Substrate processing method, method for producing semiconductor device, program, and substrate processing device

Abstract

The present invention improves the characteristics of a film formed on a substrate.　The present invention includes: (a) a step in which a raw material is supplied to a substrate; (b) a step in which a reactant is supplied to the substrate; (c) a step in which a regulating agent is supplied to the substrate to regulate the amount of at least one of the molecules of the raw material and the molecules of the reactant adsorbed to the substrate; (d) a step in which at least one of (a) and (b) is performed in an overlapping manner with (c); and (e) a step in which following (d), (a) or (b) that was performed in an overlapping manner with (c) in (d) is performed independently from (c).

Description

SUBSTRATE PROCESSING METHOD, SEMICONDUCTOR DEVICE MANUFACTURING METHOD, PROGRAM, AND SUBSTRATE PROCESSING METHOD

[0001] The present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a program, and a substrate processing apparatus.

[0002] As one step in the manufacturing process of a semiconductor device, a substrate processing step may be performed in which a source gas and a reactive gas are supplied to a substrate to form a film on the substrate (see, for example, Japanese Patent Application Laid-Open No. 2014-135475).

[0003] JP 2014-135475 A

[0004] The present disclosure provides a technique that can improve the properties of a film formed on a substrate.

[0005] According to one aspect of the present disclosure, there is provided a technique comprising: (a) a step of supplying a raw material to a substrate; (b) a step of supplying a reactant to the substrate; (c) a step of supplying an adjuster to the substrate, the adjuster adjusting the amount of at least one of the raw material molecules and the reactant molecules adsorbed to the substrate; (d) a step of performing (c) in an overlapping manner with at least one of (a) and (b); and (e) following (d), a step of performing (a) or (b), which has been performed in (d) in an overlapping manner with (c), independently on (c).

[0006] According to the present disclosure, it is possible to provide a technique that can improve the properties of a film formed on a substrate.

[0007] Fig. 1 is a longitudinal sectional view showing an outline of a vertical processing furnace of a substrate processing apparatus according to an embodiment; Fig. 2 is a schematic transverse sectional view taken along line AA in Fig. 1; Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment, showing a control system of the controller in a block diagram; Fig. 4 is a diagram showing an example of a substrate processing process according to an embodiment; Fig. 5 is a diagram showing an example of a substrate processing process according to an embodiment;

[0008] The following description will be made with reference to Figures 1 to 5. 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.

[0009] (1) Configuration of the Substrate Processing Apparatus 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.

[0010] 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 or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 (hereinafter referred to as MF 209) is disposed concentrically below the outer tube 203. The MF 209 is made of a metal such as stainless steel and has a cylindrical shape with open upper and lower ends. An O-ring 220a is provided as a sealing member between the upper end of the MF 209 and the outer tube 203. The MF 209 is supported on a heater base, so that the outer tube 203 is installed vertically.

[0011] An inner tube 204 constituting a reaction vessel is disposed inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz or SiC, and is formed in a cylindrical shape with a closed upper end and an open lower end. The outer tube 203, the inner tube 204, and the MF 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).

[0012] The processing chamber 201 is configured to accommodate wafers 200 as substrates arranged in multiple stages in the vertical direction in a horizontal position on boats 217 as supports.

[0013] Nozzles 410, 420, and 430 are provided in the processing chamber 201 so as to penetrate the sidewall of the MF 209 and the inner pipe 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.

[0014] Mass flow controllers (MFCs) 312, 322, and 332, which are flow rate controllers (flow rate control parts), are respectively provided on the gas supply pipes 310, 320, and 330 in this order from the upstream side. Also, valves 314, 324, and 334, which are on-off valves, are respectively provided on the gas supply pipes 310, 320, and 330. 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. The gas supply pipes 510, 520, and 530, which are on-off valves, are respectively provided on the gas supply pipes 510, 520, and 530 in this order from the upstream side. 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 respectively provided.

[0015] Nozzles 410, 420, and 430 are connected to the tips of the gas supply pipes 310, 320, and 330, respectively. 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 MF 209 and the inner pipe 204. The vertical portions of the nozzles 410, 420, and 430 protrude radially outward from the inner pipe 204 and are provided inside the channel-shaped (groove-shaped) pre-chamber 201a, which is formed to extend vertically. The vertical portions of the nozzles 410, 420, and 430 are provided in the pre-chamber 201a along the inner wall of the inner pipe 204, facing upward (upward in the arrangement direction of the wafers 200)

[0016] The nozzles 410, 420, and 430 are provided to extend from a lower region of the processing chamber 201 to an upper region of the processing chamber 201. A plurality of gas supply holes 410a, 420a, and 430a are provided in the nozzles 410, 420, and 430 at positions facing the wafer 200. Thus, processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, respectively. The gas supply holes 410a, 420a, and 430a are provided in plurality from the lower portion to the upper portion of the inner tube 204. The gas supply holes 410a, 420a, and 430a each have the same opening area. The gas supply holes 410a, 420a, and 430a are arranged at the same pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-described configuration. For example, the opening areas of the gas supply holes 410 a, 420 a, and 430 a may be gradually increased from the bottom to the top of the inner tube 204. This makes it possible to more uniform the flow rates of gas supplied to the wafers 200 from the gas supply holes 410 a, 420 a, and 430 a.

[0017] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in plurality from the bottom to the top of the boat 217. 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 from the bottom to the top of the boat 217. 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 are preferably provided so as to extend to near the ceiling of the boat 217.

[0018] From the gas supply pipe 310, a raw material is supplied as a processing gas into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410. In this disclosure, the raw material is also referred to as a raw material agent or a source.

[0019] A reactant is supplied as a processing gas from the gas supply pipe 320 into the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420. In this disclosure, the reactant is also referred to as a reactant or a reactant.

[0020] A processing gas, which is different from a reactant and inhibits adsorption of elements contained in the raw material, is supplied from the gas supply pipe 330 into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 430. In the present disclosure, the processing gas is also referred to as a modifier, an adsorption suppressant, a reaction inhibitor, or a surface conditioner.

[0021] In this disclosure, the term "agent" as used herein includes at least one of a gaseous substance and a liquid substance. Liquid substances include mist-like substances. That is, the adjusting agent may contain a gaseous substance, a liquid substance such as a mist-like substance, or both. Furthermore, when a gaseous substance is contained, it can be referred to as a source gas, a reaction gas, or an adjusting gas, respectively.

[0022] From the gas supply pipes 510, 520, and 530, an inert gas such as nitrogen (N ２ ) gases are supplied into the processing chamber 201 via MFCs 512, 522, and 532, valves 514, 524, and 534, and nozzles 410, 420, and 430, respectively. ２ An example using gas will be described. As an inert gas, N ２ In addition to the gas, for example, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas may be used.

[0023] When a raw material is flowed from the gas supply pipe 310, a raw material supply system (first 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 considered to be included in the raw material supply system. When a reactant is flowed from the gas supply pipe 320, a reactant supply system (third 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 considered to be included in the reactant supply system. When an adjuster is flowed from the gas supply pipe 330, a adjuster supply system (second 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 considered to be included in the adjuster supply system. The raw material supply system, the reactant supply system, and the adjuster 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] The gas supply pipe 310 may be provided with a reservoir 701 for storing the processing gas, and a valve 702 at the downstream side (processing chamber 201 ) of the reservoir 701 .

[0025] In this embodiment, gas is delivered into the inner pipe 204 via nozzles 410, 420, and 430 arranged in a preliminary chamber 201a in a circular, vertically elongated space defined by the inner wall of the inner pipe 204 and the ends of the multiple wafers 200. The gas is then ejected into the inner pipe 204 from multiple gas supply holes 410a, 420a, and 430a provided in the nozzles 410, 420, and 430 at positions facing the wafers 200. More specifically, raw materials and the like are ejected in a direction parallel to the surfaces of the wafers 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.

[0026] 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. The gas that flows into the exhaust path 206 then flows into the exhaust pipe 231 and is discharged to the outside of the processing furnace 202.

[0027] The exhaust hole 204a is provided at a position facing the plurality of wafers 200. 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.

[0028] An exhaust pipe 231 for exhausting the atmosphere in the process chamber 201 is connected to an exhaust port 231a provided in the MF 209. The exhaust pipe 231 is connected to, in order from upstream, a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure in the process 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 of the process chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the APC valve 243 can adjust the pressure in the process chamber 201 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.

[0029] A seal cap 219 (hereinafter, SC219) serving as a furnace port cover capable of airtightly closing the lower end opening of the MF 209 is provided below the MF 209. The SC 219 is configured to abut against the lower end of the MF 209 from below in the vertical direction. The SC 219 is made of a metal such as SUS and is formed in a disk shape. An O-ring 220b serving as a seal member abutting against the lower end of the MF 209 is provided on the upper surface of the SC 219. A rotation mechanism 267 is installed on the opposite side of the SC 219 from the process chamber 201, rotating a boat 217 that accommodates wafers 200. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the SC 219. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafers 200. The SC 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 (hereinafter, referred to as BE 115) as a lifting mechanism installed vertically outside the outer tube 203. The BE 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by lifting and lowering the SC 219. The BE 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.

[0030] The boat 217 is configured to hold multiple wafers 200, for example, 25 to 200, arranged horizontally and with their centers aligned and spaced apart in the vertical direction. The boat 217 is made of a heat-resistant material such as quartz or SiC. Dummy substrates 218, also 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 SC 219. However, this embodiment is not limited to the above 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.

[0031] 2, a temperature sensor 263 serving as a temperature detector is installed inside the inner pipe 204. The substrate processing apparatus 10 is configured to adjust the amount of power supplied to the heater 207 based on temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution inside 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 pipe 204.

[0032] 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 connected to the CPU 121a via an internal bus so as to be able to exchange data. An input / output device 122, such as a touch panel, is connected to the controller 121. The substrate processing apparatus may be configured to include one or more control units. That is, control for performing the processing sequence described below may be performed using one control unit or multiple control units. Furthermore, the multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and control for performing the processing sequence described below may be performed by the entire control system. In this specification, when the term "control unit" is used, it may include one control unit, multiple control units, or a control system configured by multiple control units.

[0033] The storage device 121c is configured, for example, with a flash memory or an HDD (Hard Disk Drive). 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 (substrate processing method) described later, and other information. The process recipe is a combination of processes (steps) in a semiconductor device manufacturing method (substrate processing method) described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe and the control program 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 for temporarily storing programs, data, and other information read by the CPU 121a.

[0034] 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, 702, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, BE 115, etc.

[0035] The CPU 121 a is configured to read and execute a control program from the storage device 121 c, and also to read a process recipe or the like from the storage device 121 c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a is configured to be able to control, in accordance with the contents of the read process recipe, the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 512, 522, and 532, the opening and closing operation of the valves 314, 324, 334, 514, 524, 534, and 702, the gas storage operation in the storage section 701 by the valve 702, the opening and closing operation of the APC valve 243, 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 BE 115, and the operation of storing the wafers 200 in the boat 217.

[0036] The controller 121 can be configured by installing the above-mentioned program stored in an external storage device (e.g., a magnetic disk such as a hard disk, an optical disk such as a CD or DVD, or a semiconductor memory such as a USB memory or a memory card) 123 onto 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 storage device 121c and the external storage device 123. The program (program product) 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.

[0037] (2) Substrate Processing Step As one step in the manufacturing process of a semiconductor device, an example of a step of forming a silicon nitride (SiN) film, which is used as a charge trap film for 3D NAND, on a wafer 200 will be described with reference to FIGS. 4 and 5 . The step of forming the SiN film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. Note that in this embodiment, an example will be described in which the wafer 200 is a substrate (wafer) having recesses such as trenches and holes formed in its surface. In the following description, the operation of each component of the substrate processing apparatus 10 is configured to be controllable by the controller 121.

[0038] In the substrate processing process (semiconductor device manufacturing process) according to this embodiment, the following steps are performed a predetermined number of times to form a film of elements contained in the raw material on the wafer 200: (a) a step of supplying raw material to the wafer 200; (b) a step of supplying a reactant to the wafer 200; (c) a step of supplying an adjuster to the wafer 200, which adjusts the amount of at least one of raw material molecules and reactant molecules adsorbed on the wafer 200; (d) a step of overlapping at least one of (a) and (b) with (c); and (e) following (d), a step of independently performing (a) or (b), which was performed in (d) while overlapping with (c), on (c).

[0039] In the present disclosure, the above-described film formation sequence includes the sequences shown in (A) to (J) below. The same notations as those below will be used in the description of other embodiments. Note that (A) to (E) below correspond to (A) to (E) in FIG. 4. (F) to (H) below correspond to (F) to (H) in FIG. 5.

[0040] (A) (modifier → raw material + modifier → raw material → reactant) × Xa (B) (modifier + raw material + modifier → reactant) × Xb (C) (raw material → raw material + modifier → raw material → reactant) × Xc (D) (raw material → raw material + modifier → reactant) × Xd (E) (raw material → raw material + modifier → modifier → reactant) × Xe (F) (raw material → modifier → reactant + modifier → reactant) × Xf (G) (raw material → reactant + modifier → reactant) × Xg (H) (raw material → reactant → reactant + modifier → reactant) × Xh (I) (raw material → reactant + modifier → reactant) × Xi (J) (raw material → reactant → reactant + modifier → modifier) ​​× Xj Here, Xa to Xj are natural numbers (integers of 1 or greater). "→" means to supply in order, and "+" means to supply simultaneously. The simultaneous supply means that there is an overlapping period. The purge shown in Figures 4 and 5 is not necessarily required, and is therefore omitted from the above description.

[0041] 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."

[0042] 1, the boat 217 supporting the wafers 200 is lifted by the BE 115 and loaded into the processing chamber 201. The boat 217 supporting the wafers 200 is then housed in the processing vessel. In this state, the SC 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0043] (Pressure Regulation and Temperature Regulation) The processing chamber 201 is evacuated by the vacuum pump 246 so that the processing chamber 201, i.e., the space in which the wafer 200 is present, reaches a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245. Then, based on the pressure information measured by the pressure sensor 245, the APC valve 243 is feedback-controlled (pressure regulation). The vacuum pump 246 remains in a constantly operating state at least until the processing of the wafer 200 is completed. Furthermore, the processing chamber 201 is heated by the heater 207 so that the processing chamber 201 reaches a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the processing chamber 201 achieves a desired temperature distribution (temperature regulation). Heating of the processing chamber 201 by the heater 207 continues at least until the processing of the wafer 200 is completed.

[0044] (Adjusting Agent Supply Process: First Process) The controller 121 opens the valve 334 to flow the adjusting agent into the gas supply pipe 330. The adjusting agent is supplied into the processing chamber 201 from the gas supply hole 430a of the nozzle 430 after the flow rate is adjusted by the MFC 332. The adjusting agent supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. At this time, the adjusting agent is supplied to the wafer 200. At this time, the controller 121 opens the valve 534 to supply N 2 into the gas supply pipe 530. ２ An inert gas such as N gas may be flowed through the gas supply pipe 530. ２ The gas is supplied into the processing chamber 201 together with the adjusting agent after the flow rate is adjusted by the MFC 532. ２ The gas is exhausted from the exhaust pipe 231. At this time, in order to prevent the adjusting agent from entering the nozzles 410 and 420, the controller 121 opens the valves 512 and 524 to supply N 2 into the gas supply pipes 510 and 520. ２ Gas may be flowed. ２ Gas is supplied into the processing chamber 201 through gas supply pipes 310 and 320 and nozzles 410 and 420 and is exhausted from an exhaust pipe 231 .

[0045] At this time, the controller 121 adjusts the APC valve 243 to set the pressure in the processing chamber 201 to, for example, a pressure in the range of 1 to 3990 Pa, for example, 1000 Pa. The supply flow rate of the adjuster controlled by the MFC 332 is set to, for example, a flow rate in the range of 0.005 to 5.0 slm. Here, the controller 121 adjusts the pressure in the processing chamber 201 and the supply flow rate and supply time of the adjuster into the processing chamber 201 so that the exposure amount of the adjuster to the wafer 200 becomes a first exposure amount. Note that the first exposure amount in the present disclosure is calculated, for example, by the product of the partial pressure of the adjuster in the processing chamber 201 and the supply time of the adjuster into the processing chamber 201 (partial pressure x time). Furthermore, the first exposure amount is less than a second exposure amount, which will be described later. The N controlled by the MFCs 512, 522, and 532 ２ The gas supply flow rate is set to, for example, a range of 0.1 to 5.0 slm, in order to prevent gas containing a Group 15 element from entering each of the nozzles 410, 420, and 430. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is, for example, 250 to 800°C, preferably 600 to 700°C. 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. The first exposure amount may be the product of the supply flow rate of the adjuster into the processing chamber 201 and the supply time (supply flow rate × supply time), the product of the total pressure in the processing chamber 201 and the supply time of the adjuster into the processing chamber 201 (total pressure × supply time), or the product of the partial pressure (total pressure) in the processing chamber 201 and the supply flow rate and supply time of the adjuster into the processing chamber 201 (partial pressure (total pressure) × supply flow rate × supply time). The supply flow rate of the adjuster into the processing chamber 201 is affected by the volume of the processing vessel, the pattern of the recesses formed on the wafer 200, and the like. Therefore, it is preferable that the first exposure amount be the product of the partial pressure in the processing chamber 201 and the supply time of the adjuster into the processing chamber 201.

[0046] Preferably, the exposure amount of the adjuster to the wafer 200 (first exposure amount, adsorption amount) is an amount at which the adjuster molecules are saturated and adsorbed to the wafer 200. More preferably, the exposure amount of the adjuster to the wafer 200 (first exposure amount) is an amount at which the adjuster molecules are saturated and adsorbed to the opening side of the recess (upper side of the recess) of the wafer 200 having a recess formed on its surface. In other words, preferably, the exposure amount of the adjuster to the wafer 200 is an amount at which the adsorption of the adjuster molecules to the wafer 200 is saturated. More preferably, the exposure amount of the adjuster to the wafer 200 is an amount at which the adsorption of the adjuster molecules to the opening side of the recess (upper side of the recess) of the wafer 200 having a recess formed on its surface is saturated.

[0047] In the present disclosure, "saturation" does not necessarily mean that all adsorption sites on the wafer 200 are filled, but rather that the adsorption site is substantially saturated. In other words, to improve productivity, a state that is not completely saturated is acceptable, in other words, a state in which the reaction has not completely converged. Furthermore, in a combination of a gas species and a film species in which the characteristics of the reaction amount versus gas supply time have a saturation curve in a region longer than a certain supply time, a state that is not completely saturated on the saturation curve may also be referred to as saturated adsorption in the present disclosure. A single supply time on the saturation curve can achieve at least one of the effects of the present disclosure. Setting the supply time within a supply time region in which such a saturation curve is obtained can also be referred to as supply utilizing saturated adsorption characteristics.

[0048] The conditioning agent supplied to the wafer 200 is, for example, a halogen-containing agent. The halogen-containing agent is a substance containing at least one of Group 17 elements. Examples of such substances include hydrogen halide agents such as hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), and hydrogen iodide (HI). The conditioning agent may also be a substance composed of a halogen element, such as fluorine (F ２ ), chlorine (Cl ２ ), bromine (Br ２ ), and iodine (I ２ ) and the adjuster may be nitrogen trifluoride (NF ３ ), and chlorine trifluoride (ClF３ ) may be a substance containing two types of halogen elements. Preferably, a substance with high polarity is used as the adjuster. Such a substance with high polarity is, for example, a hydrogen halide, specifically HCl. Molecules of such a substance with high polarity are easily adsorbed to the wafer 200. Furthermore, a substance with high polarity can suppress the adsorption of the raw material itself, as described below, as well as the adsorption of decomposition products (decomposition products) generated by the decomposition of the raw material. When the adsorption to the wafer 200 is not taken into consideration, it is preferable to use an adjuster containing Cl. ２ A substance such as the following can be used. ２ Although Cl has a smaller polarizability than the hydrogen halide, its molecular size is larger than that of the hydrogen halide. ２ The large molecular size of the SiO2 has the effect of preventing the adsorption of raw material molecules and decomposition products generated by the decomposition of the raw material. In other words, the adsorption inhibitors act as steric hindrance. The decomposition products of the raw material may be generated on the surface of the wafer 200 or in the space above the wafer 200.

[0049] By supplying such an adjusting agent to the wafer 200, adsorption inhibitors are formed on the surface of the wafer 200. The adsorption inhibitors are molecules containing halogen elements or halogen elements themselves.

[0050] Furthermore, by exposing (supplying) the adjuster to the wafer 200 at a first exposure amount, the adjuster molecules or a portion of the adjuster molecules can be adsorbed onto the upper side of the recess formed on the surface of the wafer 200.

[0051] The adjuster is not limited to the inorganic substances described above, but may be an organic adjuster. An organic adjuster is, for example, a substance containing an alkyl group (alkyl ligand). The alkyl group is, for example, a methyl group. The methyl group is electrically negative and repels the negative source molecules, making it difficult for the methyl group to bond with the source molecules. For example, a methyl group (Me-) and a halogen (Cl-) contained in a source molecule are both electrically negative and therefore difficult to bond with each other. Here, Me means methyl. In other words, by adsorbing a substance containing an alkyl group to a specific location on the wafer 200, it is possible to prevent subsequently supplied source materials from being adsorbed to the specific location on the wafer 200. Examples of substances containing an alkyl group include hexamethyldisilazane, dimethylaminotrimethylsilane, trimethylsilanol, and triethylsilanol.

[0052] After a predetermined time has elapsed since the start of supply of the adjuster, for example, 1 to 600 seconds, the controller 121 closes the valve 334 of the gas supply pipe 330 to stop the supply of the adjuster. At this time, the controller 121 leaves the APC valve 243 of the exhaust pipe 231 open and causes the vacuum pump 246 to evacuate the processing chamber 201, thereby removing from the processing chamber 201 any adjuster that remains unreacted or that has contributed to the formation of adsorption inhibitors.

[0053] As shown in FIGS. 4 and 5, the timing of performing the first step is adjusted as appropriate.

[0054] (Source Material Supply Process: Second Process) The controller 121 opens the valve 314 to flow the source material into the gas supply pipe 310. The source material is supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410 after the flow rate is adjusted by the MFC 312. The source material supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. In this way, the source material is supplied to the wafer 200. At this time, the controller 121 opens the valve 514 to supply N 2 into the gas supply pipe 510. ２ An inert gas such as N 2 gas is flowed through the gas supply pipe 510. ２ The gas is supplied into the processing chamber 201 together with the raw material after the flow rate is adjusted by the MFC 512.２ The gas is exhausted from the exhaust pipe 231. At this time, in order to prevent the raw material from entering the nozzles 420 and 430, the controller 121 opens the valves 524 and 534 to supply N 2 into the gas supply pipes 520 and 530. ２ Gas may be flowed. ２ The gas is supplied into the processing chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430 , and then exhausted from the exhaust pipe 231 .

[0055] At this time, the controller 121 adjusts the APC valve 243 to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 3990 Pa, for example, to 500 Pa. The supply flow rate of the raw material controlled by the MFC 312 is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. Here, the raw material supply conditions are set so that the amount of exposure of the raw material to the wafer 200 is a second exposure amount that is greater than the first exposure amount. Note that the second exposure amount in this disclosure is, for example, the product of the partial pressure of the raw material inside the processing chamber 201 and the supply time of the raw material into the processing chamber 201 (partial pressure x time). The N controlled by the MFCs 512, 522, and 532 ２ The gas supply flow rates are set to, for example, a range of 0.1 to 5.0 slm. The temperature of the heater 207 is set so that the temperature of the wafer 200 is, for example, 250 to 800°C, preferably 600 to 700°C. The second exposure amount in the present disclosure may also be the product of the supply flow rate of the source material into the processing chamber 201 and the supply time (supply flow rate × supply time), the product of the total pressure in the processing chamber 201 and the supply time of the source material into the processing chamber 201 (total pressure × supply time), or the product of the partial pressure (total pressure) in the processing chamber 201, the supply flow rate of the source material into the processing chamber 201, and the supply time (partial pressure (total pressure) × supply flow rate × supply time). The supply flow rate of the source material into the processing chamber 201 is affected by the volume of the processing vessel, the pattern of the recesses formed on the wafer 200, and the like. Therefore, the second exposure amount is preferably the product of the partial pressure in the processing chamber 201 and the supply time of the source material into the processing chamber 201.

[0056] Furthermore, the amount of gas exposure to the wafer 200 in this disclosure can also be rephrased as the amount of gas molecules adsorbed on the surface of the wafer 200. As described above, this amount of adsorption can be adjusted, for example, by the product (partial pressure x time) of the partial pressure of the gas (adjuster or raw material) in the process chamber 201 and the supply time of the gas (adjuster is raw material) into the process chamber 201.

[0057] In the present disclosure, the second exposure amount (adsorption amount) can be made larger than the first exposure amount (adsorption amount) by adjusting at least one of the partial pressure, total pressure, supply flow rate, and supply time related to the second exposure amount to be larger than at least one of the partial pressure, total pressure, supply flow rate, and time related to the first exposure amount.

[0058] 7, the second exposure amount (adsorption amount) of the source material is preferably an amount that does not cause saturation of adsorption of the source material molecules onto the wafer 200. In other words, the second exposure amount (adsorption amount) of the source material is preferably an amount that does not cause saturation of adsorption of the source material molecules onto the wafer 200.

[0059] The raw material may be stored in the storage section 701 and supplied from the storage section 701 into the processing chamber 201. When the raw material stored in the storage section 701 is supplied into the processing chamber 201, the supply time of the raw material into the processing chamber 201 may be shorter than the supply time of the adjuster into the processing chamber 201. In this case, for example, the exposure amounts (first exposure amount and second exposure amount) of the raw material and the adjuster are adjusted so that the product of the partial pressure (total pressure) of the raw material in the processing chamber 201 and the supply time of the raw material into the processing chamber 201 is greater than the product of the partial pressure (total pressure) of the adjuster in the processing chamber 201 and the supply time of the adjuster into the processing chamber 201. In the raw material supply step (third step), the raw material may be supplied into the processing chamber 201 not only once but also multiple times. When the supply of the raw material into the processing chamber 201 is performed multiple times, the supply of the raw material into the processing chamber 201 is stopped between a predetermined supply and the next supply. Furthermore, when the supply of the raw material into the processing chamber 201 is performed multiple times, the raw material stored in the storage section 701 may be supplied into the processing chamber 201 at least once. For example, when the supply of the raw material into the processing chamber 201 is performed two or more times, the raw material stored in the storage section 701 is supplied into the processing chamber 201 the first time, and the raw material is supplied into the processing chamber 201 without being stored in the storage section 701 the second time. Note that the supply of the raw material into the processing chamber 201 is stopped between the first and second times. Furthermore, the processing chamber 201 may be evacuated (reduced in pressure) in accordance with the stop of the supply of the raw material into the processing chamber 201, or an inert gas may be supplied into the processing chamber 201 in accordance with the evacuation. The supply and stop of the raw material into the processing chamber 201 is controlled by, for example, opening and closing a valve 702 .

[0060] The raw material supplied to the wafer 200 includes, for example, a main element constituting the film formed on the wafer 200. The main element is, for example, Si. For example, a silane-based gas containing Si can be used as the raw material. For example, a gas containing Si and a halogen, i.e., a halosilane gas, can be used as the silane-based gas. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. For example, a chlorosilane gas containing Si and Cl can be used as the halosilane gas.

[0061] The raw material is, for example, monochlorosilane (SiH ３ Cl) gas, dichlorosilane (SiH ２ Cl ２ ) gas, trichlorosilane (SiHCl ３ ) gas, tetrachlorosilane (SiCl ４ ) gas, hexachlorodisilane gas (Si ２ Cl ６ , abbreviated as HCDS) gas and octachlorotrisilane (Si ３ Cl ８ As the raw material, one or more of these can be used.

[0062] As the raw material, in addition to chlorosilane gas, for example, tetrafluorosilane (SiF4) gas, difluorosilane (SiH ２ F ２ ) gas, tetrabromosilane (SiBr ４ ) gas, dibromosilane (SiH ２ Br ２ ) gas, bromosilane gas such as tetraiodosilane (SiI ４ ) gas, diiodosilane (SiH ２ I ２ As the raw material, one or more of these can be used.

[0063] In addition to these, a gas containing Si and an amino group, i.e., an aminosilane gas, can also be used as a raw material. An amino group is a monovalent functional group formed by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and is represented by -NH ２ , -NHR, -NR ２ where R represents an alkyl group, and —NR ２ The two R's may be the same or different.

[0064] The raw material is, for example, tetrakis(dimethylamino)silane (Si[N(CH ３ ) ２ ] ４) gas, tris(dimethylamino)silane (Si[N(CH ３ ) ２ ] ３ H) gas, bis(diethylamino)silane (Si[N(C ２ H ５ ) ２ ] ２ H ２ ) gas, bis(tert-butylamino)silane (SiH ２ [NH(C ４ H ９ )] ２ ) gas, and (diisopropylamino)silane (SiH ３ [N(C ３ H ７ ) ２ As the raw material, one or more of these can be used.

[0065] In this disclosure, an example using HCDS gas as a source material will be described. When HCDS gas is used as a source material, a silicon (Si)-containing layer containing chlorine (Cl) of a predetermined thickness can be formed as a first layer on the top surface of the wafer 200. The Cl-containing Si-containing layer can be formed on the top surface of the wafer 200 by physical adsorption or chemical adsorption of source material molecules, physical adsorption or chemical adsorption of molecules of a substance formed by decomposition of at least a portion of the source material molecules (also referred to as a decomposition product), or deposition of Si due to thermal decomposition of the source material. In this disclosure, the decomposition product is also referred to as a ligand of the source material or a portion of the ligand of the source material. When HCDS is used as a source material, the decomposition product is, for example, SiClx, where x is 2, 3, or 4. The Cl-containing Si-containing layer can be an adsorption layer (physical adsorption layer or chemical adsorption layer) of chlorosilane gas molecules or molecules of a substance formed by decomposition of a portion of the chlorosilane gas, or a deposition layer of Cl-containing Si. When the above-described chemical adsorption layer or the above-described deposition layer is formed on the outermost surface of the wafer 200, Si contained in the chlorosilane gas is adsorbed onto the outermost surface of the wafer 200. In the present disclosure, the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.

[0066] Furthermore, before the supply of HCDS gas, a regulator is supplied, and the regulator may form adsorption inhibitors on the surface of the wafer 200. For example, this is the case in sequence (A) of FIG. 4. When HCl gas is used as the regulator, adsorption inhibitors such as HCl and Cl, which is a part of HCl, are formed on the surface of the wafer 200. Such adsorption inhibitors suppress the adsorption of HCDS gas molecules and SiClx. In other words, the presence of adsorption inhibitors can suppress the adsorption of some of the ligands of the raw material. Furthermore, depending on the structure of the molecules (atoms) that make up the adsorption inhibitors, it is possible to suppress the adsorption of a specific number x of SiClx molecules among SiClx molecules.

[0067] The raw material supply period (also referred to as timing) and the adjuster supply period can be set as shown in (A), (B), (C), (D), and (E) of Figure 4. In this disclosure, the "supply period" refers to the time required from the start of supplying raw materials (adjuster, reactants described below) to the stop of supplying them.

[0068] 4A, 4B, 4C, 4D, and 4E, there is a period in which the supply of the raw material and the supply of the adjuster overlap, in other words, there is a period in which the raw material and the adjuster are supplied to the wafer 200 simultaneously.

[0069] Also, as shown in (C), (D), and (E) of FIG. 4, the supply of the adjusting agent can be started after the supply of the raw material has started.

[0070] Also, as shown in (A), (B), and (C) of FIG. 4, there may be a period in which the raw material is supplied after the supply of the adjuster is stopped.

[0071] Also, as shown in FIG. 4A, there may be a period in which the adjuster is supplied alone before the supply of the raw material is started.

[0072] 4(E), there may be a period in which the adjuster is supplied alone after the supply of the raw material is stopped. This is also referred to as continuing the supply of the adjuster after the supply of the raw material is stopped.

[0073] (Removal of Residual Gas) After a predetermined time has elapsed since the start of the supply of raw materials, for example, 1 to 60 seconds, the controller 121 closes the valve 314 of the gas supply pipe 310 to stop the supply of raw materials. That is, the time for supplying raw materials to the wafer 200 is set to, for example, a time within a range of 1 to 60 seconds. At this time, the controller 121 leaves the APC valve 243 of the exhaust pipe 231 open and causes the vacuum pump 246 to evacuate the processing chamber 201, thereby removing any raw materials remaining in the processing chamber 201 that have not reacted or that have contributed to layer formation. That is, the controller 121 evacuates the atmosphere in the processing chamber 201. At this time, the controller 121 leaves the valves 514, 524, and 534 open and causes the N ２ The supply of gas into the processing chamber 201 may be maintained. ２ The gas acts as a gas for suppressing the intrusion of gas into each of the nozzles 410, 420, and 430, and also acts as a purge gas. ２ When the gas is supplied, it is possible to enhance the effect of removing raw materials remaining in the processing chamber 201 that have not reacted or that have contributed to layer formation from the processing chamber 201 .

[0074] (Reactant Supply: Third Step) After removing the residual gas from the processing chamber 201, the controller 121 opens the valve 324 to flow the reactant into the gas supply pipe 320. The reactant is supplied into the processing chamber 201 from the gas supply hole 420a of the nozzle 420 after the flow rate is adjusted by the MFC 322. The reactant supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. At this time, the reactant is supplied to the wafer 200. At this time, the controller 121 also controls the flow rate of N 2 gas into the gas supply pipes 510, 520, and 530 while keeping the valves 514, 524, and 534 open. ２ The gas supply is maintained. N2 flows through the gas supply pipes 510, 520, and 530. ２ The flow rates of the gases are adjusted by MFCs 512, 522, and 532. N ２ The gas is supplied into the processing chamber 201 together with the reactants through the gas supply pipe 320 and the nozzle 420, and then exhausted from the exhaust pipe 231. ２The gas is supplied into the processing chamber 201 through the gas supply pipe 330 and the nozzle 430, and then exhausted from the exhaust pipe 231. ２ The gas is supplied into the processing chamber 201 through the gas supply pipe 310 and the nozzle 410, and then exhausted from the exhaust pipe 231. This prevents reactants from entering the nozzle 410.

[0075] At this time, the controller 121 adjusts the APC valve 243 to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 13,300 Pa, for example, 5,000 Pa. The supply flow rate of the reactant controlled by the MFC 322 is set within a range of, for example, 1 to 50 slm, preferably 15 to 40 slm. ２ The supply flow rates of the gases are set within the range of, for example, 0.1 to 5.0 slm.

[0076] The exposure amount (adsorption amount) of the reactant to the wafer 200 is preferably an amount that saturates the adsorption of the reactant molecules to the wafer 200. In other words, the exposure amount (adsorption amount) of the reactant to the wafer 200 is preferably an amount that saturates the adsorption of the reactant molecules to the wafer 200.

[0077] The reactant supplied to the wafer 200 may be, for example, a nitrogen (N) and hydrogen (H) containing gas, which is a nitriding gas (nitriding agent). The N and H containing gas may be both an N containing gas and an H containing gas. The N and H containing gas preferably has an N-H bond.

[0078] The reactant may be, for example, ammonia (NH ３ ) gas, diazene (N ２ H ２ ) gas, hydrazine (N ２ H ４ ) gas, and N ３ H ８ A hydrogen nitride gas, such as a nitrogen-containing gas, can be used. One or more of these can be used as the reactant. When the reactant contains hydrogen, the reactant can be called a reducing agent. When the reducing agent is a gas, it can also be called a reducing gas.

[0079] In addition to these, gases containing nitrogen (N), carbon (C), and hydrogen (H) can also be used as reactants. Examples of gases containing N, C, and H include amine-based gases and organic hydrazine-based gases. The gas containing N, C, and H can be an N-containing gas, a C-containing gas, an H-containing gas, or an N- and C-containing gas.

[0080] The reactant may be, for example, monoethylamine (C ２ H ５ NH ２ ) gas, diethylamine ((C ２ H ５ ) ２ NH) gas, triethylamine ((C ２ H ５ ) ３ N) gas, and monomethylamine (CH ３ NH ２ ) gas, dimethylamine ((CH ３ ) ２ NH) gas, trimethylamine ((CH ３ ) ３ Methylamine-based gases such as monomethylhydrazine ((CH ３ ) HN ２ H ２ ) gas, dimethylhydrazine ((CH ３ ) ２ N ２ H ２ ) gas, trimethylhydrazine ((CH ３ ) ２ N ２ (CH ３ Organic hydrazine-based gases such as HCl, ...

[0081] As shown in FIG. 5, the adjusting agent may be supplied in the vicinity of the period in which the reactants are supplied.

[0082] 5(F), (G), (H), (I), and (J), the sequence may be configured to include a period in which the supply of the reactant and the supply of the conditioning agent overlap, i.e., a period in which the reactant and the conditioning agent are simultaneously supplied to the wafer 200.

[0083] Alternatively, as shown in FIG. 5F, the modifier may be fed alone before the reactants are fed.

[0084] Also, as shown in (I) and (J) of FIG. 5, the supply of the adjuster can be started after the supply of the reactants has started.

[0085] 5(J), the adjuster can be supplied alone after the supply of the reactants is stopped, which is also referred to as continuing the supply of the adjuster after the supply of the reactants is stopped.

[0086] (Removal of Residual Gas) After a predetermined time has elapsed since the start of the supply of the reactants, for example, 1 to 1200 seconds, the controller 121 closes the valve 324 of the gas supply pipe 320 to stop the supply of the reactants. Then, by a processing procedure similar to that of the second step described above, any unreacted reactants or reaction by-products remaining in the processing chamber 201 or that have contributed to the formation of a layer are removed from the processing chamber 201. That is, the controller 121 exhausts the atmosphere in the processing chamber 201.

[0087] (Performed a predetermined number of times) By performing the cycle of sequentially performing the above-mentioned first, second, and third steps at least once (a predetermined number of times (n times, where n is an integer of 1 or 2 or more)), a film of the elements contained in the raw material having a predetermined thickness is formed on the wafer 200. For example, a SiN film can be formed on the wafer 200. It is preferable to repeat the above-mentioned cycle multiple times.

[0088] (Purge and atmospheric pressure return) The controller 121 supplies N ２ The gas is supplied into the processing chamber 201. ２ The gas is exhausted from the exhaust pipe 231. ２The gas acts as a purge gas. As a result, the inside of the processing chamber 201 is purged with the inert gas, and gases and reaction by-products remaining in the processing chamber 201 are removed from the inside of the processing chamber 201. Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is returned to normal pressure.

[0089] (Wafer Unloading) Thereafter, the SC 219 is lowered by the BE 115 to open the lower end of the outer tube 203. Then, the processed wafers 200 supported by the boat 217 are unloaded from the lower end of the outer tube 203 to the outside of the outer tube 203. Thereafter, the processed wafers 200 are removed from the boat 217.

[0090] (3) Effects of this Embodiment According to this embodiment, one or more of the following effects can be obtained.

[0091] (a) By supplying the adjuster to the wafer 200, it is possible to prevent a large amount of raw material from being adsorbed to a specific location on the wafer 200. Therefore, it is possible to prevent the film thickness at a specific location on the wafer 200 from increasing, and to increase the film thickness at other locations. Furthermore, it is possible to allow raw material molecules adsorbed to a specific location on the wafer 200 to reach other locations. In other words, it is possible to reduce the amount of raw material consumed at a specific location on the wafer 200 and increase the amount of raw material consumed at other locations on the wafer 200. Here, the specific location may be, for example, the following location: a location close to the nozzle of the wafer 200, or, if a recess is formed on the wafer 200, the upper side of the recess. When the specific location is close to the nozzle of the wafer 200, it is possible to improve the film thickness uniformity within the wafer 200 as a film characteristic. When the specific location is the upper side of the recess, it is possible to reduce the amount of raw material adsorbed (consumption) at the upper side of the recess and increase the amount of raw material adsorbed (consumption) at the bottom side of the recess. This improves the uniformity of the film thickness in the depth direction of the recess, for the film formed on the wall or bottom of the recess. That is, it improves the step coverage as a film characteristic. Here, the recess refers to a trench or a hole. The hole may also include a blind hole or a through hole.

[0092] (b) Even when a gas that decomposes in the gas phase is used as a raw material, the uniformity of the film formed on the wafer 200, particularly the step coverage of the recessed portion, can be improved. The gas that decomposes in the gas phase is, for example, a chlorosilane-based gas, specifically, HCDS gas. When HCDS is used, the decomposition of HCDS produces decomposition products such as SiCl ２ and SiCl ４ Among these, SiCl ２ A CVD reaction occurs for the above. The occurrence of the CVD reaction prevents the relationship between the time the source material is supplied to the wafer 200 and the increase in the film thickness of the wafer 200 (film thickness per cycle) from becoming saturated. In other words, an unsaturated characteristic is obtained. Note that the unsaturated characteristic means that the film thickness of the wafer 200 (film thickness per cycle) does not converge to a predetermined value even if the time the source material is supplied to the wafer 200 increases. If a film is formed on the wafer 200 under conditions that result in this unsaturated characteristic, the film thickness at a specific location on the wafer 200 increases, which may result in a deterioration in the film thickness uniformity of the wafer 200. The characteristic of the film formed in the recessed portion may be a deterioration in step coverage. According to the technology disclosed herein, by supplying an adjuster to the wafer 200, the SiCl ２ It is possible to suppress the adsorption of intermediates that cause unsaturated properties such as SiCl onto the wafer 200. As a result, it is possible to improve the film thickness uniformity of the wafer 200. Furthermore, when a wafer 200 having a recess is processed, it is possible to improve the step coverage of the film formed in the recess. Among such decomposition products, SiCl ２ The amount of SiCl produced is proportional to the time that HCDS gas is supplied to the wafer 200. That is, as the time that HCDS gas is supplied to the wafer 200 increases, the amount of SiCl produced increases. ２ The amount of SiCl produced increases. ２The increase in the amount of SiCl produced is due to the fact that the residence time of HCDS molecules in the processing chamber 201 increases with the increase in the supply time of HCDS to the wafer 200. That is, when the residence time of HCDS molecules in the processing chamber 201 increases, the time for which the HCDS molecules are heated in the processing chamber 201 increases, and the number of molecules that are thermally decomposed increases. ２ The amount of SiCl produced and the amount of SiCl ２ In order to reduce the amount of adsorption, it is preferable to reduce the supply time of HCDS gas to the wafer 200. In order to reduce the supply time of HCDS gas to the wafer 200, it is preferable to use the reservoir 701 to instantaneously supply (also called flush supply) HCDS gas to the wafer 200.

[0093] (c) By using an inorganic adjuster (e.g., a gas containing a halogen element) as the adjuster, it is possible to reduce the increase in the amount of impurities caused by the adjuster in the film formed on the wafer 200. Here, impurities are elements other than the main elements constituting the film formed on the wafer 200. On the other hand, the molecular size of organic adjusters is larger than that of inorganic adjusters. Therefore, when an organic adjuster is used as the adjuster, the effect of the adjuster acting as a steric hindrance that inhibits the adsorption of raw materials onto the wafer 200 is greater than when an inorganic adjuster is used as the adjuster.

[0094] (d) As shown in (A), (B), (C), (D), and (E) of Figure 4, there is a period in which the supply of raw material and the supply of adjuster overlap. During such a period, the adjuster can prevent raw material molecules present in the space above the wafer 200 from adsorbing to the wafer 200. Furthermore, it can prevent the adsorption of raw material molecules that are not completely adsorbed to the wafer 200. This makes it possible to adjust the amount of raw material molecules adsorbed to the wafer 200. It can also prevent multiple adsorption of raw material molecules to the wafer 200. Here, multiple adsorption means that multiple raw material molecules are adsorbed to a specific location on the wafer 200.

[0095] 4C, 4D, and 4E, by starting the supply of the adjuster after starting the supply of the raw material, in addition to the effect of (d), it is possible to prevent intermediates of the raw material generated after the start of the supply of the raw material from adsorbing to the wafers 200. The adjuster inhibits the intermediates of the raw material from adsorbing to the wafers 200.

[0096] (f) As shown in (A), (B), and (C) of Figure 4, by providing a period of supplying raw material after the supply of the adjusting agent is stopped, it is possible to increase the amount of raw material adsorbed to areas of the wafer 200 where the adjusting agent is not adsorbed.

[0097] 4A, by providing a period in which the adjuster is supplied alone before the supply of the raw material is started, a layer of adjuster molecules adsorbed on the surface of the wafer 200 can be formed. By forming this layer, the amount of raw material molecules adsorbed on the wafer 200 can be reduced.

[0098] (h) As shown in (E) of Figure 4, by providing a period in which the adjuster is supplied after the supply of the raw material is stopped, it is possible to prevent raw material molecules present in the space above the wafer 200 from being adsorbed to the wafer. Furthermore, it is possible to prevent adsorption of raw material molecules that are not completely adsorbed to the wafer 200. The adjuster after the supply of the raw material in sequence (E) is also called removing (purging) the raw material.

[0099] (i) In the sequence of the comparative example of Figure 4, the adjuster adsorbed to the wafer 200 has the effect of suppressing the adsorption of raw material molecules to the wafer 200. In the sequences (A), (B), (C), (D), and (E), in addition to the effects of the comparative example, the above-mentioned effects can be obtained and the time required for each sequence cycle can be shortened. That is, in the sequences (A), (B), (C), (D), and (E), the processing time of the wafer 200 can be shortened compared to the comparative example. That is, the manufacturing throughput of semiconductor devices can be improved.

[0100] (j) As shown in (F), (G), (H), (I), and (J) of FIG. 5 , by providing a period in which the supply of the reactant and the supply of the adjuster overlap, the adjuster can prevent reactant molecules present in the space above the wafer 200 from adsorbing to the wafer 200. Furthermore, it is possible to prevent adsorption of reactant molecules that are not completely adsorbed to the wafer 200. Furthermore, it is possible to desorb reactant molecules or parts of molecules adsorbed to the wafer 200. It is also possible to prevent multiple adsorption of reactant molecules or parts of molecules to the wafer 200.

[0101] (k) As shown in Fig. 5F, by supplying an adjuster before supplying the reactant, it is possible to suppress the reactant from being adsorbed onto the wafer 200. In addition, it is possible to suppress multiple adsorption of molecules or parts of molecules of the reactant onto the wafer 200.

[0102] 5(I) and 5(J), by starting the supply of the adjuster after starting the supply of the reactant, it is possible to remove the reactant molecules from the surface side of the reactant molecules that are multiply adsorbed on the wafer 200 by the adjuster. Note that when the raw material is a material containing Si, the reactant is an agent containing nitrogen and hydrogen, and the adjuster is an agent containing halogen, it is possible to reduce at least the amount of nitrogen from the surface of the wafer 200, and it is possible to suppress a decrease in the refractive index of the film formed on the wafer 200.

[0103] (m) As shown in (J) of Figure 5, by supplying the adjuster after stopping the supply of the reactant, the amount of reactant present in the space above the wafer 200 is small, making it easy to reduce the number of reactant molecules adsorbed on the wafer 200. This makes it possible to prevent the reactant desorbed from the wafer 200 from re-adsorbing on the wafer 200. This is because the reactant can be evacuated before being re-adsorbed on the wafer 200. During the period when the adjuster is supplied alone, the adjuster is also referred to as removing (purging) the reactant.

[0104] (n) In the sequence of the comparative example of FIG. 5 , the adjuster supplied to the wafer 200 has the effect of suppressing adsorption of reactant molecules to the wafer 200. In the sequence (F), (G), (H), (I), and (J), in addition to the effects of the comparative example, the above-mentioned effects can be obtained, and the time required for each sequence cycle can be shortened. That is, in the sequence (F), (G), (H), (I), and (J), the processing time for the wafer 200 can be shortened compared to the comparative example. That is, the manufacturing throughput of semiconductor devices can be improved. Note that, although the comparative example of FIG. 5 shows an example in which the adjuster is supplied before the reactant is supplied, this is not limiting. For example, the adjuster may be supplied after the reactant is supplied.

[0105] 4A, 4B, 4C, 4D, and 4E, there are periods in which the supply of the raw material and the supply of the adjusting agent overlap, and periods in which each supply is performed independently. This allows for both the effects obtained by performing each supply independently and the effects obtained by performing each supply in an overlapping manner. Furthermore, compared to the comparative example, it is easier to control the amount of raw material adsorbed onto the wafer 200.

[0106] 5 (F), (G), (H), (I), and (J), there are periods in which the supply of the reactant and the supply of the adjuster overlap, and periods in which each supply is performed independently. This allows for both the effects obtained by performing each supply independently and the effects obtained by performing each supply independently. Furthermore, compared to the comparative example, it is easier to control the amount of reactant adsorbed on the wafer 200.

[0107] As described above, the conditioner not only suppresses the adsorption of raw material molecules to the wafer 200, but also promotes desorption of reactants from the wafer 200. In other words, it modifies the surface condition of the wafer 200. Therefore, the conditioner used here is also referred to as a post-treatment gas, post-treatment gas, treatment gas, modifying gas, or desorption-promoting gas. Furthermore, the conditioner used when supplying raw materials according to the present disclosure can also be referred to as a pre-treatment gas, pre-treatment gas, treatment gas, or modifying gas, since it changes the surface condition (surface characteristics, adsorption characteristics) of the wafer 200.

[0108] Other Aspects of the Present Disclosure The above describes specific aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0109] For example, although the above embodiment has been described using a gas containing Si as a raw material, the present disclosure is not limited thereto, and may be applied to a process using a gas containing at least one of Group 13 elements, Group 14 elements, Group 4 elements, Group 6 elements, and Group 8 elements as a raw material.

[0110] In the above embodiment, a case where a gas containing nitrogen element is used as a reactant has been described as an example, but the present disclosure is not limited to this. For example, an oxide film may be formed on the wafer 200 using a gas containing oxygen element as a reactant. Examples of the gas containing oxygen include oxygen (O ２ ) gas, water (H ２ O), hydrogen peroxide (H ２ O ２ ) gas, nitrous oxide (dinitrogen oxide) (N ２ O) gas, nitric oxide (NO) gas, and ozone (O ３ ) gases, etc. Furthermore, one or more of these gases may be activated or excited and used as reactants.

[0111] Alternatively, a gas containing hydrogen may be used as a reactant to form a film containing the element as a main component on the wafer 200. Examples of the gas containing hydrogen include hydrogen (H ２Gases composed of hydrogen elements such as silane-based gases, borane-based gases, phosphane-based gases, and germane-based gases, as well as mononuclear parent hydride gases, may be used as reactants. Examples of silane-based gases include monosilane (SiH ４ ) gas, disilane (Si ２ H ６ ) gas, and trisilane (Si ３ H ８ ) gases. Borane-based gases include monoborane (BH ３ ) gas, and diborane (B ２ H ６ ) gases. Phosphine gases include phosphine (PH ３ ) gas, and diphosphine (P ２ H ６ ) gases. Germane-based gases include monogermane (GeH ４ ) gas, digermane (Ge ２ H ６ ) gas, and trigermane (Ge ３ H ８ ) Gas, etc.

[0112] 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. However, the present disclosure is not limited to this and can also be suitably applied to film formation using a single-wafer substrate processing apparatus that processes one or several substrates at a time. In addition, in the above aspect, an example of film formation using a substrate processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to this and can also be suitably applied to film formation using a substrate processing apparatus having a cold-wall processing furnace. Even when using these substrate processing apparatuses, film formation can be performed using the same sequence and processing conditions as in the above embodiment.

[0113] In the above-described embodiment, the processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiment, and for example, one step and another step of the processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus.

[0114] It is preferable that process recipes (programs describing processing procedures, processing conditions, etc.) used to form these various thin films are individually prepared (prepared in multiple numbers) depending on the content of substrate processing (such as the type, composition ratio, film quality, film thickness, processing procedure, or processing conditions of the thin film to be formed). Then, when starting substrate processing, it is preferable to appropriately select an appropriate process recipe from the multiple process recipes depending on the content of substrate processing. Specifically, it is preferable that the multiple process recipes individually prepared depending on the content of substrate processing are pre-stored (installed) 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. Then, when starting substrate processing, it is preferable that the CPU 121a of the substrate processing apparatus appropriately selects an appropriate process recipe from the multiple process recipes stored in the storage device 121c depending on the content of substrate processing. This configuration makes it possible to versatilely and reproducibly form thin films of various film types, composition ratios, film qualities, and film thicknesses using a single substrate processing apparatus. Furthermore, the burden on the operator (such as the burden of inputting processing procedures and processing conditions) can be reduced, so that substrate processing can be started promptly while avoiding operational errors by the operator.

[0115] 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.

[0116] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and conditions in such a case may be the same as those of the above-described embodiments and modifications.

[0117] 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.

[0118] 10: Substrate processing apparatus, 121: Controller, 200: Wafer (substrate), 201: Processing chamber

Claims

1. A substrate processing method comprising the steps of: (a) supplying a raw material to a substrate; (b) supplying a reactant to the substrate; (c) supplying to the substrate an adjuster for adjusting the amount of at least one of the raw material molecules and the reactant molecules adsorbed to the substrate; (d) overlapping at least one of (a) and (b) with (c); and (e) following (d), performing (a) or (b) which has been performed in (d) overlapping with (c) solely on (c).

2. The substrate processing method according to claim 1, wherein in (d), (a) and (c) are performed in an overlapping manner, and in (e), (a) is performed alone.

3. The substrate processing method according to claim 2, wherein (e) is performed after (d).

4. The method for processing a substrate according to claim 3, further comprising the step of performing (c) before (d).

5. The method for processing a substrate according to claim 3, further comprising the step of performing (a) before (d).

6. The method for processing a substrate according to claim 2, further comprising the step of performing (d) after (e).

7. The method for processing a substrate according to claim 6, further comprising the step of performing (c) after (d).

8. The substrate processing method according to claim 1, wherein in (d), (b) and (c) are performed in an overlapping manner, and in (e), (b) is performed.

9. The method of claim 8, wherein (e) is performed after (d).

10. The method for processing a substrate according to claim 9, further comprising the step of performing (c) before (d).

11. The method for processing a substrate according to claim 10, further comprising the step of performing (b) before (d).

12. The method for processing a substrate according to claim 8, wherein (d) is carried out after (e).

13. The method for processing a substrate according to claim 12, further comprising the step of performing (c) after (d).

14. The substrate processing method according to any one of claims 1 to 13, wherein the source material contains a halogen.

15. The method of any one of claims 1 to 13, wherein the reactant is a reducing gas.

16. The substrate processing method according to any one of claims 1 to 13, wherein the regulator contains a halogen.

17. A method for manufacturing a semiconductor device comprising the steps of: (a) supplying a raw material to a substrate; (b) supplying a reactant to the substrate; (c) supplying an adjuster to the substrate for adjusting the amount of at least one of the raw material molecules and the reactant molecules adsorbed to the substrate; (d) performing at least one of (a) and (b) in combination with (c) in an overlapping manner; and (e) following (d), performing (a) or (b) in combination with (c) in (d) solely on (c).

18. A program for causing a substrate processing apparatus to execute, by a computer, the following steps: (a) a procedure for supplying raw materials to a substrate; (b) a procedure for supplying reactants to the substrate; (c) a procedure for supplying an adjuster to the substrate for adjusting the amount of at least one of the raw material molecules and the reactant molecules adsorbed to the substrate; (d) a procedure for overlapping at least one of (a) and (b) with (c); and (e) following (d), a procedure for performing (a) or (b) performed in overlap with (c) in (d) solely on (c).

19. A substrate processing apparatus comprising: a raw material supply system for supplying raw material to a substrate; a reactant supply system for supplying reactants to the substrate; an adjuster supply system for supplying an adjuster to the substrate; and a control unit configured to be capable of controlling the raw material supply system, the reactant supply system, and the adjuster supply system to perform the following: (a) a process for supplying the raw material to the substrate; (b) a process for supplying the reactants to the substrate; (c) a process for supplying the adjuster to the substrate for adjusting the amount of at least one of the raw material molecules and the reactant molecules adsorbed to the substrate; (d) a process for performing at least one of (a) and (b) and (c) in an overlapping manner; and (e) a process for performing (a) or (b) performed in (d) in an overlapping manner with (c) solely on (c) following (d).

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