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

Abstract

Provided is a technique for preventing the generation of particles.　This method comprises: (a) a step for supplying a first processing gas into a processing vessel; (b) a step for supplying a second processing gas that is different from the first processing gas into the processing vessel; (c) a step for supplying a third processing gas that is different from either of the first processing gas or the second processing gas into the processing vessel; (d) a step for performing X rounds of a cycle including steps (a) and (b) in this order; (e) a step for performing Y rounds of a cycle including steps (d) and (c); and (f) a step for changing the value of the X to be performed in the subsequent cycle including steps (d) and (c) in step (e) in accordance with the number of rounds of the cycle including steps (d) and (c) in this order.

Description

[Technical Field]

[0001] The present disclosure provides: Processing method, Processing device, program , substrate processing method and semiconductor device manufacturing method - Patents.com Regarding. [Background technology]

[0002] BACKGROUND ART As one step in the manufacturing process of a semiconductor device, a step of forming a film on a substrate in a processing chamber of a substrate processing apparatus is sometimes performed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2011 / 111498 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when a film is formed on a substrate, the film is also formed on the inner wall of the processing chamber, and if the cumulative film thickness becomes large, the film may peel off, resulting in the generation of particles.

[0005] An object of the present disclosure is to provide a technique capable of suppressing particle generation. [Means for solving the problem]

[0006] According to one aspect of the present disclosure, (a) supplying a first process gas into a process chamber; (b) supplying a second process gas, which is different from the first process gas, into the process vessel; (c) supplying a third process gas, which is different from both the first process gas and the second process gas, into the process vessel; (d) performing a cycle of steps (a) and (b) X times; (e) performing a cycle of (d) and (c) Y times; (f) (e) changing X in the next cycle of performing (d) and (c) according to the number of times the cycle of performing (d) and (c) in turn has been performed; The present invention provides a technique having: [Effects of the Invention]

[0007] According to the present disclosure, generation of particles can be suppressed. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a longitudinal cross-sectional view showing an outline of a vertical processing furnace of a substrate processing apparatus according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view taken along the line AA in FIG. [Figure 3] FIG. 2 is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment of the present disclosure, showing a control system of the controller in a block diagram. [Figure 4] FIG. 1 illustrates a process flow according to an embodiment of the present disclosure. [Figure 5] FIG. 2 is a diagram illustrating an example of gas supply in a film forming process according to an embodiment of the present disclosure. [Figure 6] FIG. 10 is a diagram illustrating an example of gas supply in a precoating process according to an embodiment of the present disclosure. [Figure 7] Figures 7(A) and 7(B) are diagrams for explaining the state of a film on the surface of the inner wall, etc., of the processing vessel formed by the pre-coating process of Figure 6. Figures 7(C) and 7(D) are diagrams for explaining the state of a film on the surface of the inner wall, etc., of the processing vessel formed when the pre-coating process is not performed. [Figure 8] FIG. 10 is a diagram illustrating a modified example of gas supply in a precoating process according to an embodiment of the present disclosure. [Figure 9] FIG. 10 is a diagram illustrating a modified example of gas supply in a precoating process according to an embodiment of the present disclosure. [Figure 10]FIG. 10 is a diagram illustrating a modified example of gas supply in a film forming process according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following description will be made with reference to Figures 1 to 7. Note that all drawings used in the following description are schematic, and the dimensional relationships, ratios, etc. of elements shown in the drawings do not necessarily match those of reality. Furthermore, the dimensional relationships, ratios, etc. of elements between multiple drawings do not necessarily match.

[0010] (1) Configuration of the substrate processing equipment The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 has a cylindrical shape and is installed vertically by being supported by a heater base (not shown) as a holding plate.

[0011] An outer tube 203 constituting a reaction tube (reaction vessel, processing vessel) is disposed concentrically inside the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. A manifold (inlet flange) 209 is disposed concentrically below the outer tube 203. The manifold 209 is made of a metal such as stainless steel (SUS) and has a cylindrical shape with open upper and lower ends. An O-ring 220a serving as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported by a heater base, so that the outer tube 203 is installed vertically.

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

[0013] The processing chamber 201 is configured to be able to accommodate wafers 200 as substrates arranged in multiple stages in the vertical direction in a horizontal position using boats 217 as supports.

[0014] Nozzles 410, 420, and 430 are provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209 and the inner tube 204. Gas supply pipes 310, 320, and 330 are connected to the nozzles 410, 420, and 430, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned configuration.

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

[0016] Nozzles 410, 420, 430 are respectively connected to the tip ends of the gas supply pipes 310, 320, 330. The nozzles 410, 420, 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, 430 are provided inside the channel-shaped (groove-shaped) preliminary chamber 201a that protrudes radially outward from the inner tube 204 and extends vertically, and are provided inside the preliminary chamber 201a facing upward (upward in the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

[0017] The nozzles 410, 420, and 430 are provided extending from the lower region of the processing chamber 201 to the upper region thereof, with multiple gas supply holes 410a, 420a, and 430a respectively positioned opposite the wafer 200. This allows the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 to supply processing gas to the wafer 200. The gas supply holes 410a, 420a, and 430a are provided in multiple locations from the lower to the upper portion of the inner tube 204, each with the same opening area and at the same opening pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above configuration. For example, the opening area may gradually increase from the lower portion to the upper portion of the inner tube 204. This allows for more uniform flow rates of gas supplied from the gas supply holes 410a, 420a, and 430a.

[0018] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided at a plurality of positions at a height from the bottom to the top of the boat 217, which will be described later. Therefore, the process gas supplied into the process chamber 201 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 is supplied to the entire area of ​​the wafers 200 accommodated in the boat 217 from the bottom to the top. The nozzles 410, 420, 430 may be provided so as to extend from the bottom region to the top region of the process chamber 201, but it is preferable that the nozzles 410, 420, 430 be provided so as to extend to near the ceiling of the boat 217.

[0019] A first process gas containing a metal element as a first element is supplied as a process gas from the gas supply pipe 310 into the process chamber 201 via the MFC 312, the valve 314, and the nozzle 410.

[0020] A second processing gas, which is a gas different from the first processing gas and contains a second element, a Group 15 element, is supplied from the gas supply pipe 320 into the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420.

[0021] A third process gas, which is different from both the first process gas and the second process gas and contains a third element, a Group 14 element, is supplied from the gas supply pipe 330 into the process chamber 201 via the MFC 332, the valve 334, and the nozzle 430.

[0022] An inert gas, such as nitrogen (N2) gas, is supplied from the gas supply pipes 510, 520, and 530 into the processing chamber 201 via the MFCs 512, 522, and 532, the valves 514, 524, and 534, and the nozzles 410, 420, and 430. An example in which N2 gas is used as the inert gas will be described below, but other than N2 gas, a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas may also be used as the inert gas.

[0023] When a first process gas is flowed from the gas supply pipe 310, a first process gas supply system is mainly composed of the gas supply pipe 310, the MFC 312, and the valve 314, but the nozzle 410 may be included in the first process gas supply system. When a second process gas is flowed from the gas supply pipe 320, a second process gas supply system is mainly composed of the gas supply pipe 320, the MFC 322, and the valve 324, but the nozzle 420 may be included in the second process gas supply system. When a third process gas is flowed from the gas supply pipe 330, a third process gas supply system is mainly composed of the gas supply pipe 330, the MFC 332, and the valve 334, but the nozzle 430 may be included in the third process gas supply system. The first process gas supply system, the second process gas supply system, and the third process gas supply system may also be referred to as a process gas supply system. The process gas supply system may include the nozzles 410, 420, and 430. The gas supply pipes 510, 520, and 530, the MFCs 512, 522, and 532, and the valves 514, 524, and 534 mainly constitute an inert gas supply system.

[0024] In the gas supply method of this embodiment, gas is transported via nozzles 410, 420, and 430 arranged in a vertically elongated annular space, a preliminary chamber 201a, defined by the inner wall of the inner tube 204 and the ends of the wafers 200. The gas is then ejected into the inner tube 204 from a plurality of gas supply holes 410a, 420a, and 430a provided in the nozzles 410, 420, and 430 at positions facing the wafers. More specifically, a first process gas, a second process gas, a third process gas, etc. are ejected in a direction parallel to the surface of the wafer 200 from 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, respectively.

[0025] The exhaust hole (exhaust port) 204a is a through-hole formed in the sidewall of the inner tube 204 at a position facing the nozzles 410, 420, and 430, and is, for example, a slit-shaped through-hole that is elongated in the vertical direction. Gas is supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 and flows over the surface of the wafer 200, and then flows through the exhaust hole 204a into a gap (into the exhaust path 206) formed between the inner tube 204 and the outer tube 203. The gas that has flowed into the exhaust path 206 then flows into the exhaust pipe 231 and is discharged to the outside of the processing furnace 202.

[0026] The exhaust hole 204a is provided at a position facing the plurality of wafers 200, and the gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafers 200 in the processing chamber 201 flows 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 configured as a plurality of holes.

[0027] The manifold 209 is provided with an exhaust pipe 231 that exhausts the atmosphere inside the processing chamber 201. The exhaust pipe 231 is connected to, in order from upstream, a pressure sensor 245 serving as a pressure detector (pressure detection unit) that detects the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 serving as a vacuum exhaust device. The APC valve 243 can evacuate and stop the vacuum exhaust inside the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening while the vacuum pump 246 is operating. An exhaust system is mainly composed of the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0028] A seal cap 219 serving as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209 is provided below the manifold 209. The seal cap 219 is configured to abut against 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 and is formed in a disk shape. An O-ring 220b serving as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cap 219. A rotation mechanism 267 that rotates a boat 217 that accommodates wafers 200 is provided on the opposite side of the seal cap 219 from the processing chamber 201. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafers 200. The seal cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 serving as a lifting mechanism that is vertically installed outside the outer tube 203. The boat elevator 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by raising and lowering the seal cap 219. The boat elevator 115 is configured as a transfer device (transfer mechanism, transfer system) that transfers the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

[0029] The boat 217 is configured to hold a plurality of wafers 200, for example, 25 to 200, arranged horizontally and with their centers aligned at intervals in the vertical direction. The boat 217 is made of a heat-resistant material such as quartz or SiC. Dummy substrates 218, made of a heat-resistant material such as quartz or SiC, are supported horizontally in multiple stages at the bottom of the boat 217. This configuration makes it difficult for heat from the heater 207 to be transmitted to the seal cap 219. However, this embodiment is not limited to the above-described configuration. For example, instead of providing the dummy substrates 218 at the bottom of the boat 217, a heat-insulating cylinder, which is a cylindrical member made of a heat-resistant material such as quartz or SiC, may be provided.

[0030] 2, a temperature sensor 263 is installed in the inner tube 204 as a temperature detector, and the amount of power supplied to the heater 207 is adjusted based on temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution within the processing chamber 201. The temperature sensor 263 is configured in an L-shape, similar to the nozzles 410, 420, and 430, and is installed along the inner wall of the inner tube 204.

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

[0032] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. The storage device 121c readably stores 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 (described later), and the like. The process recipe is a combination of processes (steps) in a semiconductor device manufacturing method (described later) that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc. are collectively referred to simply as a program. In this specification, the term "program" may refer to a process recipe alone, a control program alone, or a combination of a process recipe and a control program. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0033] The I / O port 121d is connected to the above-mentioned 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 also to read a recipe or the like from the storage device 121c in response to an input of an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 512, 522, and 532, the opening and closing operations of the valves 314, 324, 334, 514, 524, and 534, the opening and closing operation of the APC valve 243 and the pressure adjustment operation by the APC valve 243 based on the pressure sensor 245, 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 raising and lowering operation of the boat 217 by the boat elevator 115, the operation of accommodating the wafers 200 in the boat 217, and the like.

[0035] The controller 121 can be configured by installing the above-mentioned program stored in an external storage device 123 (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, or a semiconductor memory such as a USB memory or a memory card) into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the recording medium may include only the storage device 121c, only the external storage device 123, or both. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0036] (2) Treatment process 4 to 6 and 7(A) to 7(D), an example of a series of processing sequences including a film formation process for forming a film on a wafer 200 as a substrate, as one step in a manufacturing process of a semiconductor device, using the above-mentioned substrate processing apparatus 10. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by a controller 121.

[0037] In the manufacturing process of the semiconductor device according to the present disclosure, (a) supplying a first process gas into a process chamber; (b) supplying a second process gas to the process chamber; (c) supplying a third process gas into the process chamber; (d) performing a cycle of steps (a) and (b) X times; (e) performing a cycle of (d) and (c) Y times; (f) In (e), the method includes a step of changing X in the next cycle of performing (d) and (c) depending on the number of times that the cycle of performing (d) and (c) in turn has been performed.

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

[0039] <Film forming process> First, a film forming process in which the wafer 200 is loaded into the processing furnace 202 and a film is formed on the wafer 200 will be described with reference to FIGS.

[0040] [Board delivery] 1, when a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220b.

[0041] The processing chamber 201, i.e., the space in which the wafer 200 is present, is evacuated by the vacuum pump 246 to a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback-controlled (pressure adjustment) based on the measured pressure information. The processing chamber 201 is also heated by the heater 207 to a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled (temperature adjustment) based on temperature information detected by the temperature sensor 263 so that the processing chamber 201 has a desired temperature distribution. The rotation mechanism 267 also starts to rotate the wafer 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0042] [Film formation process] (First processing gas supply step S10) The valve 314 is opened to allow a first process gas to flow into the gas supply pipe 310. The flow rate of the first process gas is adjusted by the MFC 312, and the first process gas is supplied into the process chamber 201 through the gas supply holes 410a of the nozzle 410 and exhausted through the exhaust pipe 231. At the same time, the valve 514 is opened to allow an inert gas, such as N2 gas, to flow into the gas supply pipe 510. The flow rate of the inert gas flowing through the gas supply pipe 510 is adjusted by the MFC 512, and the inert gas is supplied into the process chamber 201 together with the first process gas and exhausted through the exhaust pipe 231. At this time, in order to prevent the first process gas from entering the nozzles 420 and 430, the valves 524 and 534 are opened to allow the inert gas to flow into the gas supply pipes 520 and 530. The inert gas is supplied into the process chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430 and exhausted through the exhaust pipe 231.

[0043] At this time, the APC valve 243 is adjusted to set the pressure inside the process chamber 201 to, for example, 1 to 3990 Pa. The supply flow rate of the first process gas controlled by the MFC 312 is set to, for example, 0.1 to 2.0 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, and 532 are each set to, for example, 0.1 to 20 slm. In the following description, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is set to, for example, 300 to 650°C. The time for supplying the first process gas to the wafer 200 is set to, for example, 0.01 to 30 seconds. Note that in this disclosure, a numerical range such as "1 to 3990 Pa" means that the lower limit and upper limit are included in the range. Therefore, for example, "1 to 3990 Pa" means "1 Pa or more and 3990 Pa or less." The same applies to other numerical ranges.

[0044] At this time, a first process gas is supplied to the wafer 200. Here, the first process gas may be, for example, a gas containing titanium (Ti, also called titanium) as a metal element, such as titanium tetrafluoride (TiF4) gas, titanium tetrachloride (TiCl4) gas, titanium tetrabromide (TiBr4) gas, or other gas containing a halogen element. One or more of these may be used as the first process gas.

[0045] (Purge step S11) After a predetermined time has elapsed since the start of the supply of the first process gas, the valve 314 is closed to stop the supply of the first process gas. At this time, the APC valve 243 of the exhaust pipe 231 is left open, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove any unreacted first process gas remaining in the processing chamber 201 or any part of the first process gas that has contributed to film formation from the processing chamber 201. At this time, the valves 514, 524, and 534 are left open to maintain the supply of the inert gas into the processing chamber 201. The inert gas acts as a purge gas, and can enhance the effect of removing any unreacted first process gas remaining in the processing chamber 201 or any part of the first process gas that has contributed to film formation from the processing chamber 201.

[0046] (Second processing gas supply step S12) After a predetermined time has elapsed since the start of purging, valve 324 is opened to allow a second process gas to flow into gas supply pipe 320. The flow rate of the second process gas is adjusted by MFC 322, and the second process gas is supplied into processing chamber 201 through gas supply holes 420a of nozzle 420 and exhausted through exhaust pipe 231. At the same time, valve 524 is opened to allow an inert gas to flow into gas supply pipe 520. Furthermore, to prevent the second process gas from entering nozzles 410 and 430, valves 514 and 534 are opened to allow an inert gas to flow into gas supply pipes 510 and 530.

[0047] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 3990 Pa. The supply flow rate of the second processing gas controlled by the MFC 322 is set within a range of, for example, 0.1 to 30 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, and 532 are each set within a range of, for example, 0.1 to 20 slm. The time for which the second processing gas is supplied to the wafer 200 is set within a range of, for example, 0.01 to 30 seconds.

[0048] At this time, a second process gas is supplied to the wafer 200. Here, the second process gas may be, for example, an N-containing gas containing nitrogen (N) as a Group 15 element. Examples of the N-containing gas include ammonia (NH) gas, diazene (NH), hydrazine (NH), and NH gas, among other hydrogen nitride gases. One or more of these gases may be used as the second process gas.

[0049] (Purge step S13) After a predetermined time has elapsed since the supply of the second process gas started, the valve 324 is closed to stop the supply of the second process gas. Then, by the same process procedure as in step S11, the second process gas remaining in the process chamber 201, which has not reacted or has contributed to film formation, is removed from the process chamber 201.

[0050] (Performed a specified number of times) The cycle of sequentially performing the above-described steps S10 to S13 is performed one or more times (a predetermined number of times (n times)), thereby forming a film of a predetermined thickness on the wafer 200. It is preferable to repeatedly perform the above-described cycle multiple times. Here, a film containing a metal element and a Group 15 element, such as a titanium nitride (TiN) film, is formed on the wafer 200.

[0051] (After purging and atmospheric pressure recovery) An inert gas is supplied into the processing chamber 201 through the gas supply pipes 510, 520, and 530 and exhausted through the exhaust pipe 231. The inert gas acts as a purge gas, thereby purging the processing chamber 201 with the inert gas, and gases and 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 the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0052] [Board removal] Thereafter, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the outer tube 203. Then, the processed wafers 200, on which a predetermined film has been formed, are carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 (boat unloading) while being supported by the boat 217. Thereafter, the processed wafers 200 are removed from the boat 217 (wafer discharging).

[0053] As shown in FIG. 7(C), when the above-described film formation process is performed, deposits including thin films such as TiN films formed on wafers 200 adhere to and accumulate on the surfaces of components within the process chamber, such as the inner walls of outer tube 203 and inner tube 204, the outer surfaces of nozzles 410, 420, and 430, the inner surfaces of gas supply holes 410a, 420a, and 430a, the inner surface of manifold 209, the surface of boat 217, and the upper surface of seal cap 219. As shown in FIG. 7(D), if the amount of deposits, i.e., the cumulative film thickness, becomes too thick, peeling of the deposits may occur, resulting in a rapid increase in the number of particles. Therefore, a cleaning process is performed to remove the deposits accumulated within the process chamber before the cumulative film thickness (amount of deposits) reaches a predetermined thickness (predetermined amount) before peeling or falling of the deposits occurs.

[0054] <Cleaning process> In the cleaning process, an empty boat 217, i.e., a boat 217 not loaded with wafers 200, is loaded into the processing vessel. Then, a cleaning gas is supplied into the processing chamber 201 and exhausted from the exhaust pipe 231. This removes deposits that have accumulated on the surfaces of components in the processing chamber 201, for example, inside the processing vessel.

[0055] After the cleaning process, a pre-coating process is performed on the processing chamber. Performing a film formation process without a pre-coating process can result in a film thickness drop phenomenon, where the film formed on the wafer 200 is thinner than the target film thickness. One possible reason for this is that the state inside the processing chamber after the cleaning process differs from the state inside the processing chamber when film formation processes are repeatedly performed. During film formation, the processing gas is consumed on the surfaces of components inside the processing chamber, resulting in an insufficient amount of processing gas being supplied to the surface of the wafer 200. Performing a pre-coating process after the cleaning process and before the film formation process can prevent the film thickness drop phenomenon from occurring and stabilize the film thickness formed on the wafer 200. The sequence of operations in the pre-coating process is described below with reference to FIG. 6.

[0056] <Pre-coating process> After the cleaning process is completed and before the film formation process is performed, a pre-coat film is formed on the surfaces of the components inside the process vessel, such as the inner walls of the outer tube 203 and the inner tube 204, the outer surfaces of the nozzles 410, 420, and 430, the inner surfaces of the gas supply holes 410a, 420a, and 430a, the inner surface of the manifold 209, the surface of the boat 217, and the upper surface of the seal cap 219, while the empty boat 217 remains inside the process vessel. That is, a pre-coat process is performed by a coating method that coats the inner walls of the process vessel with a pre-coat film. Note that the pre-coat process may also be performed with the boat 217 removed.

[0057] (First processing gas supply step S20) A first process gas is supplied into the process chamber 201, which is a processing vessel, by a process procedure similar to that of step S10 described above. That is, the valve 314 is opened, and the first process gas is flowed into the gas supply pipe 310. The flow rate of the first process gas is adjusted by the MFC 312, and the first process gas is supplied into the process chamber 201 through the gas supply holes 410a of the nozzle 410 and exhausted through the exhaust pipe 231. At the same time, the valve 514 is opened, and an inert gas such as N2 gas is flowed into the gas supply pipe 510. The flow rate of the inert gas flowing through the gas supply pipe 510 is adjusted by the MFC 512, and the inert gas is supplied into the process chamber 201 together with the first process gas and exhausted through the exhaust pipe 231. At this time, in order to prevent the first process gas from entering the nozzles 420 and 430, the valves 524 and 534 are opened, and the inert gas is flowed into the gas supply pipes 520 and 530. The inert gas is supplied into the processing chamber 201 through gas supply pipes 320 and 330 and nozzles 420 and 430 and is exhausted from an exhaust pipe 231 .

[0058] That is, at this time, the first processing gas is supplied to the wafer 200. As described above, the first processing gas may be, for example, a gas containing titanium (Ti) as a metal element, and one example of such a gas may be a gas containing a halogen element.

[0059] (Purge step S21) By the same process procedure as in step S11 described above, the first process gas remaining in the process chamber 201 without reacting or after contributing to the formation of the pre-coat film is removed from the process chamber 201.

[0060] (Second processing gas supply step S22) A second process gas is supplied into the process chamber 201 using the same process procedure as in step S12 described above. That is, after a predetermined time has elapsed since the start of purging, the valve 324 is opened to allow the second process gas to flow into the gas supply pipe 320. The flow rate of the second process gas is adjusted by the MFC 322, and the second process gas is supplied into the process chamber 201 through the gas supply holes 420a of the nozzle 420 and exhausted through the exhaust pipe 231. At the same time, the valve 524 is opened to allow an inert gas to flow into the gas supply pipe 520. Furthermore, to prevent the second process gas from entering the nozzles 410 and 430, the valves 514 and 534 are opened to allow an inert gas to flow into the gas supply pipes 510 and 530.

[0061] At this time, the second process gas is supplied to the wafer 200. As described above, the second process gas may be, for example, an N-containing gas containing nitrogen (N) as a group 15 element.

[0062] (Purge step S23) The second process gas remaining in the process chamber 201 without reacting or after contributing to the formation of the pre-coat film is removed from the process chamber 201 by the same process procedure as in step S13 described above.

[0063] (Performed a predetermined number of times Step S24) By repeating the cycle of steps S20 to S23 in order a predetermined number of times (X times, where X is an integer equal to or greater than 1), a pre-coat film of a predetermined thickness is formed on the surface of the inner wall of the processing vessel, etc. It is preferable to repeat the above cycle multiple times.

[0064] That is, in a state where the wafer 200 is not present in the processing vessel, steps similar to steps S10 to S13 in the above-described film formation process are performed in this order in the processing vessel a predetermined number of times (X times, where X is an integer equal to or greater than 1). The processing procedures and processing conditions in each step are the same as those in the above-described film formation, except that each gas is supplied into the processing vessel instead of being supplied to the wafer 200.

[0065] (Third processing gas supply step S25) Then, after performing step S24 a predetermined number of times (X times, where X is an integer greater than or equal to 1), in which steps S20 to S23 are performed in this order, a third process gas is supplied into the process chamber 201. That is, the valve 334 is opened to allow the third process gas to flow into the gas supply pipe 330. The flow rate of the third process gas is adjusted by the MFC 332, and the third process gas is supplied into the process chamber 201 through the gas supply holes 430a of the nozzle 430 and exhausted through the exhaust pipe 231. At the same time, the valve 534 is opened to allow the inert gas to flow into the gas supply pipe 530. Furthermore, to prevent the third process gas from entering the nozzles 410 and 420, the valves 514 and 524 are opened to allow the inert gas to flow into the gas supply pipes 510 and 520.

[0066] At this time, the APC valve 243 is adjusted to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 3990 Pa. The supply flow rate of the third processing gas controlled by the MFC 332 is set within a range of, for example, 0.1 to 10 slm. The supply flow rates of the inert gases controlled by the MFCs 512, 522, and 532 are each set within a range of, for example, 0.1 to 20 slm. The time for which the third processing gas is supplied to the wafers 200 is set within a range of, for example, 0.01 to 60 seconds.

[0067] At this time, a third process gas is supplied to the wafer 200. Here, the third process gas may be, for example, a gas containing silicon (Si) as a Group 14 element, such as a silane-based gas, such as monosilane (SiH4) gas, disilane (Si2H6) gas, or trisilane (Si3H8) gas. One or more of these may be used as the third process gas.

[0068] (Purge step S26) After a predetermined time has elapsed since the supply of the third process gas started, the valve 334 is closed to stop the supply of the third process gas. Then, by the same process procedures as in steps S21 and S23, the third process gas remaining in the process chamber 201, which has not reacted or has contributed to film formation, is removed from the process chamber 201.

[0069] (Performed a predetermined number of times Step S27) Next, by repeating a cycle of sequentially performing the above-mentioned steps S24 to S26 a predetermined number of times (Y times, where Y is an integer greater than or equal to 1), that is, by repeating a cycle of sequentially performing the above-mentioned steps S20 to S23 a predetermined number of times (X times, where X is an integer greater than or equal to 1), and then repeating a cycle of performing steps S25 and S26 a predetermined number of times (Y times, where Y is an integer greater than or equal to 1), a film containing the first element, the second element, and the third element of a predetermined thickness is formed.

[0070] In this way, by alternately and repeatedly supplying a first process gas containing a first element and a second process gas containing a second element into the process chamber 201, and then supplying a third process gas containing a third element, a film containing the first element, the second element, and the third element is formed as a pre-coat film on the quartz surface of the inner wall of the process vessel. For example, a titanium silicon nitride (TiSiN) film containing Ti, a metal element, N, a Group 15 element, and Si, a Group 14 element, is formed. This improves adhesion to the inner wall of the process vessel, making it less likely for the film to peel off from the inner wall. In addition, the surface roughness of the initial pre-coat film can be reduced.

[0071] In this step, the ratio of X to Y is changed by changing the number of times X is performed depending on the number of times Y is performed. In this way, depending on the ratio of X to Y, a film having a different ratio between the metal element as the first element and the Group 14 element as the third element is formed on the inner wall of the processing vessel or the like.

[0072] Specifically, the number of times X, which is the number of cycles for performing steps S20 to S23, is increased according to the number of times Y is performed in this step; for example, the number of times X is increased each time the number of times Y is performed increases by a predetermined number. By increasing the number of times X according to the number of times Y is performed, it is possible to form a film in which the concentration of the third element contained in the third process gas decreases with each increase in X. In other words, it is possible to control the concentration of the third element to vary stepwise on the surface of the inner wall or the like of the process container from the base of the pre-coat film to the surface of the pre-coat film.

[0073] That is, by changing the number of times X is performed according to the number of times Y is performed, it is possible to form a film with a different composition, and depending on the ratio of X to Y, a film with a different ratio of metal elements contained in the first processing gas and Group 14 elements contained in the third processing gas is formed on the inner wall of the processing vessel, etc.

[0074] Furthermore, the supply amount of the third process gas in step S25 may be changed depending on the number of times Y is performed in step S27. The supply amount is calculated as the product of the supply flow rate and the supply time. That is, depending on the number of times Y is performed in step S27, either the supply time or the supply flow rate of the third process gas in step S25, or both, may be changed. Even in this case, the concentration of the third element can be controlled to vary stepwise from the base of the pre-coat film toward the surface of the pre-coat film.

[0075] For example, the supply time of the third process gas is changed so that the supply time T1 of the third process gas until Y reaches a predetermined number of times and the supply time T2 of the third process gas after Y reaches the predetermined number of times satisfy the relationship T1 > T2. In this way, by shortening the supply time of the third process gas after Y reaches the predetermined number of times compared to the supply time before Y reaches the predetermined number of times, it is possible to reduce the Si content on the surface of the TiSiN film formed during the Y cycles, and to make it closer to the TiN film formed on the wafer 200. Furthermore, shortening the supply time of the third process gas makes it possible to shorten the processing time, thereby improving the throughput in the semiconductor device manufacturing process.

[0076] For example, a TiN film is not formed in one layer per cycle. If X is continuously changed depending on the number of times Y is performed, the supply amount of the third process gas may change before one TiN layer is formed, which may prevent the formation of a precoat layer with the desired composition. By changing the number of times X is performed depending on the number of times Y is performed and controlling it in stages, a precoat layer with the desired composition can be formed. In other words, it is possible to modulate the composition for each layer.

[0077] 7(A), a TiSiN film having a lattice constant similar to that of quartz is formed on the surface side of the quartz in contact with quartz (SiO2), and a TiSiN film having a different Si content (also referred to as Si content rate or Si concentration) is formed on the quartz surface such as the inner wall of outer tube 203 from the base side of the pre-coat film, which is the surface side of the quartz, toward the surface side of the pre-coat film according to the ratio of X and Y. That is, when a gas containing Ti, a metal element, is used as the first process gas, a gas containing N, a Group 15 element, is used as the second process gas, and a gas containing Si, a Group 14 element, is used as the third process gas, a TiSiN film having a different ratio of Ti, a metal element, and Si, a Group 14 element, between the base side and the surface side of the pre-coat film is formed on the quartz surface such as the inner wall of outer tube 203.

[0078] (Performed a predetermined number of times Step S28) Next, by performing the cycle of steps S20 to S23 in sequence a predetermined number of times (Z times, where Z is an integer greater than or equal to 1), a film containing the first element and the second element, which have the same components as the film to be formed on wafer 200, is formed on the surface of the film containing the first element, the second element, and the third element as a pre-coat film.

[0079] Specifically, as shown in FIG. 7(B), a TiN film having the same composition as the film to be formed on the wafer 200 and a lattice constant similar to that of the TiN film to be formed on the wafer 200 is formed on the surface of a TiSiN film having a different Si content as the pre-coat film. The number of times Z does not change each time the number of times Y increases by a predetermined number. In this way, by performing the cycle of steps S20 to S23 in order a predetermined number of times (Z times, where Z is an integer equal to or greater than 1), the surface of the pre-coat film can be covered with a TiN film. Covering the surface of the pre-coat film with a TiN film prevents the TiSiN film from being exposed, and improves the processing uniformity of the film for each substrate processing.

[0080] That is, a film containing TiSiN, which contains Ti, a metal element that is the first element, N, a group 15 element that is the second element, and Si, a group 14 element, is formed on the surface of quartz, such as the inner wall of the processing vessel, and a TiN film is formed on the surface of the pre-coat film.

[0081] Therefore, it is possible to form a film whose composition is modulated from a film containing Ti, N, and Si, which is a film containing the first, second, and third elements, to a film containing Ti and N, which is a film containing the first and second elements. In this way, by forming the top surface of the pre-coat film as a TiN film, it is possible to make the consumption amount of processing gas when forming a TiN film on the wafer 200 uniform for each film formation, and it is possible to make the processing quality uniform for each film formation.

[0082] Here, depending on whether the surface of the pre-coat film is a TiN film or a TiSiN film, the consumption amount of the process gas used during the film formation process on the wafer 200 may change. For example, the amount of adsorption of the first process gas as the process gas may change between a TiN film and a TiSiN film. That is, the first process gas may be consumed by the inner wall of the process container, etc., and the amount of the first process gas supplied to the wafer 200 may change. This may change the film quality of the TiN film formed on the wafer 200, such as the film thickness, crystallinity, film continuity, and film surface roughness.

[0083] In the present disclosure, a TiSiN film containing Si is formed as a precoat film on the base side (surface side of the processing vessel) of the precoat film, and the Si content decreases toward the surface side of the precoat film, forming a TiN film that does not contain Si on the outermost surface.

[0084] That is, the base side of the precoat film (the surface side of the processing vessel) is a TiSiN film containing Si contained in quartz (SiO2), which is the material of the processing vessel. This improves adhesion to the inner wall of the processing vessel, making it less likely for the film to peel off from the inner wall. Also, the surface roughness of the initial precoat film can be reduced. Furthermore, neither film contains any elements other than those contained in the film (TiN film) formed on the wafer 200, and the processing gas used in the film formation process can be used for each precoat. This eliminates the need for an additional gas supply system for precoating, thereby reducing the cost of the substrate processing apparatus.

[0085] Furthermore, by forming the top surface of the precoat film as the same TiN film as the film formed on the wafer 200, the consumption of the processing gas used when forming the TiN film on the wafer 200 can be made uniform for each film formation (each batch processing), and the processing quality of the wafers for each film formation can be made uniform.

[0086] For example, X=1 in the first half of the precoating process, then X=3 after a predetermined number of times, and then X=5 after a further predetermined number of times, gradually increasing the number of X. As a result, the base side of the precoat film becomes a high-concentration Si film, and the top surface of the precoat film is formed as a TiN film that does not contain Si.

[0087] The pre-coating process is completed through the above series of operations. The pre-coating process described above suppresses particle generation in the processing chamber 201, and improves the processing quality, such as the characteristics of the film formed on the wafer 200.

[0088] (Unloading empty boats) After the pre-coating process is completed, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the empty boat 217 is carried out from the lower end of the manifold 209 to the outside of the outer tube 203 (boat unloading).

[0089] (3) Effects of this embodiment According to the present disclosure, one or more of the following advantages can be obtained. (a) The generation of particles can be suppressed. That is, the generation of particles due to film peeling inside the processing chamber (processing vessel) can be suppressed. (b) The throughput in the manufacturing process of semiconductor devices is improved. (c) The processing quality, such as the characteristics of the film formed on the wafer 200, can be improved and made uniform.

[0090] (4) Other embodiments Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above-described embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0091] (Variation 1) 8 illustrates a modified gas supply in the pre-coating process according to an embodiment of the present disclosure, which further includes a step of supplying a fourth process gas, which is different from any of the first process gas, the second process gas, and the third process gas, into the process container.

[0092] That is, in the pre-coating process, after performing a cycle of steps S20 to S23 of the above-described step S24 X times, a cycle of supplying the fourth process gas, purging, the above-described step S25, and the above-described step S26 is performed Y times, and then the fourth process gas is further supplied and purged, and the above-described step S28 is performed. That is, the fourth process gas is supplied after step S24 and after step S27. Note that the fourth process gas may be supplied either after step S24 or after step S27. In this modification, the number of times X is changed according to the number of times Y. This makes it possible to improve the processing quality, such as the characteristics of the film formed on the wafer 200, while suppressing film peeling of the pre-coat film.

[0093] Here, the fourth processing gas may be, for example, oxygen (O2) gas, ozone (O3) gas, plasma-excited O2 (O2 * Oxygen-containing gases (also called oxidizing gases) such as oxidizing gas (O2) gas, O2 gas + hydrogen (H2) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, and carbon dioxide (CO2) gas can be used. One or more of these can be used as the fourth process gas. By oxidizing the precoat film during its formation, the film stress of the precoat film can be reduced, and peeling of the precoat film can be suppressed. Furthermore, by supplying an oxygen-containing gas during the formation of the precoat film, a dividing layer of crystals such as TiN and TiSiN can be formed. This suppresses abnormal crystal growth and reduces the surface roughness of the precoat film.

[0094] (Variation 2) FIG. 9 illustrates a modified example of gas supply in the precoating process according to an embodiment of the present disclosure. In this modification, a third process gas is partially supplied in parallel with a first process gas supply. That is, the first process gas supply, simultaneous first and third process gas supply, third process gas supply, purge, second process gas supply, and purge are performed in this order a predetermined number of times (X times, where X is an integer), followed by the third process gas supply and purge. These are then performed a predetermined number of times (Y times, where Y is an integer) before performing step S28. In this modification, the number of times X is changed depending on the number of times Y is performed. This can improve the processing quality, such as the characteristics of the film formed on the wafer 200, while suppressing film peeling of the precoat film. Furthermore, the crystal continuity of the precoat film can be improved, thereby reducing the surface roughness of the precoat film.

[0095] (Variation 3) 10 shows a modified example of gas supply in a film formation process according to an embodiment of the present disclosure. In this modified example, when a first process gas is supplied, a third process gas is partially supplied in parallel. That is, the following steps are performed in this order: first process gas supply, simultaneous supply of the first and third process gases, third process gas supply, purging, second process gas supply, and purging. This improves the continuity of the crystals on the surface of the precoat film, and reduces the surface roughness of the precoat film.

[0096] Furthermore, the film forming process of the above-described Modification 3 may be carried out after the pre-coating process of the above-described Modification 2. By carrying out the above process from the initial stage of the pre-coating film in this way, the crystal continuity and surface roughness of the pre-coating film can be reduced.

[0097] In the above embodiment, the third process gas in the pre-coating step is a gas containing Si, a Group 14 element, as the third element. However, the present disclosure is not limited to this. Alternatively, the third process gas may be O2 gas, an oxygen-containing gas containing oxygen (O), a Group 16 element, as the third element. In this case, a film containing titanium oxynitride (TiON) containing Ti, a metal element as the first element, N, a Group 15 element as the second element, and O, a Group 16 element, is formed on the surface of the quartz inner wall of the process chamber, and a TiN film is formed on the surface of the pre-coating film. Therefore, a film whose composition is modulated from a film containing Ti, O, and N to a film containing Ti and N can be formed.

[0098] Furthermore, in the above embodiment, Si is used as an example of a Group 14 element, but carbon (C) or germanium (Ge) may also be applicable.

[0099] In addition, in the above embodiment, Ti was described as the metal element contained in the first processing gas, but in addition to Ti, at least one or more metals such as molybdenum (Mo), ruthenium (Ru), hafnium (Hf), zirconium (Zr), tungsten (W), etc. may also be used.

[0100] Furthermore, in the above embodiment, an example of film formation using a substrate processing apparatus that is a batch-type vertical apparatus that processes multiple substrates at a time has been described, but the present disclosure is not limited to this and can also be suitably applied to film formation using a single-wafer type substrate processing apparatus that processes one or several substrates at a time.

[0101] Furthermore, it is preferable to prepare (prepare) a plurality of process recipes (programs describing processing procedures and processing conditions) used for forming various thin films individually according to the contents of substrate processing (such as the type, composition ratio, film quality, and film thickness of the thin film to be formed, the processing procedures, and processing conditions). When starting substrate processing, it is preferable to appropriately select an appropriate process recipe from the plurality of process recipes according to the contents of substrate processing. Specifically, it is preferable to store (install) the plurality of process recipes individually prepared according to the contents of substrate processing in advance in the storage device 121c of the substrate processing apparatus via an electric communication line or a recording medium (external storage device 123) on which the process recipes are recorded. When starting substrate processing, it is preferable for the CPU 121a of the substrate processing apparatus to appropriately select an appropriate process recipe from the plurality of process recipes stored in the storage device 121c according to the contents of substrate processing. This configuration enables a single substrate processing apparatus to flexibly and reproducibly form thin films of various film types, composition ratios, film qualities, and film thicknesses. Furthermore, the operational burden on the operator (such as the burden of inputting processing procedures and processing conditions) can be reduced, and substrate processing can be started promptly while avoiding operational errors.

[0102] 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 an electric communication line or a recording medium on which the process recipe is recorded, or the process recipe itself can be changed to the process recipe according to the present disclosure by operating an input / output device of the existing substrate processing apparatus.

[0103] Although various exemplary embodiments of the present disclosure have been described above, the present disclosure is not limited to these embodiments and can be used in appropriate combinations. [Explanation of symbols]

[0104] 10. Substrate processing equipment 121 Controller 200 wafers (substrates) 201 Processing Room 202 Processing furnace

Claims

1. (a) supplying a first process gas containing a metal element into a process vessel in which no substrate has been loaded; (b) supplying a second process gas containing a Group 15 element into the process vessel; (c) supplying a third process gas containing a Group 14 element or a Group 16 element into the process vessel; (d) performing X cycles of sequentially performing (a) and (b); (e) performing a cycle of (d) and (c) Y times; (f) in (e), changing X in the next cycle of performing (d) and (c) according to the number of times the cycle of performing (d) and (c) in sequence has been performed; and the inner wall of the processing vessel is made of quartz; In (f), a film containing the metal element, the Group 15 element, and the Group 14 element or the Group 16 element is formed on the surface of the quartz; A processing method for forming a precoat film having different compositions on the base side and the surface side on the surface of the member in the processing vessel.

2. (f) In (e), the value of X in the next cycle in which (d) and (c) are performed is increased according to the number of times that the cycle in which (d) and (c) are performed in sequence. The processing method according to claim 1 .

3. (f) In (e), each time the number of times that the cycle of (d) and (c) is executed in sequence increases by a predetermined number, X is increased.

3. The processing method according to claim 1 or 2.

4. (g) after (e), further comprising a step of performing a cycle of sequentially performing (a) and (b) Z times; The method according to any one of claims 1 to 3.

5. In (g), the number of times Z is not changed regardless of the value of Y. The processing method according to claim 4.

6. The third process gas contains the Group 14 element, In (f), a film containing the metal element, the Group 15 element, and the Group 14 element is formed on the surface of the quartz; (h) supplying a fourth process gas containing oxygen element into the process vessel; (h) is carried out after (d) and / or after (e).

6. The method according to any one of claims 1 to 5.

7. In (f), a film having a different ratio between the metal element and the Group 14 element or a different ratio between the metal element and the Group 16 element is formed depending on the ratio between the X and the Y.

7. The method according to any one of claims 1 to 6.

8. The third process gas contains the Group 14 element, In (f), a film containing the metal element, the Group 15 element, and the Group 14 element is formed on the surface of the quartz.

8. The method of claim 1.

9. the metal element is titanium, the Group 15 element is nitrogen; the Group 14 element is silicon; In (f), a film containing the titanium, the nitrogen, and the silicon is formed on the surface of the quartz. The processing method according to claim 8.

10. The third process gas contains the Group 16 element, In (f), a film containing the metal element, the group 15 element, and the group 16 element is formed on the surface of the quartz.

8. The method of claim 1.

11. the metal element is titanium, the Group 15 element is nitrogen; the Group 16 element is oxygen, In (f), a film containing the titanium, the nitrogen, and the oxygen is formed on the surface of the quartz. The method of claim 10.

12. In (d), (c) is partially performed in parallel when (a) is performed.

10. The method of claim 1.

13. In (g), (c) is partially performed in parallel when (a) is performed.

6. The processing method according to claim 4 or 5.

14. In (e), the supply amount of the third process gas in (c) is changed depending on the number of times that the cycle of (d) and (c) is performed in sequence.

14. The method of claim 1.

15. In (e), the supply time of the third process gas in (c) is changed depending on the number of times the cycle of (d) and (c) is performed in sequence.

15. The method of claim 1.

16. In (e), the supply flow rate of the third process gas in (c) is changed depending on the number of times that the cycle of (d) and (c) is performed in sequence.

16. A processing method according to any one of claims 1 to 15.

17. A processing vessel having an inner wall made of quartz; a gas supply system that supplies into the processing vessel a first processing gas containing a metal element, a second processing gas containing a Group 15 element, and a third processing gas containing a Group 14 element or a Group 16 element; (a) supplying the first process gas into the process vessel without a substrate being loaded therein; (b) supplying the second process gas into the process vessel; (c) supplying the third process gas into the process vessel; (d) performing a cycle of (a) and (b) in turn X times; (e) a process of performing a cycle of (d) and (c) Y times; (f) changing X in the next cycle of performing (d) and (c) in accordance with the number of times that the cycle of performing (d) and (c) in sequence has been performed in (e); (f) a control unit configured to be able to control the gas supply system so that a film containing the metal element, the Group 15 element, and the Group 14 element or the Group 16 element is formed on the surface of the quartz, and a pre-coat film having different compositions on a base side and a surface side is formed on a surface of a member in the processing vessel; A processing device having:

18. (a) supplying a first process gas containing a metal element into a process vessel in which no substrate has been loaded; (b) supplying a second process gas containing a Group 15 element into the process vessel; (c) supplying a third process gas containing a Group 14 element or a Group 16 element into the process vessel; (d) performing X cycles of steps (a) and (b); (e) performing a cycle of (d) and (c) Y times; (f) in (e), changing X in the next cycle of performing (d) and (c) according to the number of times that the cycle of performing (d) and (c) in turn has been performed; A program for causing a processing device to execute the above by a computer, The inner wall of the processing vessel is made of quartz, and in (f), a film containing the metal element, the Group 15 element, and the Group 14 element or the Group 16 element is formed on the surface of the quartz, and a precoat film having different compositions on the base side and the surface side is formed on the surface of a member inside the processing vessel.

19. (a) supplying a first process gas containing a metal element into a process vessel in which no substrate has been loaded; (b) supplying a second process gas containing a Group 15 element into the process vessel; (c) supplying a third process gas containing a Group 14 element or a Group 16 element into the process vessel; (d) performing X cycles of sequentially performing (a) and (b); (e) performing a cycle of (d) and (c) Y times; (f) changing X in the next cycle of performing (d) and (c) in accordance with the number of times the cycle of performing (d) and (c) in turn has been performed in (e); the inner wall of the processing vessel is made of quartz; In (f), a film containing the metal element, the Group 15 element, and the Group 14 element or the Group 16 element is formed on the surface of the quartz; forming a pre-coat film having different compositions on a base side and a surface side on a surface of the member in the processing vessel; processing the substrate in the processing chamber after the step of forming the precoat film; A substrate processing method comprising:

20. (a) supplying a first process gas containing a metal element into a process vessel in which no substrate has been loaded; (b) supplying a second process gas containing a Group 15 element into the process vessel; (c) supplying a third process gas containing a Group 14 element or a Group 16 element into the process vessel; (d) performing X cycles of sequentially performing (a) and (b); (e) performing a cycle of (d) and (c) Y times; (f) changing X in the next cycle of performing (d) and (c) in accordance with the number of times the cycle of performing (d) and (c) in turn has been performed in (e); the inner wall of the processing vessel is made of quartz; In (f), a film containing the metal element, the Group 15 element, and the Group 14 element or the Group 16 element is formed on the surface of the quartz; forming a pre-coat film having different compositions on a base side and a surface side on a surface of the member in the processing vessel; processing the substrate in the processing chamber after the step of forming the precoat film; A method for manufacturing a semiconductor device having the above structure.

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