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

Abstract

Provided is a technique capable of controlling the decomposition rate of a processing gas supplied to a substrate. (a) The substrate disposed in the processing space is processed by controlling the decomposition rate according to a predetermined relationship between the decomposition rate of the processing gas supplied into the processing space and the residence time.

Description

Technical Field

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

[0002] In Patent Document 1, as one step of a manufacturing process of a semiconductor device, the following technique is disclosed: a source gas and / or a reaction gas are supplied respectively for a supply time corresponding to a concentration distribution in a substrate surface of a by-product formed on a substrate.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-208883 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] However, when forming a film on a substrate, if the decomposition rate of a processing gas is high, the step coverage deteriorates, and if the decomposition rate of the processing gas is low, the film formation rate decreases.

[0008] The present disclosure provides a technique capable of controlling the decomposition rate of a processing gas supplied to a substrate.

[0009] Means for Solving the Problems

[0010] According to one aspect of the present disclosure, the following technique is provided:

[0011] (a) The decomposition rate is controlled according to a specified relationship between the decomposition rate and the residence time of a processing gas supplied into a processing space, whereby a substrate disposed in the processing space is processed.

[0012] Effects of the Invention

[0013] According to the present disclosure, the decomposition rate of a processing gas supplied to a substrate can be controlled. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is a longitudinal sectional view showing an outline of a substrate processing apparatus in one embodiment of the present disclosure.

[0015] Figure 2 is showing Figure 1 a longitudinal sectional view showing details of a substrate support portion in.

[0016] Figure 3 (A) of is a diagram showing a first gas supply system in one embodiment of the present disclosure, Figure 3(B) is a diagram showing a second gas supply system in an embodiment of the present disclosure. Figure 3 (C) is a diagram showing a third gas supply system in an embodiment of the present disclosure.

[0017] Figure 4 (A) is a diagram showing an exhaust system of a processing chamber in an embodiment of the present disclosure. Figure 4 (B) is a diagram showing an exhaust system of a transfer chamber in an embodiment of the present disclosure.

[0018] Figure 5 is a schematic structural diagram of a controller of a substrate processing apparatus in an embodiment of the present disclosure, and is a diagram showing a control system of the controller in a block diagram.

[0019] Figure 6 is a diagram showing a substrate processing sequence in an embodiment of the present disclosure.

[0020] Figure 7 is a diagram showing the relationship between the residence time of a first gas and the decomposition rate.

[0021] Figure 8 is a diagram showing the relationship between the flow rate of a first gas and the decomposition rate.

[0022] Figure 9 (A) is a diagram showing the relationship between the elapsed time and the supply amount of a first gas. Figure 9 (B) is a diagram showing the relationship between the elapsed time and the residence time of a first gas. Figure 9 (C) is a diagram showing the relationship between the elapsed time and the flow rate of a first gas.

[0023] Figure 10 (A) to Figure 10 (C) is a diagram showing an example of the chemical structural formula of a first gas in an embodiment of the present disclosure. Detailed Embodiments

[0024] Hereinafter, mainly with reference to Figures 1 to 10 an embodiment of the present disclosure will be described. In addition, the drawings used in the following description are all schematic, and the dimensional relationships of the respective elements shown in the drawings, the ratios of the respective elements, etc. are not necessarily the same as the actual situation. Further, the dimensional relationships of the respective elements and the ratios of the respective elements are not necessarily the same among the plurality of drawings.

[0025] (1) Structure of Substrate Processing Apparatus

[0026] Using Figure 1 the structure of the substrate processing apparatus 10 will be described.

[0027] The substrate processing apparatus 10 has a reaction tube accommodation chamber 206b, and within the reaction tube accommodation chamber 206b, there are: a reaction tube 210 having a cylindrical shape extending in the vertical direction, a heater 211 disposed on the outer periphery of the reaction tube 210 as a heating unit (furnace body), a gas supply structure 212 as a gas supply unit, and a gas exhaust structure 213 as a gas exhaust unit. The gas supply unit may include an upstream rectifying unit 214, nozzles 223 and 224 described later. Additionally, the gas exhaust unit may also include a downstream rectifying unit 215 described later. The partition in the reaction tube 210 for processing the substrate S is referred to as a processing chamber 201. Additionally, the processing chamber 201 may also be referred to as a processing space in which the substrate S is disposed inside.

[0028] The gas supply structure 212 is disposed upstream in the gas flow direction of the reaction tube 210, and gas is supplied from the gas supply structure 212 into the reaction tube 210, and the gas is supplied to the substrate S in the horizontal direction. The gas exhaust structure 213 is disposed downstream in the gas flow direction of the reaction tube 210, and the gas in the reaction tube 210 is discharged from the gas exhaust structure 213. The gas supply structure 212, the inside of the reaction tube 210, and the gas exhaust structure 213 communicate with each other in the horizontal direction.

[0029] An upstream rectifying unit 214 for rectifying the gas flow supplied from the gas supply structure 212 is provided on the upstream side of the reaction tube 210 between the reaction tube 210 and the gas supply structure 212. Additionally, a downstream rectifying unit 215 for rectifying the gas flow discharged from the reaction tube 210 is provided on the downstream side of the reaction tube 210 between the reaction tube 210 and the gas exhaust structure 213. The lower end of the reaction tube 210 is supported by a manifold 216.

[0030] The reaction tube 210, the upstream rectifying unit 214, and the downstream rectifying unit 215 are continuous structures, and are formed of materials such as quartz or SiC, for example. They are composed of heat-permeable members, and the heat-permeable members allow the heat radiated from the heater 211 to pass through. The heat of the heater 211 heats the substrate S or the gas.

[0031] The gas supply structure 212 is connected to a gas supply pipe 251 and a gas supply pipe 261, and has a distribution unit 225 for distributing the gas supplied from each gas supply pipe. A plurality of nozzles 223 and nozzles 224 are provided on the downstream side of the distribution unit 225. The gas supply pipe 251 and the gas supply pipe 261 supply different types of gas as described later. The nozzles 223 and 224 are arranged in an up-and-down relationship and a horizontally arranged relationship. In this embodiment, the gas supply pipe 251 and the gas supply pipe 261 are collectively referred to as a gas supply pipe 221. Each nozzle is also referred to as a gas ejection unit. The distribution unit 225 is configured to supply each gas from the gas supply pipe 251 to the nozzle 223 and supply each gas from the gas supply pipe 261 to the nozzle 224.

[0032] The upstream-side rectifying section 214 has a housing 227 and a partition plate 226. The partition plate 226 has a structure that extends in the horizontal direction and is continuous without holes. The horizontal direction mentioned here indicates the side wall direction of the housing 227. A plurality of partition plates 226 are arranged in the vertical direction. The partition plate 226 is fixed to the side wall of the housing 227 and is configured such that gas does not move to adjacent regions below or above the partition plate 226.

[0033] Each partition plate 226 is provided at a position corresponding to each substrate S. Nozzles 223 and 224 are provided between the partition plates 226 or between the partition plate 226 and the housing 227. The gas ejected from the nozzles 223 and 224 rectifies the air flow through the partition plate 226 and is supplied to the surface of the substrate S. That is, when viewed from the substrate S, the gas is supplied from the lateral direction of the substrate S.

[0034] The downstream-side rectifying section 215 is configured such that, in a state where the substrate S is supported by a substrate support member 300 described later, the top is higher than the uppermost substrate S in configuration, and the bottom is lower than the lowermost substrate S in the substrate support member 300.

[0035] The downstream-side rectifying section 215 has a housing 231 and a partition plate 232. The partition plate 232 has a structure that extends in the horizontal direction and is continuous without holes. The horizontal direction mentioned here indicates the side wall direction of the housing 231. And a plurality of partition plates 232 are arranged in the vertical direction. The partition plate 232 is fixed to the side wall of the housing 231 and is configured such that gas does not move to adjacent regions below or above the partition plate 232. A flange 233 is provided on the side of the housing 231 that contacts the gas exhaust structure 213.

[0036] The partition plate 232 is provided at positions corresponding to the substrates S respectively and at positions corresponding to the partition plates 226 respectively. The corresponding partition plates 226 and 232 are preferably of the same height. And when processing the substrate S, it is preferable to make the height of the substrate S coincide with the heights of the partition plates 226 and 232.

[0037] By arranging the partition plates 226 and 232 in the above-described positional relationship, it is possible to make the pressure loss uniform in the vertical direction upstream and downstream of each substrate S. That is, it is possible to reliably form a horizontal air flow as indicated by the arrows in the figure, in which the flow in the vertical direction is suppressed on the partition plate 226, the substrate S, and the partition plate 232. Therefore, the pressure difference of the gas on each substrate S can be reduced. As a result, each substrate S can be uniformly processed. In addition, on each substrate S, the difference in the residence time τ and / or the flow velocity v of the first gas described later can be reduced. As a result, the difference in the decomposition rate X of the first gas supplied to each substrate S can be reduced.

[0038] The gas exhaust structure 213 is provided downstream of the downstream rectifying section 215. The gas exhaust structure 213 mainly consists of a housing 241 and an exhaust pipe connecting section 242. A flange 243 is provided on the side of the downstream rectifying section 215 in the housing 241. The housing 231 and the housing 241 have a continuous structure in terms of the height of their respective tops and bottoms. An exhaust hole 244 is formed on the downstream side and the lower side or the horizontal direction of the housing 241, and the exhaust hole 244 exhausts the gas that has passed through the downstream rectifying section 215. The gas exhaust structure 213 is provided laterally of the reaction tube 210 and is a lateral exhaust structure for exhausting gas from the lateral direction of the substrate S.

[0039] The transfer chamber 217 is provided below the reaction tube 210 with the manifold 216 interposed therebetween. In the transfer chamber 217, the substrate S is placed (loaded) on a substrate support member (hereinafter, sometimes simply referred to as a boat) 300 via the substrate transfer port by a vacuum transfer robot, or the substrate S is taken out from the substrate support member 300 by the vacuum transfer robot.

[0040] The substrate support member 300, the partition plate support section 310, and the vertical drive mechanism section 400 can be accommodated inside the transfer chamber 217. The vertical drive mechanism section 400 drives the substrate support member 300 and the partition plate support section 310 (collectively referred to as the substrate holding member) in the vertical direction and the rotational direction. In Figure 1 shows a state where the substrate support member 300 is lifted by the vertical drive mechanism section 400 and accommodated inside the reaction tube 210.

[0041] The vertical drive mechanism section 400 includes: a rotational drive mechanism 430 that rotates the substrate support member 300 and the partition plate support section 310 together; a boat vertical mechanism 420 that drives the substrate support member 300 relative to the partition plate support section 310 in the vertical direction. The rotational drive mechanism 430 and the boat vertical mechanism 420 are fixed to a base flange 401 that serves as a cover, and the base flange 401 is supported by a side plate 403 on a base plate 402. An O-ring 446 for vacuum sealing is provided on the upper surface of the base flange 401. As Figure 1 shown, by driving with an up-down drive motor 410 to raise the upper surface of the base flange 401 to a position where it abuts against the transfer chamber 217, the inside of the reaction tube 210 can be maintained airtight. A support member 440 fixed to the partition plate support section 310 and a support section 441 fixed to the substrate support member 300 are connected by a vacuum bellows 443.

[0042] Next, Figure 1 、 Figure 2 will be used to describe the details of the substrate support section.

[0043] The substrate support portion is composed of at least a substrate support member 300 that supports the substrate S and is accommodated in the reaction tube 210. The substrate S is disposed directly below the inner wall of the top plate of the reaction tube 210. In addition, the substrate support portion transfers the substrate S via a substrate transfer port (not shown) inside the transfer chamber 217 by a vacuum transfer robot, or transfers the transferred substrate S into the reaction tube 210 to form a thin film on the surface of the substrate S. The substrate transfer port is provided, for example, on the side wall of the transfer chamber 217. In addition, it is also possible to consider including a separator support portion 310 in the substrate support portion.

[0044] In the substrate support member 300, a plurality of substrates S are placed at a predetermined interval in the vertical direction (perpendicular direction) by a plurality of support rods 315 supported by a base portion 311. The plurality of substrates S supported by the support rods 315 are separated by a disk-shaped separator 314, and the separator 314 is fixed (supported) to a support column 313 at a predetermined interval. The support column 313 is supported by the separator support portion 310. Here, the separator 314 is disposed directly below the substrate S, and is disposed on one or both of the upper and lower portions of the substrate S. The separator 314 blocks the space of each substrate S. The predetermined interval between the plurality of substrates S placed on the substrate support member 300 is the same as the vertical interval between the separators 314 fixed to the separator support portion 310. In addition, the diameter of the separator 314 is formed to be larger than the diameter of the substrate S.

[0045] The base portion 311, the separator 314, and the plurality of support rods 315 are formed of materials such as quartz or SiC, for example. In addition, an example in which 5 substrates S are supported by the substrate support member 300 is shown here, but it is not limited thereto. For example, the substrate support member 300 can also be configured to support about 5 to 50 substrates S. In addition, the separator 314 is also referred to as a separator.

[0046] In addition, the expression of the numerical range such as "5 to 50 sheets" in this specification means that the lower limit value and the upper limit value are included in this range. Therefore, for example, "5 to 50 sheets" means "5 sheets or more and 50 sheets or less". The same applies to other numerical ranges.

[0047] In the process of forming a thin film on the substrate S, the separator 314 is preferably located at a height corresponding to the dividing plate 226 and / or the dividing plate 232. More preferably, the heights of the separator 314, the dividing plate 226, and the dividing plate 232 are aligned.

[0048] By using such a substrate support portion, it is easy to form a horizontal air flow that suppresses the flow in the vertical direction on the partition plate 226, the substrate S, and the partition plate 232. As a result, the difference in gas pressure on each substrate S becomes uniform, and thus, each substrate S can be uniformly processed. In addition, on each substrate S, it is possible to reduce the difference in the residence time τ and / or the flow velocity v of the first gas described later. Thereby, it is possible to reduce the difference in the decomposition rate X of the first gas supplied to each substrate S.

[0049] The vertical drive mechanism portion 400 drives the partition plate support portion 310 and the substrate support 300 in the vertical direction between the reaction tube 210 and the transfer chamber 217 and in the rotational direction around the center of the substrate S supported by the substrate support 300.

[0050] Next, use Figure 3 of (A) to Figure 3 of (C) to describe the details of the gas supply system.

[0051] As Figure 3 shown in (A) of FIG., in the gas supply pipe 251, a first gas source 252, a mass flow controller (flow control unit) MFC 253 as a flow controller, a valve 275 as an on-off valve, a tank 259 as a storage unit for storing gas, and a valve 254 as an on-off valve are sequentially provided from the upstream direction.

[0052] The first gas source 252 is a source of a first gas containing a first element (also referred to as a "gas containing a first element"). The first gas is a raw material gas, that is, one of the process gases.

[0053] The first gas supply system 250 (also referred to as a raw material gas supply system or a process gas supply system) is mainly composed of the gas supply pipe 251, the MFC 253, the valve 275, the tank 259, and the valve 254. The first gas source 252 may be included in the first gas supply system 250.

[0054] A gas supply pipe 255 is connected between the valve 275 and the tank 259 in the gas supply pipe 251. In the gas supply pipe 255, an inert gas source 256, an MFC 257, and a valve 258 as an on-off valve are sequentially provided from the upstream direction. An inert gas is supplied from the inert gas source 256.

[0055] The first inert gas supply system is mainly composed of the gas supply pipe 255, the MFC 257, and the valve 258. The inert gas supplied from the inert gas source 256 functions as a purge gas for purging the gas remaining in the reaction tube 210 during the substrate processing step. The inert gas source 256 may be included in the first inert gas supply system. The first inert gas supply system may be added to the first gas supply system 250.

[0056] As shown Figure 3 in (B) of

[0056] , the following components are sequentially arranged in the gas supply pipe 261 from the upstream direction: a second gas source 262, an MFC 263, a valve 276, a tank 269, and a valve 264.

[0057] The second gas source 262 is a source of a second gas containing a second element (hereinafter also referred to as "second element-containing gas"). The second gas is a gas different from the first gas and can also be one of the processing gases. In addition, the second gas can also be considered as a reaction gas that reacts with the precursor of the first gas as a raw material gas or a modifying gas that modifies the surface of the substrate S.

[0058] The second gas supply system 260 (also referred to as a reaction gas supply system or a processing gas supply system) is mainly composed of the gas supply pipe 261, the MFC 263, the valve 276, the tank 269, and the valve 264. The second gas source 262 can also be included in the second gas supply system 260.

[0059] A gas supply pipe 265 is connected between the valve 276 and the tank 269 in the gas supply pipe 261. The following components are sequentially arranged in the gas supply pipe 265 from the upstream direction: an inert gas source 266, an MFC 267, and a valve 268 as an on-off valve. An inert gas is supplied from the inert gas source 266.

[0060] The second inert gas supply system is mainly composed of the gas supply pipe 265, the MFC 267, and the valve 268. The inert gas supplied from the inert gas source 266 functions as a purge gas for purging the gas remaining in the reaction tube 210 during the substrate processing step. The inert gas source 266 can be included in the second inert gas supply system. The second inert gas supply system can also be added to the second gas supply system 260.

[0061] As shown Figure 3 in (C) of , the following components are sequentially arranged in the gas supply pipe 271 from the upstream direction: a third gas source 272, an MFC 273, and a valve 274. The gas supply pipe 271 is connected to the transfer chamber 217. When the transfer chamber 217 is in an inert gas atmosphere or in a vacuum state, an inert gas is supplied.

[0062] The third gas source 272 is an inert gas source. The third gas supply system 270 is mainly composed of the gas supply pipe 271, the MFC 273, and the valve 274. The third gas source 272 can be included in the third gas supply system 270. The third gas supply system 270 is also referred to as a transfer chamber supply system.

[0063] Next, the exhaust system will be described using Figure 4 (A) of and Figure 4 (B) of .

[0064] An exhaust system 280 for exhausting the atmosphere of the reaction tube 210 has an exhaust pipe 281 communicating with the reaction tube 210 and is connected to the housing 241 via an exhaust pipe connection portion 242.

[0065] As Figure 4 shown in (A) of [], the exhaust pipe 281 is connected to a vacuum pump 284 as a vacuum exhaust device via a valve 282 and an APC (Auto Pressure Controller) valve 283 as a pressure regulator (pressure regulating portion), and is configured to be able to perform vacuum exhaust so that the pressure in the reaction tube 210 becomes a specified pressure (vacuum degree). The exhaust pipe 281, the valve 282, and the APC valve 283 are collectively referred to as the exhaust system 280. The exhaust system 280 is also referred to as a process chamber exhaust system. In addition, the exhaust system 280 may include the vacuum pump 284. An exhaust system 290 for exhausting the atmosphere of the transfer chamber 217 is connected to the transfer chamber 217 and has an exhaust pipe 291 communicating with the inside thereof.

[0066] As Figure 4 shown in (B) of [], the exhaust pipe 291 is connected to the vacuum pump 294 via a valve 292 and an APC valve 293, and is configured to be able to perform vacuum exhaust so that the pressure in the transfer chamber 217 becomes a specified pressure. The exhaust pipe 291, the valve 292, and the APC valve 293 are collectively referred to as the exhaust system 290. The exhaust system 290 is also referred to as a transfer chamber exhaust system. In addition, the exhaust system 290 may also include the vacuum pump 294.

[0067] Next, Figure 5 a description will be given of a controller as a control unit (control unit). The substrate processing apparatus 10 has a controller 600 that controls the operations of the respective parts of the substrate processing apparatus 10.

[0068] Figure 5 shows an overview of the controller 600. The controller 600 is configured as a computer having the following parts: a CPU (Central Processing Unit) 601, a RAM (Random Access Memory) 602, a storage device 603 as a storage unit, and an I / O port 604. The RAM 602, the storage device 603, and the I / O port 604 are configured to be able to perform data exchange with the CPU 601 via an internal bus 605.

[0069] The storage device 603 is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. In the storage device 603, a control program for controlling the operation of the substrate processing apparatus 10, a process such as a process of substrate processing or conditions, etc. are stored in a readable manner.

[0070] In addition, the process is combined in such a way that the controller 600 can execute each process in the substrate processing process described below to obtain a specified result, and functions as a program. Hereinafter, the process or control program, etc. will also be collectively referred to as a program. In addition, when the term "program" is used in this specification, there are cases where it only includes the process alone, cases where it only includes the control program alone, or cases where it includes both. In addition, the RAM 602 is configured as a storage area (work area) that temporarily stores programs or data read by the CPU 601.

[0071] The I / O port 604 is connected to the above-mentioned up-down direction drive mechanism unit 400, heater 211, APC valves 283, 293, vacuum pumps 284, 294, MFCs 253, 257, 263, 267, 273, valves 254, 258, 264, 268, 274, 275, 276, rotation drive mechanism 430, etc.

[0072] The CPU 601 is configured to: read and execute the control program from the storage device 603, and read the process from the storage device 603 according to the input of an operation command from the input / output device 681, etc. And the CPU 601 is configured to: control the following actions according to the content of the read process: the lifting action of the substrate support 300 by the up-down direction drive mechanism unit 400, the heating action of the heater 211, the opening and closing actions of the APC valves 283, 293, the start and stop of the vacuum pumps 284, 294, the flow rate adjustment actions of various gases by the MFCs 253, 257, 263, 267, 273, the opening and closing actions of the valves 254, 258, 264, 268, 274, 275, 276, the rotation and rotation speed adjustment actions of the substrate support 300 by the rotation drive mechanism 430, etc.

[0073] Regarding the controller 600, by installing the program on a computer or the like using an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a DVD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory) 682 that stores the above program, the controller 600 of this mode can be configured. In addition, the means for supplying the program to the computer is not limited to the case of supplying via the external storage device 682. For example, communication means such as the Internet or a dedicated line can also be used to supply the program without going through the external storage device 682. In addition, the storage device 603 and the external storage device 682 are configured as computer-readable storage media that record programs. Hereinafter, they will be collectively referred to as storage media. In addition, in this specification, when the term "storage medium" is used, there are cases where it only includes the storage device 603 alone, cases where it only includes the external storage device 682 alone, or cases where it includes both.

[0074] Next, as one of the semiconductor manufacturing processes, Figures 6 to 10 A process of forming a thin film on the substrate S using the substrate processing apparatus 10 having the above structure will be described. In addition, in the following description, each part of the substrate processing apparatus 10 is controlled by the controller 600 to operate.

[0075] Here, a film formation process of forming a film in concave portions such as grooves or holes of the substrate S using a first gas and a second gas will be described. As the first gas, for example, Figure 10 the dichlorosilane hexachloride (Si2Cl6, hexachloroethylsilane, abbreviation: HCDS) gas described in (A) of

[0076] The term "substrate" used in this specification sometimes refers to the substrate itself and sometimes refers to a laminate of the substrate and a specified layer or film formed on its surface. The term "surface of the substrate" used in this specification sometimes refers to the surface of the substrate itself and sometimes refers to the surface of a specified layer or the like formed on the substrate. When it is described in this specification that "a specified layer is formed on the substrate", sometimes it means that the specified layer is directly formed on the surface of the substrate itself, and sometimes it means that the specified layer is formed on a layer or the like formed on the substrate. The case where the term "wafer" is used in this specification has the same meaning as the case where the term "substrate" is used.

[0077] (S102)

[0078] The transfer chamber pressure adjustment process S102 will be described. Here, the pressure in the transfer chamber 217 is set to the same level as that of an unillustrated vacuum transfer chamber adjacent to the transfer chamber 217. Specifically, the exhaust system 290 is operated to exhaust the atmosphere in the transfer chamber 217 so that the atmosphere in the transfer chamber 217 becomes a vacuum level.

[0079] (S104)

[0080] Next, the substrate loading process S104 will be described.

[0081] After the transfer chamber 217 becomes a vacuum level, the substrate S is started to be transferred. After the substrate S reaches the vacuum transfer chamber, the gate valve is released, and the vacuum transfer robot transfers the substrate S into the transfer chamber 217.

[0082] At this time, the substrate support member 300 stands by in the transfer chamber 217, and the substrate S is transferred to the substrate support member 300. After a specified number of substrates S are transferred to the substrate support member 300, the vacuum transfer robot is retracted, and the substrate support member 300 is raised by the vertical drive mechanism unit 400 to move the substrate S into the reaction tube 210. At this time, the surface of the substrate S is positioned to be at the same height as the partition plates 226 and 232.

[0083] (S106)

[0084] Next, the heating process S106 will be described. After the substrate S is carried into the reaction tube 210, the pressure inside the reaction tube 210 is controlled to a specified pressure, and the surface temperature of the substrate S is controlled to a specified temperature. When, for example, HCDS gas is used as the first gas, the temperature of the heater 211 is controlled such that the temperature of the substrate S is, for example, 100°C to 1500°C, preferably 200°C to 1000°C, and more preferably 400°C to 800°C. In addition, the pressure inside the reaction tube 210 is, for example, set to 5 Pa to 100 kPa considering various factors.

[0085] (S108)

[0086] Next, the film treatment process S108 will be described. In the film treatment process S108, according to the process, the concave portions of the substrate S are subjected to the above-described first gas supply process and second gas supply process one or more times, and a specified film is formed on the substrate S having concave portions on its surface. In the first gas supply process, the first gas is rapidly supplied to the substrate S, and in the second gas supply process, the second gas is rapidly supplied to the substrate S.

[0087] <First gas supply process, step S1>

[0088] In this step, the first gas is rapidly supplied to the processing chamber 201 in which the substrate S is disposed. Here, rapid supply means supplying a large flow rate of gas into the reaction tube 210 in a short time.

[0089] Specifically, in this step, the first gas is reserved in advance in the tank 259 provided in the gas supply pipe 251. When, for example, HCDS gas is used as the first gas, the pressure inside the tank 259 at this time is, for example, 100 to 100×10 3 Pa, preferably 1.0×10 3 to 80×10 3 Pa, and more preferably 5.0×10 3 Pa to 60×10 3 Pa.

[0090] Then, when supplying the first gas, the valve 254 provided on the downstream side of the tank 259 between the tank 259 and the nozzle 223 is opened, and the first gas is supplied from the tank 259 in which the first gas is stored in advance into the gas supply pipe 251. At this time, the pressure (total pressure) inside the processing chamber 201 is set to, for example, 10 to 1.0×10 3Pa. Then, after a predetermined time has elapsed since the supply of the first gas started, the valve 254 is closed to stop the supply of the first gas into the gas supply pipe 251. When, for example, HCDS gas is used as the first gas, the valve 254 is closed after a time within the range of 0.1 to 10 seconds, for example, to stop the supply of the first gas into the gas supply pipe 251.

[0091] After the first gas is supplied in a large amount from the gas supply structure 212 to the reaction tube 210 via the upstream rectifying section 214 in a short time, it is exposed and exhausted via the space on the substrate S, the downstream rectifying section 215, the gas exhaust structure 213, and the exhaust pipe 281. At this time, the valve 282 and the APC valve 283 are in an open state. Here, during the supply of the first gas into the processing chamber 201, the valve 275 may be in an open state or a closed state.

[0092] At this time, the decomposition rate of the first gas in the processing chamber 201 varies within the range of 0% to 100% as the residence time τ of the first gas changes. Here, when the decomposition rate includes 0%, the decomposition rate of 0% means that the decomposition rate of the first gas does not change with time. That is, the state where the first gas supplied into the processing chamber 201 is discharged from the processing chamber 201 in the state of the first gas is defined as the decomposition rate of 0%. In addition, the state where all of the first gas supplied into the processing chamber 201 is discharged from the processing chamber 201 in a state other than the first gas is defined as the decomposition rate of 100%. This is the same in the following description.

[0093] Here, the residence time of the gas means a numerical value that is an index of the time until the gas supplied into the processing chamber 201 is discharged from the processing chamber 201. In the following description, the residence time of the first gas is defined as the time until the first gas supplied into the processing chamber 201 is discharged from the processing chamber 201. In addition, it may be defined as a numerical value that is an index of the time until the gas supplied into the processing chamber 201 is discharged from the processing chamber 201. In addition, it may also be defined as a numerical value that is an index of the time until the gas that has reached the processing space escapes to the outside of the processing space.

[0094] In the following description, the residence time of the first gas is defined as the time from when the first gas reaches the substrate S until it detaches from the substrate S. In addition, as the residence time of the first gas, for example, it can also be defined as the time from when the first gas reaches the processing space until it detaches from the processing space. Additionally, the time from when the first gas is ejected from a gas supply section such as the nozzle 223 until it reaches the exhaust hole 244 can also be used. Moreover, the time from the start of the supply of the first gas to the end of the supply can be used, for example, the time from when the valve 254 on the downstream side of the tank 259 is opened until it is closed, etc., which is the time of a specified component of the substrate processing apparatus 10 from the moment of starting or ending a specified operation until the moment of starting or ending a specified operation. Additionally, it can be set as the value obtained by dividing the diameter of the substrate S by the flow rate of the first gas on the substrate S. Additionally, it can be set as the value obtained by dividing the volume of the processing chamber 201 by the volume of the gas discharged from the processing chamber 201 per unit time. Additionally, it can also be set as the time until the number of molecules of the first gas in the processing chamber at a certain time point decreases to a specified value.

[0095] In this step, according to the specified relationship between the residence time τ of the first gas in the processing chamber 201 and the decomposition rate X of the first gas in the processing chamber 201, the residence time τ of the first gas corresponding to the decomposition rate X of the first gas is set. That is, by controlling the residence time τ of the first gas, the decomposition rate X of the first gas supplied to the substrate S is controlled.

[0096] Here, use Figure 7 to illustrate the relationship between the residence time τ (seconds) and the decomposition rate X (%) of the first gas in the processing chamber 201 at a specified pressure within the range of 10 to 1.0×10 3 Pa. Figure 7 It is a semi-logarithmic line graph in logarithmic representation, with the horizontal axis representing the residence time τ (seconds) of the first gas in logarithmic scale and the vertical axis representing the decomposition rate X (%) of the first gas.

[0097] As Figure 7 shown, the decomposition rate X of the first gas has a relationship such that the longer the residence time τ in the processing chamber 201, the higher the logarithm. Here, according to Figure 7 , for example, by setting the residence time τ of the first gas to τa, it is possible to supply the first gas with a decomposition rate X of 50% to the substrate S. Additionally, by setting the residence time τ of the first gas to be less than τa, it is possible to supply the first gas with a decomposition rate X of 50% or less to the substrate S. Additionally, by setting the residence time τ of the first gas to be less than τb, it is possible to supply the first gas with a decomposition rate X near 0% to the substrate S. That is, it is possible to control the decomposition rate according to the specified relationship between the decomposition rate and the residence time of the first gas in the processing space. In other words, it is possible to predict the decomposition rate according to the specified relationship between the decomposition rate and the residence time of the first gas in the processing space under certain conditions.

[0098] That is, by setting the value of the residence time τ of the first gas to be equal to or less than the first time τ1 at which the decomposition rate X becomes the first decomposition rate X1, the value of the decomposition rate X can be controlled within the range (the first range) of the first decomposition rate X1 or less. That is, by making the residence time τ of the first gas shorter than a specified value, the decomposition rate of the first gas can be made lower than the decomposition rate of the first gas when the residence time τ of the first gas is the specified value. In addition, within the range where the value of the residence time τ of the first gas is set to be equal to or less than a second time τ2 that is longer than the first time τ1, the value of the decomposition rate at the second time τ2 is the second decomposition rate X2 that is higher than the first decomposition rate X1. Thus, the value of the decomposition rate X can be controlled within the range (the second range) of the second decomposition rate X2 or less. That is, by making the residence time τ of the first gas longer than a specified value, the decomposition rate of the first gas can be made higher than the decomposition rate of the first gas when the residence time τ of the first gas is the specified value.

[0099] Here, the residence time τ of the first gas in the processing chamber 201 can be controlled by controlling the flow rate v of the first gas in the processing chamber 201. That is, by increasing (also referred to as accelerating) the flow rate v of the first gas, the residence time of the first gas in the processing chamber 201 can be shortened. In addition, by decreasing (also referred to as decelerating) the flow rate v of the first gas, the residence time of the first gas in the processing chamber 201 can be extended.

[0100] Here, the flow rate of the gas refers to the numerical value that is an index of the distance traveled by the gas supplied into the processing chamber 201 per unit time. In addition, it can also be set as the numerical value that is an index of the distance traveled by the gas in the processing chamber 201 per unit time. In addition, it can also be set as the numerical value that is an index of the distance traveled by the gas in the processing space per unit time of the index.

[0101] In the following description, as the flow rate v of the first gas, the average flow rate of the first gas on the substrate S is set. In addition, as the flow rate v of the first gas, for example, the average flow rate from when the first gas is ejected from a gas supply unit such as the nozzle 223 into the processing chamber 201 until it reaches the exhaust hole 244, or the average flow rate during the period from a certain part (or region) to another part (or region) can be used. In addition, the average flow rate of the first gas in the processing space can also be used. In addition, the average flow rate of the first gas in the processing chamber 201 can also be used. In addition, as an alternative to the average flow rate of the first gas in the above example, the flow rate of the first gas at a certain point on the substrate S, or in the processing space, or in the processing chamber 201 can also be used.

[0102] In addition, as the residence time or flow rate of the above-mentioned first gas, for example, the value measured, calculated, or estimated by some means can be used, or the value obtained through simulation can also be used.

[0103] Here, useFigure 8 The relationship between the flow rate v (m / s) of the first gas in the processing chamber 201 at a specified pressure within the range of 10 to 1.0×10 3 Pa and the decomposition rate X (%) will be described. Figure 8 The horizontal axis represents the flow rate v (m / s) of the first gas, and the vertical axis represents the decomposition rate X (%) of the first gas.

[0104] As Figure 8 shown, the decomposition rate X of the first gas has a relationship such that it decreases more and more slowly as the flow rate v in the processing chamber 201 increases. Here, according to Figure 8 , for example, by setting the flow rate v of the first gas to va, it is possible to supply the first gas with a decomposition rate X of 50% to the substrate S. In addition, by making the flow rate v of the first gas va or more, it is possible to supply the first gas with a decomposition rate X of 50% or less to the substrate S. That is, it is possible to control the decomposition rate according to the specified relationship between the decomposition rate and the flow rate of the first gas in the processing space. In other words, it is possible to predict the decomposition rate according to the specified relationship between the decomposition rate and the flow rate of the first gas in the processing space under certain conditions.

[0105] That is, by making the flow rate v of the first gas v1 or more as the first flow rate, it is possible to supply the first gas with a decomposition rate X of the first decomposition rate X1 or less to the substrate S. That is, by making the flow rate v of the first gas larger than the specified value, it is possible to make the decomposition rate of the first gas lower than the decomposition rate of the first gas when the flow rate v of the first gas is the specified value. In addition, by making the flow rate v of the first gas v2 or more, which is smaller than the first flow rate v1, it is possible to supply the first gas with a decomposition rate X of the second decomposition rate X2 or less, which is higher than the first decomposition rate X1, to the substrate S. That is, by making the flow rate v of the first gas smaller than the specified value, it is possible to make the decomposition rate of the first gas higher than the decomposition rate of the first gas when the flow rate v of the first gas is the specified value.

[0106] When using, for example, HCDS gas as the first gas, by controlling the residence time τ of the first gas in this step within the range of 1.00 to 0.01 seconds, it is possible to make the decomposition rate X of the first gas within the range of 0% to 100%. In addition, by controlling within the range of 1.00 to 0.10 seconds, it is possible to make the decomposition rate X within the range of 50% to 100%. In addition, by controlling within the range of 0.10 to 0.01 seconds, it is possible to make the decomposition rate X within the range of 0% to 50%. In addition, by controlling to 0.01 seconds or more, it is possible to make the decomposition rate X 0%, that is, it is possible to make the first gas undissociated. In addition, by setting it to more than 1.00 seconds, it is possible to make the decomposition rate X 100%.

[0107] When using, for example, HCDS gas as the first gas, by controlling the flow rate v of the first gas in this step to be 5.0 m / s or more, the decomposition rate X of the first gas can be within the range of 0% to 50%. Additionally, by making the flow rate v of the first gas, for example, 10 m / s or more, the decomposition rate X can be within the range of 0% to 25%. Additionally, by making the flow rate v of the first gas, for example, 15 m / s or more, the decomposition rate X can be within the range of 0% to 15%. Additionally, by controlling it to be 20.0 m / s or more, the decomposition rate X can be 0%, that is, the first gas can be undecomposed. Additionally, by setting it to be less than 5.0 m / s, the decomposition rate X can be 50 to 100%.

[0108] Herein, Figure 9 of (A), Figure 9 of (B), Figure 9 of (C) respectively represent schematic diagrams of the temporal changes in the supply amount, residence time τ, and flow rate v of the first gas in the processing chamber 201 of this step.

[0109] In the following description, in this step, the period from the start of supplying the first gas to t1 seconds is set as the entry region a1, and the period from t1 seconds to t2 seconds is set as the exposure region a2. The end time t1 of the entry region a1 and the end time t2 of the exposure region a2 are appropriately set according to the object to be processed and the processing content. As Figure 9 shown in (A) of, at the start of supplying the first gas, the supply amount of the first gas becomes the maximum, and the supply amount of the first gas decreases sharply in the entry region a1. And, continuously therewith, the supply amount of the first gas decreases slowly in the exposure region a2. Additionally, as Figure 9 shown in (B) of, the residence time of the first gas becomes extremely long in the entry region a1, and continuously therewith, the residence time of the first gas becomes long slowly in the exposure region a2. Additionally, as Figure 9 shown in (C) of, at the start of supplying the first gas, the flow rate of the first gas becomes the fastest (high flow rate), and it drops sharply in the entry region a1. And, continuously therewith, the flow rate of the first gas decreases slowly in the exposure region a2.

[0110] In the entry region a1, the first gas has a relatively high flow rate, and the residence time of the first gas in the processing chamber 201 can be shortened. That is, as Figure 7 shown, according to the relationship between the residence time of the first gas and the decomposition rate X of the first gas, a first gas with a decomposition rate in the first range of low decomposition rate, such as 0 to 50%, preferably 0 to 15%, and more preferably 0%, can be supplied to the substrate S.

[0111] In addition, in the inlet region a1, the flow rate of the first gas is relatively high, and the supply amount of the first gas is relatively high. That is, a large flow rate of the first gas is supplied in a short time from the start of supplying the first gas. In such a case, during the period from the generation of the reaction by-products described below to the adsorption on the surface of the substrate S, the adsorbed amount of one or both of the processing gas adsorbed on the surface of the substrate S and the first element-containing substance described below increases. Therefore, the film formation rate can be increased. In addition, the amount of the first gas reaching the deep side of the recess in a short time from the start of supplying the first gas increases. As a result, during the period from the generation of the reaction by-products to the adsorption on the substrate S, the adsorbed amount of one or both of the processing gas and the first element-containing substance increases. Therefore, the step coverage can be improved.

[0112] In addition, when forming a film in the recess (or groove, trench, hole) formed on the substrate S, the higher the reactivity of the gas, the higher the easiness of adsorption to the opening side of the recess, and the more difficult it is to adsorb to the deep side of the recess. Therefore, when using a gas (e.g., HCDS gas) that generates a more reactive substance by decomposition as the first gas for film formation in the recess, the shorter the residence time τ of the first gas and / or the higher the flow rate v of the first gas, the lower the decomposition rate X, and the step coverage can be improved. In addition, it is preferable for improving the step coverage to control the residence time τ of the first gas and / or the flow rate v of the first gas so that the decomposition rate X of the first gas is 0%. In addition, it is preferable for improving the step coverage to control the residence time τ of the first gas and / or the flow rate v of the first gas so that the decomposition rate X of the first gas is 0% in at least a part of the inlet region a1.

[0113] When using, for example, HCDS gas as the first gas, in the inlet region a1, by setting the flow rate of the first gas to, for example, 10 m / s or more, the decomposition rate X can be set to a relatively low value of 0% to 25%, which is beneficial for improving the step coverage. In addition, by setting the flow rate of the first gas to, for example, 15 m / s or more, the decomposition rate can be set to an even lower value in the range of 0% to 15%, which is preferable for improving the step coverage. In addition, by controlling to 20.0 m / s or more, the decomposition rate can be made 0%, that is, the first gas can be made undecomposed, which is further preferable for improving the step coverage. In addition, in the inlet region a1, the film formation rate can also be controlled by setting the flow rate of the first gas to, for example, 5 to 10 m / s and setting the decomposition rate X to 25% to 50%.

[0114] In addition, in the exposure region a2, the first gas becomes a low flow rate, and the residence time of the first gas in the processing chamber 201 can be extended. That is, as Figure 7As shown, according to the relationship between the residence time of the first gas and the decomposition rate X of the first gas, it is possible to supply the substrate S with the first gas having a high decomposition rate within the second range, for example, 15 to 100%, preferably 25 to 100%, and more preferably 50 to 100%. Therefore, the film formation rate can be controlled by the decomposition rate X.

[0115] When using, for example, HCDS gas as the first gas, in the exposure area a2, if the flow rate of the first gas is set to, for example, 5.0 m / second or less, the decomposition rate of the first gas can be set to 50% or more. If it is set to 10 m / second or less, the decomposition rate of the first gas can be set to 25% or more. If it is set to 15 m / second or less, the decomposition rate of the first gas can be set to 15% or more. Therefore, the film formation rate can be controlled by the decomposition rate X.

[0116] That is, in this step, by quickly supplying the first gas, the decomposition rate X of the first gas supplied to the substrate S can be changed. In addition, in this step, by quickly supplying the first gas, the flow rate of the first gas is controlled. Thus, the residence time of the first gas in the processing chamber 201 is controlled, and the decomposition rate X of the first gas can be controlled.

[0117] In addition, in this step, by quickly supplying the first gas, the supply amount of the first gas can be increased when starting to supply the first gas. When using, for example, HCDS gas as the first gas, the supply amount of the first gas per unit time per substrate S can be, for example, 0.001 to 15 slm, preferably 0.05 to 10 slm, and more preferably 0.010 to 5 slm. If it is less than 0.001 slm, the partial pressure of the first gas in the processing chamber 201 decreases, and sometimes the film formation rate decreases. If it is greater than 15 slm, due to the increase in the partial pressure of the first gas in the processing chamber 201, the decomposition of the first gas may proceed excessively. If it is 0.001 to 15 slm, the decrease in the film formation rate and the excessive decomposition of the first gas can be suppressed, and the flow rate is changed by controlling the flow rate of the first gas. In addition, if it is 0.05 to 10 slm, the decrease in the film formation rate and the decomposition of the first gas can be further suppressed, and the flow rate is changed by controlling the flow rate of the first gas. If it is 0.010 to 5 slm, the decrease in the film formation rate and the excessive decomposition of the first gas can be sufficiently suppressed, and the flow rate is changed by controlling the flow rate of the first gas.

[0118] In addition, by quickly supplying the first gas, the first gas whose pressure has increased (boosted) in the tank 259 can be supplied into the processing chamber 201. Thereby, the flow rate of the first gas at the start of supply can be increased.

[0119] That is, this step has the following processes: a process of controlling the decomposition rate X of the first gas within a first range, for example, 0 to 25%; a process of controlling the decomposition rate X of the first gas within a second range, for example, 25 to 100%. In addition, in this step, by quickly supplying the first gas, after the supply at a low decomposition rate with a short residence time of the first gas, the supply at a high decomposition rate with a long residence time is continuously carried out. Thus, the first gas with different decomposition rates can be continuously supplied, and it is possible to suppress the adsorption of reaction by-products and the like on the adsorption sites when purging and exhausting the inside of the processing chamber 201. In addition, by performing the high decomposition rate supply after the low decomposition rate supply with a large amount supplied in a short time, it is possible to suppress the adsorption of the reaction by-products described later on the adsorption sites.

[0120] In this way, in the process of controlling the decomposition rate X of the first gas within the first range, the step coverage performance can be improved, and in the process of controlling within a second range that is at least partially different from the first range, the film formation rate can be improved. That is, it is possible to balance the improvement of the step coverage performance and the improvement of the film formation rate.

[0121] In addition, as described above, in this step, the valve 282 and the APC valve 283 are in an open state, and during the supply of the first gas into the processing chamber 201, the reaction tube 210 is evacuated by the vacuum pump 284. As a result, the pressure inside the processing chamber 201 becomes low, the flow rate of the first gas increases, and the residence time τ of the first gas inside the processing chamber 201 can be shortened.

[0122] In addition, during the supply of the first gas into the processing chamber 201, the valve 258 can be opened, and a gas having a molecular weight smaller than that of the first gas can be introduced into the gas supply pipe 251 as a low molecular weight gas via the gas supply pipe 255. That is, a mixed processing gas formed by mixing the low molecular weight gas and the first gas can be supplied to the processing chamber 201. Here, the low molecular weight gas is preferably a gas having low reactivity with the first gas. In addition, as the low molecular weight gas, an inert gas can also be used. In addition, in order to prevent the first gas from invading the gas supply pipe 261, the valves 268 and 264 can be opened to allow the inert gas to flow into the gas supply pipe 261. In this case, it can be considered that the inert gas supplied from the gas supply pipe 261 is also included in the mixed processing gas.

[0123] Here, as the low molecular weight gas, for example, nitrogen (N2), helium (He), argon (Ar), etc. can be used.

[0124] By using the mixed processing gas, the average molecular weight of the gas supplied in this step can be reduced. When supplying the mixed processing gas and the first gas with equal kinetic energy under the same conditions, the flow rate of the mixed processing gas with a small gas average molecular weight is larger than that of the first gas. Thus, the flow rate of the mixed processing gas can be made faster than that of the first gas.

[0125] Here, the amount of the low molecular weight gas in the mixed processing gas can be, for example, 50 times or less. If it is greater than 50 times the amount of the first gas, as the proportion of the low molecular weight gas in the mixed processing gas increases, the partial pressure of the first gas in the processing chamber 201 decreases, sometimes resulting in a decrease in the film formation rate and the step coverage. If the amount of the low molecular weight gas in the mixed processing gas is within the range of 50 times or less the amount of the first gas in the mixed processing gas, the influence of the decrease in the partial pressure of the first gas can be suppressed, and the flow rate of the first gas can be controlled. In addition, if the amount of the low molecular weight gas in the mixed processing gas is set to, for example, 40 times or less, the influence of the decrease in the partial pressure of the first gas can be further suppressed. In addition, if it is, for example, 30 times or less, the influence of the decrease in the partial pressure of the first gas is further significantly suppressed. Therefore, the decomposition rate is controlled, and for the concave portion with a high aspect ratio, the step coverage is not easily reduced.

[0126] In addition, in at least a part of this step, the volume of the first gas supplied into the processing chamber 201 per unit time can be 0.0005 to 6 times, preferably 0.0015 to 3 times, and more preferably 0.0030 to 1 times the volume of the processing chamber 201. If it is less than 0.0005 times, the partial pressure of the first gas in the processing chamber 201 decreases, and sometimes the film formation rate decreases. If it is greater than 6 times, since the partial pressure of the first gas in the processing chamber 201 increases, the decomposition of the first gas sometimes proceeds excessively. If it is 0.0005 to 6 times, the decrease in the film formation rate and the excessive decomposition of the first gas can be suppressed, and the flow rate is changed by controlling the flow rate of the first gas. In addition, if it is 0.0015 to 3 times, the decrease in the film formation rate and the decomposition of the first gas can be further suppressed, and the flow rate is changed by controlling the flow rate of the first gas. If it is 0.0030 to 1 times, the decrease in the film formation rate and the excessive decomposition of the first gas can be sufficiently suppressed, and the flow rate is changed by controlling the flow rate of the first gas.

[0127] In addition, in at least a part of this step, the volume of the gas discharged from the processing chamber 201 per unit time can be set to 50 to 4000 times, preferably 100 to 2000 times, and more preferably 300 to 1000 times the volume of the processing chamber 201. If it is less than 50 times, the time until the pressure in the processing chamber 201 rises after the first gas is supplied becomes short, and it may be difficult to make the flow rate of the first gas high. Therefore, it may be difficult to perform control such as maintaining a state where the decomposition rate of the first gas is low (for example, a state where the decomposition rate of the first gas is 25% or less, 15% or less, 0% or less) for a certain period of time. If it is more than 4000 times, the partial pressure of the first gas in the processing chamber 201 decreases, and the film formation rate may decrease. If it is 50 to 4000 times, the decrease in the film formation rate of the first gas is suppressed, and it is easy to perform control to maintain a state where the decomposition rate of the first gas is low for a certain period of time. In addition, if it is 100 to 2000 times, the decrease in the film formation rate of the first gas is further suppressed, and it is easier to perform control to maintain a state where the decomposition rate of the first gas is low for a certain period of time. In addition, if it is 300 to 1000 times, the decrease in the film formation rate of the first gas is sufficiently suppressed, and it is easy to sufficiently perform control to maintain a state where the decomposition rate of the first gas is low for a certain period of time.

[0128] In addition, before this step and before starting to supply the first gas into the processing chamber 201, the APC valve 283 can be adjusted, and the reaction tube 210 can be evacuated using the vacuum pump 284. As a result, the flow rate of the first gas, particularly the flow rate at the start of supply, that is, the flow rate in the above-described entry region, increases, and the residence time τ of the first gas in the processing chamber 201 can be shortened.

[0129] In addition, the temperature in the processing chamber 201 in this step can also be set higher than the decomposition temperature of the first gas. As a result, the film formation rate can be improved by increasing the reactivity of the first gas, and the increase in the decomposition rate of the first gas can be suppressed by shortening the residence time of the first gas in the processing chamber 201.

[0130] This step can be performed in such a manner that at least a part of the adsorption sites on the surface of the substrate S becomes a first element site chemically adsorbed with a first element-containing substance, where the first element-containing substance is a substance containing the first element included in the first gas.

[0131] In the above-described embodiments, for example, group XIV elements such as silicon (Si) and germanium (Ge), and group XIII elements such as aluminum (Al), gallium (Ga), and indium (In) can be used as the first element. Additionally, for example, transition metal elements can also be used as the first element. As transition metal elements, for example, group IV elements such as titanium (Ti), zirconium (Zr), hafnium (Hf), group V elements such as niobium (Nb), tantalum (Ta), group VI elements such as molybdenum (Mo), tungsten (W), group VII element such as manganese (Mn), group VIII element such as ruthenium (Ru), group IX element such as cobalt (Co), group X element such as nickel (Ni), etc. can be used as the first element.

[0132] As the first gas, for example, a Si-containing gas containing Si as the first element can be used. As the Si-containing gas, for example, a gas containing Si and chlorine (Cl) can be used. As the gas containing Si and Cl, for example, Figure 10 the raw material gas containing an Si-Si bond such as the HCDS gas described in (A) of Figure 10 can be used. As shown in (A) of Figure 10 , the HCDS gas contains Si and a chlorine group (chloride) in its chemical structural formula (per molecule). Additionally, as the gas containing Si and Cl, for example, 1,2,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated: TCDMDS), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated: DCTMDS) can be used. As described in (B) of Figure 10 , TCDMDS has an Si-Si bond and further contains a chlorine group and an alkylene group. Additionally, as described in (C) of Figure 10 , DCTMDS has an Si-Si bond and further contains a chlorine group and an alkylene group. As the first gas, one or more of these gases can be used.

[0133] As the inert gas, for example, N2 gas, Ar gas, He gas, noble gases such as neon (Ne) gas, xenon (Xe) gas, etc. can be used. As the inert gas, one or more of these gases can be used. This is the same for each step described later.

[0134] When, for example, HCDS gas is used as the first gas, if the HCDS gas is decomposed and the bonding between Si bonds is cut off, SiCl4 and SiCl2 with higher reactivity than the HCDS gas are generated. That is, the HCDS gas decomposes as shown below.

[0135] HCDS (Si2Cl6) → SiCl4 + SiCl2

[0136] SiCl4 and SiCl2 have higher reactivity compared to HCDS. Therefore, the decomposition rate of HCDS is high, and as the decomposition of HCDS proceeds, the reaction proceeds. Also, when using, for example, ammonia (NH3) gas as the second gas described later, SiCl2 and SiCl4 react with the NH groups described later to form a SiN layer, and reaction by-products such as hydrogen chloride (HCl) are generated at this time.

[0137] At least a part of the adsorption sites on the surface of the substrate S becomes Si sites that chemically adsorb a Si-containing substance, i.e., a Si-containing material, but reaction by-products such as HCl adsorb to the adsorption sites on the substrate S, hindering the adsorption of the Si-containing material. In this step, by rapidly supplying the first gas, a large amount of the first gas is supplied to the substrate S in a short time from the start of supply. Therefore, it is possible to reduce the adsorption sites of reaction by-products such as HCl on the substrate S and increase the adsorption amount of the Si-containing material. Thereby, the film formation rate can be increased, and the step coverage performance can be improved.

[0138] <Purge, step S2>

[0139] In this step, a purge gas is supplied to the processing chamber 201 in which the substrate S is disposed inside. That is, after the rapid supply of the first gas in step S1, the Si-containing material that is not adsorbed to the adsorption sites and the reaction by-products that are re-adsorbed to the surface of the substrate S are removed and removed from the inside of the reaction tube 210.

[0140] Specifically, with the valve 254 open, the valve 275 is closed, the valves 258, 268, and 264 are opened, and an inert gas as the purge gas is supplied into the gas supply pipes 251 and 261 via the gas supply pipes 255 and 265. Also, with the valves 282 of the exhaust pipe 281 and the APC valve 283 open, the inside of the reaction tube 210 is evacuated using the vacuum pump 284.

[0141] <Second gas supply process, step S3>

[0142] Next, a second gas that reacts with the first gas is supplied to the processing chamber 201 in which the substrate S is disposed inside. Specifically, in this step, the second gas is previously stored in the tank 269 provided in the gas supply pipe 261. And when supplying the second gas, the valve 264 provided on the downstream side of the tank 269 between the tank 269 and the nozzle 224 is opened, and the second gas is supplied from the tank 269 in which the second gas is previously stored into the gas supply pipe 261. Then, after a predetermined time has elapsed since the start of supplying the second gas, the valve 264 is closed, and the supply of the second gas into the gas supply pipe 261 is stopped.

[0143] After the second gas is supplied in a large amount from the gas supply structure 212 to the inside of the reaction tube 210 via the upstream rectifying section 214 in a short time, it is exposed and then discharged via the space on the substrate S, the downstream rectifying section 215, the gas exhaust structure 213, and the exhaust pipe 281. At this time, the valve 282 and the APC valve 283 are in an open state. Here, during the supply of the second gas into the processing chamber 201, the valve 276 can be in an open state or a closed state. In addition, the valve 268 can be opened to allow an inert gas such as N2 gas to flow into the gas supply pipe 261 via the gas supply pipe 265. In addition, in order to prevent the second gas from invading the gas supply pipe 251, the valves 258 and 254 can be opened to allow an inert gas to flow into the gas supply pipe 251. At this time, the second gas is supplied in a large amount at once in a horizontal direction relative to the substrate S from the side of the substrate S via the gas supply structure 212 communicating with the inside of the reaction tube 210.

[0144] In addition, the temperature inside the processing chamber 201 at this time can be set higher than the decomposition temperature of the second gas. In addition, in this step, similar to the above step S1, the residence time τ of the second gas can be set according to the specified relationship between the decomposition rate X of the second gas in the processing chamber 201 and the residence time τ of the second gas in the processing chamber 201, thereby controlling the decomposition rate X of the second gas.

[0145] As the second gas, for example, a gas containing a second element different from the first gas can be used. The second element is, for example, one of N, oxygen (O), and carbon (C). As the second gas, for example, a gas containing hydrogen (H) and N gas can be used. As the gas containing H and N gas, for example, ammonia (NH3) gas, diazene (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas, etc., which are hydrogen nitride-based gases containing N-H bonds, can be used. As the second gas, one or more of them can be used.

[0146] <Purge, Step S4>

[0147] In this step, a purge gas is supplied to the processing chamber 201 in which the substrate S is disposed inside through the same processing procedure as in Step S2. That is, after the rapid supply of the second gas in Step S3, the second gas that is not adsorbed on the adsorption sites and the reaction by-products generated by the reaction with the second gas and re-adsorbed on the surface of the substrate S are removed from the inside of the reaction tube 210.

[0148] Specifically, with valve 264 open, valve 276 is closed, and valves 268, 258, and 254 are opened. An inert gas as a purge gas is supplied into gas supply pipes 251 and 261 via gas supply pipes 255 and 265. Also, with valves 282 of exhaust pipe 281 and APC valve 283 open, the inside of reaction tube 210 is evacuated using vacuum pump 284. Thereby, the reaction between the first gas and the second gas in the gas phase existing in reaction tube 210 can be suppressed.

[0149] (Number of implementation regulations)

[0150] The cycles of the above-described first gas supply process and second gas supply process are performed successively and non-simultaneously for a specified number of times (n times, where n is an integer of 1 or more). Thereby, a film with a specified thickness is formed on substrate S having a concave portion. For example, when using HCDS gas as the first gas and a gas containing H and N as the second gas, a SiN film is formed. Thereby, a film with improved step coverage performance and increased film formation rate can be formed on substrate S having a concave portion.

[0151] (S110)

[0152] Next, the substrate unloading process S110 will be described. In S110, the processed substrate S is unloaded outside transfer chamber 217 in a process opposite to the above-described substrate loading process S104.

[0153] (S112)

[0154] Next, determination S112 will be described. Here, it is determined whether the substrate has been processed a specified number of times. If it is determined that the specified number of times has not been processed, the process returns to substrate loading process S104 to process the next substrate S. If it is determined that the specified number of times has been processed, the process ends.

[0155] In addition, in the above, it appears horizontal in the formation of the air flow, but as long as the main gas flow is formed in the horizontal direction as a whole, and within the range that does not affect the uniform processing of multiple substrates, it can also be an air flow that diffuses in the vertical direction.

[0156] In addition, in the above, there are expressions such as the same degree, equivalent, equal, etc. Of course, they include expressions that are substantially the same.

[0157] (Other embodiments)

[0158] The embodiments of this method have been specifically described above, but are not limited thereto, and various modifications can be made without departing from its spirit.

[0159] In the above-described manner, the case where the tank 259 is provided in the first gas supply system 250 described above has been described, but the present manner is not limited thereto. That is, in the first gas supply system 250, the tank 259 may not be provided, and the first gas may be supplied by a non-rapid supply method. In this case, the same effects as those in the above-described manner can also be obtained.

[0160] Similarly, the case where the tank 269 is provided in the second gas supply system 260 described above has been described, but the present manner is not limited thereto. That is, in the second gas supply system 260, the tank 269 may not be provided, and the second gas may be supplied by a non-rapid supply method. In this case, the same effects as those in the above-described manner can also be obtained.

[0161] In addition, in the above-described manner, the case where the first gas and the second gas are used to form a film on the substrate S in the film formation process performed by the substrate processing apparatus has been described as an example, but the present manner is not limited thereto. That is, other types of gases can be used as the processing gas for the film formation process to form other types of thin films. Also, even when three or more types of processing gases are used, the present manner can be applied.

[0162] In addition, in the above-described manner, the film formation process is cited as an example of the process performed by the substrate processing apparatus, but the present manner is not limited thereto. That is, the present manner can also be applied to film formation processes other than the film formation process cited as an example in the above-described manner.

[0163] In addition, in the above-described manner, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described manner. For example, when forming a film using a single-substrate processing apparatus that processes one or several substrates at a time, it can also be appropriately applied. In addition, in the above-described manner, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-described manner, and it can also be appropriately applied when forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0164] When using these substrate processing apparatuses, each process can also be performed with the same processing procedure and processing conditions as those in the above-described manner or modification example, and the same effects as those in the above-described manner or modification example can be obtained.

[0165] The above-described manner or modification example can be used in appropriate combination. The processing procedure and processing conditions at this time can be set to be the same as those of the above-described manner or modification example, for example.

[0166] Symbol Description

[0167] S Substrate

[0168] 201 Processing Chamber.

Claims

1. A substrate processing method, characterized in that, It has the following processes: (a) Control the decomposition rate according to the specified relationship between the decomposition rate and the residence time of the processing gas supplied into the processing space, whereby the substrate disposed in the processing space is processed.

2. The substrate processing method according to claim 1, wherein: In (a), the following processes are performed: (a1) Control the value of the decomposition rate within a first range; and (a2) Control the value of the decomposition rate within a second range that is at least partially different from the first range.

3. The substrate processing method according to claim 1, wherein: In (a), the value of the residence time is within a range below a first time, and the value of the decomposition rate at the first time is a first decomposition rate, whereby the value of the decomposition rate is controlled within a range below the first decomposition rate.

4. The substrate processing method according to claim 1, wherein: In (a), the following processes are performed: (a1) Make the value of the residence time within a range below a first time, and the value of the decomposition rate at the first time is a first decomposition rate, whereby the value of the decomposition rate is controlled within a range below the first decomposition rate; and (a2) Make the value of the residence time within a range below a second time that is longer than the first time, and the value of the decomposition rate at the second time is a second decomposition rate higher than the first decomposition rate, whereby the value of the decomposition rate is controlled within a range below the second decomposition rate.

5. The substrate processing method according to claim 1, wherein: In (a), the residence time is controlled by controlling the flow rate of the processing gas in the processing space.

6. The substrate processing method according to any one of claims 1 to 5, wherein: In (a), before starting to supply the processing gas to the processing space, the processing space is evacuated.

7. The substrate processing method according to any one of claims 1 to 5, wherein: In (a), during the supply of the processing gas to the processing space, the processing space is evacuated.

8. The substrate processing method according to claim 7, wherein: In at least a part of (a), the volume of the gas discharged from the processing space per unit time is 50 to 4000 times the volume of the processing space.

9. The substrate processing method according to any one of claims 1 to 5, wherein: In (a), the supply amount of the processing gas is the largest at the start of the supply of the processing gas.

10. The substrate processing method according to any one of claims 1 to 5, wherein: In (a), the pressurized processing gas is supplied to the processing space.

11. The substrate processing method according to any one of claims 1 to 5, wherein: In at least a part of (a), the volume of the processing gas supplied to the processing space per unit time is 0.0005 to 6 times the volume of the processing space.

12. The substrate processing method according to any one of claims 1 to 5, wherein: In (a), the processing gas is mixed with a low molecular weight gas having a molecular weight smaller than that of the processing gas and supplied to the processing space.

13. The substrate processing method according to any one of claims 1 to 5, characterized in that: In (a), the temperature in the processing space is higher than the decomposition temperature of the processing gas.

14. The substrate processing method according to any one of claims 1 to 5, characterized in that: The processing gas contains a first element. In (a), at least a part of the adsorption sites on the surface of the substrate is a first element site chemically adsorbing a first element-containing substance, where the first element-containing substance is a substance containing the first element.

15. The substrate processing method according to any one of claims 1 to 5, characterized in that: The processing gas is hexachloroethylsilane gas.

16. The substrate processing method according to any one of claims 1 to 5, characterized in that: The substrate processing method further has the following steps: (b) A reaction gas that reacts with the processing gas is supplied to the processing space.

17. A method for manufacturing a semiconductor device, characterized in that, Having the following steps: (a) The decomposition rate is controlled according to a specified relationship between the decomposition rate of the processing gas supplied to the processing space and the residence time, whereby the substrate disposed in the processing space is processed.

18. A substrate processing apparatus, characterized in that, Having: A processing space in which a substrate is disposed inside; A processing gas supply system that supplies a processing gas to the processing space; and A control unit that can control the processing gas supply system and can control the decomposition rate according to a specified relationship between the decomposition rate of the processing gas in the processing space and the residence time.

19. A program, characterized in that: The program causes a substrate processing apparatus to execute a process having the following process by a computer: (a) The decomposition rate is controlled according to a specified relationship between the decomposition rate of the processing gas supplied to the processing space and the residence time, whereby the substrate disposed in the processing space is processed.

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