mo-containing film may deteriorate.

[0069] (Variation 2) In this modified example, as shown in FIG. 6, the pressure in the processing chamber 201 in the fifth step is made higher than the pressure in the processing chamber 201 in the first step. By setting such a pressure, similar to Modified Example 1, the decomposition of the first layer that occurs in the step of forming the metal-containing film can be suppressed. Further, the pressure in the processing chamber 201 in the first step may be made higher than the pressure in the processing chamber 201 in the third step. In other words, the pressure in the processing chamber 201 in the third step is made lower than the pressure in the processing chamber 201 in the first step. Also, the pressure in the processing chamber 201 in the third step is made lower than the pressure in the processing chamber 201 in the fifth step. By setting such a pressure, in the third step, the reaction amount of the first layer and the metal-containing gas can be made less than the reaction amount of the first layer and the reducing gas in the fifth step. That is, in the third step, the decomposition of the first layer by the metal-containing gas can be suppressed. Further, in the third step, it is possible to suppress the state in which the metal element covers the surface of the first layer for reduction by the metal-containing gas and the reducing gas supplied in the fifth step cannot reach the surface of the first layer. That is, in the fifth step, the decomposition of the surface of the first layer by the reducing gas can be suppressed.

[0070] (Modified Example 3) In this modified example, as shown in FIG. 7, in the first step, before starting the supply of the gas containing a Group 15 element, the supply of the reducing gas is started, and the supply of the gas containing a Group 15 element is stopped during the supply of the reducing gas.

[0071] Before starting the supply of the gas containing a Group 15 element, by starting the supply of the reducing gas, it is possible to suppress the decomposition reaction of the gas containing a Group 15 element that may occur immediately after the supply of the gas containing a Group 15 element. Also, before starting the supply of the gas containing a Group 15 element, it is preferable to increase the pressure in the processing chamber 201 to a predetermined pressure with the reducing gas. By increasing the pressure to a predetermined pressure with the reducing gas, the molecules of the reducing gas can be dispersed in the processing chamber 201, and the contact between the molecules of the Group 15 element-containing material and the reducing gas in the processing chamber 201 can be improved. Thereby, the decomposition reaction of the Group 15 element-containing material can be suppressed.

[0072] Also, by stopping the supply of the gas containing a Group 15 element during the supply of the reducing gas, the decomposition reaction of the gas containing a Group 15 element remaining in the processing chamber 201 can be suppressed. By suppressing the decomposition of the gas containing a Group 15 element remaining in the processing chamber 201, it is possible to suppress the exposure of the Group 15 element simple substance generated by the decomposition of the Group 15 element-containing material on the surface of the first layer formed in the first step to the surface of the wafer 200 (first layer). The surface of the first layer is preferably in a state where the Group 15 element-containing material is adsorbed. By making the surface of the first layer in a state where the Group 15 element-containing material is adsorbed, the reaction between the Mo-containing gas supplied in the third step and the Group 15 element-containing material can be promoted.

[0073] In addition, in the first step, before starting the supply of the gas containing a Group 15 element, starting the supply of the reducing gas and stopping the supply of the gas containing a Group 15 element during the supply of the reducing gas may be performed only one of them. If only one of them is performed, the effect can be obtained. By performing both, both effects can be obtained.

[0074] (Modification 4) In this modification, as shown in FIG. 8, it has a step of performing the third to sixth steps X times and a step of performing them Y times. The supply time of the reducing gas in the fifth step (the step of supplying the reducing gas) in the step performed X times is set longer than the supply time of the reducing gas in the fifth step in the step performed Y times. By configuring in this way, at the initial stage of forming the Mo-containing film, decomposition of the first layer can be suppressed, and the first layer can be left on the wafer 200. Further, when the Mo-containing layer is formed to a certain extent, the Mo-containing layer formed initially becomes a cap film for the first layer, and it is possible to suppress the desorption from the wafer 200 due to thermal decomposition of the first layer. Here, X and Y are each an integer of 1 or more.

[0075] In addition, in the above embodiment, the case where MoO 2 Cl 2 gas is used as the metal-containing gas (Mo-containing gas) has been described as an example, but the present disclosure is not limited to this.

[0076] Also, in the above embodiment, the case where the same type of gas is used for the reducing gas used in the first step and the reducing gas used in the fifth step has been described as an example, but the present disclosure is not limited to this. Different molecular structure gases may be used for the reducing gas used in the first step and the reducing gas used in the fifth step. For example, in the first step, H 2 gas is used, and in the fifth step, D 2 gas or activated H 2 gas may be used. Further, in the fifth step, at least one of PH 3 gas, a silane-based gas and a borane-based gas described later may be used. Also, as the reducing gas used in the first step, a gas having at least one of the characteristics of suppressing decomposition of the group 15 element-containing material and serving as a carrier for the group 15 element-containing material may be used. Also, as the reducing gas used in the fifth step, a gas having at least one of the characteristics of reducing the Mo-containing gas as the source gas and suppressing decomposition of the first layer may be used.

[0077] In the above embodiment, the case where a gas containing P and H is used as the gas containing a Group 15 element has been described as an example. However, the present disclosure is not limited thereto. For example, monosilane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas, trisilane (Si 3 H 8 ) gas, tetrasilane (Si 4 H 10 ), and other reducing gases such as silane-based gases, monoborane (BH 3 ), diborane (B 2 H 6 ), and other borane-based gases can be used. However, with these gases, it is difficult to obtain easily detachable by-products such as POCl 3 generated when PH 4 is used, so the characteristics of the Mo-containing film may deteriorate. Therefore, as the gas containing a Group 15 element, a gas containing P is preferable. More preferably, a gas containing P and H is preferable.

[0078] In the above embodiment, the case where a gas containing the Mo element is used as the raw material gas (metal element-containing gas) has been described as an example. However, the present disclosure is not limited thereto. For example, it may be applicable to a process using a gas containing at least one element of ruthenium (Ru) element and tungsten (W) element as the raw material gas.

[0079] In the above embodiment, an example of film formation using a substrate processing apparatus, which is a batch-type vertical apparatus for processing a plurality of substrates at once, has been described. However, the present disclosure is not limited thereto, and it can also be preferably applied to the case of film formation using a single-wafer substrate processing apparatus for processing one or several substrates at once. 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.

[0080] Process recipes (programs describing processing procedures and processing conditions, etc.) used for forming these various thin films are preferably prepared individually (prepared in multiple copies) according to the content of substrate processing (film type, composition ratio, film quality, film thickness, processing procedure, processing conditions, etc. of the thin film to be formed). When starting substrate processing, it is preferable to appropriately select an appropriate process recipe from among a plurality of process recipes according to the content of the substrate processing. Specifically, it is preferable to pre-store (install) a plurality of process recipes prepared individually according to the content of the substrate processing in the storage device 121c provided in the substrate processing apparatus via a telecommunication line or a recording medium (external storage device 123) on which the process recipe is recorded. When starting substrate processing, it is preferable for the CPU 121a provided in the substrate processing apparatus to appropriately select an appropriate process recipe from among the plurality of process recipes stored in the storage device 121c according to the content of the substrate processing. By configuring in this way, it becomes possible to generally and reproducibly form thin films of various film types, composition ratios, film qualities, and film thicknesses with one substrate processing apparatus. In addition, the operation burden on the operator (input burden of processing procedures and processing conditions, etc.) can be reduced, and substrate processing can be started quickly while avoiding operation errors.

[0081] In addition, the present disclosure can also be realized, for example, by changing the process recipe of an existing substrate processing apparatus. When changing the process recipe, the process recipe according to the present disclosure can be installed in the existing substrate processing apparatus via a telecommunication line or a recording medium on which the process recipe is recorded, or the input / output device of the existing substrate processing apparatus can be operated to change the process recipe itself to the process recipe according to the present disclosure.

[0082] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above-described embodiments, and various modifications can be made without departing from the gist thereof.

Explanation of Reference Numerals

[0083] 10... Substrate processing apparatus, 121... Controller, 200... Wafer (substrate), 201... Processing chamber

Claims

1. (a) A step of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate; (b) A step of supplying a gas containing Mo element to the substrate; (c) A step of supplying a reducing gas to the substrate; (d) A step of performing (b) and (c) a predetermined number of times in an atmosphere that suppresses the decomposition of the first layer, and forming a film containing Mo element on the first layer, making the pressure of the processing atmosphere of the substrate in (c) higher than the pressure of the processing atmosphere of the substrate in (b) Substrate processing method.

2. In (a), making the processing atmosphere of the substrate an atmosphere that suppresses the decomposition of the Group 15 element-containing material contained in the gas containing the Group 15 element The substrate processing method according to Claim 1.

3. In (a), supplying a reducing gas while at least supplying the gas containing the Group 15 element The substrate processing method according to Claim 1 or 2.

4. Making the flow rate of the reducing gas supplied in (c) larger than the supply flow rate of the reducing gas supplied in (a) The substrate processing method according to Claim 3.

5. Making the pressure of the processing atmosphere of the substrate in (c) higher than the pressure of the processing atmosphere of the substrate in (a) The substrate processing method according to Claim 3 or 4.

6. In (a), making the partial pressure of the gas containing the Group 15 element in the processing atmosphere of the substrate smaller than the partial pressure of at least one of the reducing gas and the inert gas supplied to the processing atmosphere of the substrate The substrate processing method according to Claim 3 or 4.

7. In (a), starting the supply of the reducing gas before starting the supply of the gas containing the Group 15 element The substrate processing method according to any one of Claims 3 to 6.

8. In (a), raising the pressure of the processing atmosphere of the substrate with the reducing gas before starting the supply of the gas containing the Group 15 element The substrate processing method according to any one of Claims 3 to 7.

9. In (a), stopping the supply of the gas containing the Group 15 element while supplying the reducing gas The substrate processing method according to any one of Claims 3 to 8.

10. The reducing gas contains a hydrogen element The substrate processing method according to any one of Claims 3 to 9.

11. The reducing gas is a gas composed of hydrogen alone The substrate processing method according to any one of Claims 3 to 10.

12. The reducing gas supplied in (a) and the reducing gas supplied in (c) are gases with different molecular structures The substrate processing method according to any one of claims 3 to 10.

13. (a) A step of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate; (b) A step of supplying a gas containing Mo element to the substrate; (c) A step of supplying a reducing gas to the substrate; (d) In an atmosphere that suppresses the decomposition of the first layer, (b) and (c) are performed a predetermined number of times to form a film containing Mo element on the first layer. In (d), there are a step of performing (b) and (c) X times and a step of performing (b) and (c) Y times after X times, and the time of (c) in the step of performing X times is made longer than the time of (c) in the step of performing Y times (X and Y are each an integer of 1 or more) Substrate processing method.

14. The temperature of the substrate in (a) is made equal to or lower than the temperature of the substrate in (c). The substrate processing method according to any one of claims 1 to 13.

15. The concentration of the gas containing the Group 15 element supplied to the substrate in (a) is set to 0.1 to 50%. The substrate processing method according to any one of claims 1 to 14.

16. The Group 15 element is phosphorus. The substrate processing method according to any one of claims 1 to 15.

17. The gas containing the Group 15 element is a gas containing hydrogen element. The substrate processing method according to any one of claims 1 to 16.

18. (a) A step of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate; (b) A step of supplying a gas containing Mo element to the substrate; (c) A step of supplying a reducing gas to the substrate; (d) In an atmosphere that suppresses the decomposition of the first layer, (b) and (c) are performed a predetermined number of times to form a film containing Mo element on the first layer. The pressure of the processing atmosphere of the substrate in (c) is made higher than the pressure of the processing atmosphere of the substrate in (b). Method for manufacturing a semiconductor device.

19. (a) A step of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate; (b) A step of supplying a gas containing Mo element to the substrate; (c) A step of supplying a reducing gas to the substrate; (d) forming a film containing Mo element on the first layer by performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer; In (d), there are a step of performing (b) and (c) X times and a step of performing (b) and (c) Y times after X times, and the time of (c) in the step of performing X times is made longer than the time of (c) in the step of performing Y times (X and Y are each an integer of 1 or more). A method of manufacturing a semiconductor device.

20. A gas supply system for supplying at least one of a gas containing Mo element, a reducing gas, and a gas containing a Group 15 element to a substrate; (a) supplying a gas containing a Group 15 element to the substrate to form a first layer containing the Group 15 element on the substrate; (b) supplying a gas containing the Mo element to the substrate; (c) supplying the reducing gas to the substrate; (d) forming a film containing Mo element on the first layer by performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer; a control unit configured to be able to control the gas supply system so as to perform a process of making the pressure of the processing atmosphere of the substrate in (c) higher than the pressure of the processing atmosphere of the substrate in (b); A substrate processing apparatus having the above.

21. A gas supply system for supplying at least one of a gas containing Mo element, a reducing gas, and a gas containing a Group 15 element to a substrate; (a) supplying a gas containing a Group 15 element to the substrate to form a first layer containing the Group 15 element on the substrate; (b) supplying a gas containing the Mo element to the substrate; (c) supplying the reducing gas to the substrate; (d) forming a film containing Mo element on the first layer by performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer; In (d), there are a step of performing (b) and (c) X times and a step of performing (b) and (c) Y times after X times, and the time of (c) in the step of performing X times is made longer than the time of (c) in the step of performing Y times (X and Y are each an integer of 1 or more), and a control unit configured to be able to control the gas supply system so as to perform the above process; A substrate processing apparatus having the above.

22. (a) a procedure of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate; Procedure of supplying a gas containing Mo element to the substrate, Procedure of supplying a reducing gas to the substrate, Procedure of performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer to form a film containing Mo element on the first layer, Procedure of making the pressure of the processing atmosphere of the substrate in (c) higher than the pressure of the processing atmosphere of the substrate in (b), A program for causing a computer to execute the substrate processing apparatus.

23. (a) Procedure of supplying a gas containing a Group 15 element to a substrate to form a first layer containing the Group 15 element on the substrate, Procedure of supplying a gas containing Mo element to the substrate, Procedure of supplying a reducing gas to the substrate, Procedure of performing (b) and (c) a predetermined number of times in an atmosphere that suppresses decomposition of the first layer to form a film containing Mo element on the first layer, In (d), it has a procedure of performing (b) and (c) X times and a procedure of performing (b) and (c) Y times after X times, and making the time of (c) in the procedure of performing X times longer than the time of (c) in the procedure of performing Y times (X and Y are integers of 1 or more), A program for causing a computer to execute the substrate processing apparatus.

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