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

Abstract

The present invention has: a step (a) for forming a film of a prescribed substance containing a first element on a substrate by performing a cycle for a prescribed number of times, said cycle including a step (a1) for forming a first substance containing the first element on the surface of the substrate by supplying a first gas to the substrate having a recess on the surface thereof under prescribed conditions; the predetermined conditions satisfy a temperature condition in which the temperature of the substrate is set to be equal to or higher than the decomposition temperature of the first gas, and a first condition in which, during a first period after the start of supply of the first gas, the amount of adsorption of the first substance at the opening of the recess is increased, i.e., the amount of adsorption of the opening is increased, and during a second period after the start of supply of the first gas, the amount of adsorption of the first substance at the opening of the recess is decreased. In a second period after the first period, the opening adsorption amount is gradually brought close to a predetermined value, and in a third period after the second period, the opening adsorption amount is increased, and (a1) ends in the second period.

Description

Technical Field

[0001] This invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a process. Background Technology

[0002] When gas is supplied to the substrate, the substrate temperature is sometimes set above the gas decomposition temperature and the substrate is processed (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-13630 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] The present invention provides a technology that can improve at least one of the properties of a membrane and its stepped coverage.

[0008] Technical means to solve the problem

[0009] According to one aspect of the present invention, a technique is provided comprising: step (a), which involves performing a cycle including step (a1) a predetermined number of times to form a film containing a predetermined substance containing a first element on a substrate, wherein step (a1) involves supplying a first gas to the substrate having recesses on its surface under predetermined conditions, and forming a first substance containing the first element on the surface of the substrate.

[0010] The above-mentioned conditions must satisfy both the temperature condition and condition 1.

[0011] This temperature condition is achieved by setting the temperature of the substrate above the decomposition temperature of the first gas.

[0012] The first condition is that, during a first period after the supply of the first gas begins, the amount of the first substance adsorbed at the opening of the recess (i.e., the opening adsorption amount) is increased; during a second period following the first period, the opening adsorption amount is gradually brought closer to a predetermined value; and during a third period following the second period, the opening adsorption amount is increased.

[0013] (a1) Ends during the second period mentioned above.

[0014] Technical effect

[0015] According to the present invention, at least one of the properties of the membrane and the stepped coverage can be improved. Attached Figure Description

[0016] Figure 1This is a schematic longitudinal cross-sectional view of a substrate processing apparatus according to one embodiment of the present invention.

[0017] Figure 2 (A) in the figure represents the first gas supply system in one embodiment of the present invention. Figure 2 (B) in the figure represents the second gas supply system in one embodiment of the present invention. Figure 2 (C) in the figure represents the exhaust system in one embodiment of the present invention.

[0018] Figure 3 This is a schematic structural diagram of the controller of the substrate processing apparatus according to an embodiment of the present invention, which is a block diagram representing the control system of the controller.

[0019] Figure 4 This is a schematic diagram of a longitudinal section of a recess formed on a substrate according to an embodiment of the present invention.

[0020] Figure 5 In this context, (A) represents the amount of adsorption at the opening in one embodiment of the present invention. top A diagram illustrating the changes over time. Figure 5 In this context, (B) represents the deep adsorption amount A in one embodiment of the present invention. btm A diagram illustrating the changes over time.

[0021] Figure 6 (A) is a graph schematically showing the change in the decomposition rate of the first gas in the processing chamber over time elapsed since the supply of the first gas in one embodiment of the present invention. Figure 6 (B) is a graph schematically showing the change in the flow rate of the first gas in the processing chamber over time elapsed since the supply of the first gas began, according to one embodiment of the present invention. Figure 6 (C) in the figure is a schematic diagram showing the change in pressure in the processing chamber over time from the start of the supply of the first gas in one embodiment of the present invention.

[0022] Figure 7 (A) is a flowchart of a substrate processing step in one embodiment of the present invention. Figure 7 (B) is a flowchart of a processing step in one embodiment of the present invention. Figure 7 (C) is a flowchart of the first gas supply process in one embodiment of the present invention. Figure 7 (D) is a flowchart of the preparation process in one embodiment of the present invention. Detailed Implementation

[0023] Hereinafter, one aspect of the present invention will be described primarily with reference to... Figure 1 , Figure 2 (A) to Figure 2 (C) Figure 3 , Figure 4 , Figure 5 (A) Figure 5 (B) Figure 6 (A) to Figure 6 (C) Figure 7 (A) to Figure 7 The following explanation will be provided along the (D) side. Furthermore, the accompanying drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to actual dimensions. Additionally, the dimensional relationships and ratios of elements may not be consistent between multiple drawings.

[0024] (1) Structure of the substrate processing device

[0025] The following describes the structure of the substrate processing apparatus 10 using... Figure 1 Let me explain.

[0026] The substrate processing apparatus 10 includes a reaction tube storage chamber 206b. Within the reaction tube storage chamber 206b are a reaction tube 210, a heater 211 (serving as a heating unit, furnace body, or temperature control unit) disposed around the outer periphery of the reaction tube 210, a gas supply structure 212 (serving as a gas supply unit), and a gas exhaust structure 213 (serving as a gas exhaust unit). The gas supply unit may also include an upstream rectifier 214 and nozzles 223 and 224 (described later). Furthermore, the gas exhaust unit may also include a downstream rectifier 215 (described later). The area within the reaction tube 210 where the substrate S is processed is referred to as a processing chamber 201. Alternatively, the processing chamber 201 may also be referred to as a processing space in which the substrate S is disposed.

[0027] The gas supplied from the gas supply structure 212 to the reaction tube 210 moves horizontally relative to the substrate S and is discharged from the gas exhaust structure 213. An upstream rectifier 214 is provided between the reaction tube 210 and the gas supply structure 212. Furthermore, a downstream rectifier 215 is provided 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. The heat from the heater 211 heats the substrate S and the gas in the processing chamber 201.

[0028] Gas supply structure 212 is connected to gas supply pipe 251 and gas supply pipe 261, and has a distribution section 225 for distributing the gas supplied from each gas supply pipe. Multiple nozzles 223 and 224 are provided downstream of the distribution section 225. In this embodiment, gas supply pipe 251 and gas supply pipe 261 are collectively referred to as gas supply pipe 221. Each nozzle is also referred to as a gas discharge section. The distribution section 225 is configured to supply gas from gas supply pipe 251 to nozzles 223 and from gas supply pipe 261 to nozzles 224. The upstream rectifier section 214 has a frame 227 and a partition plate 226. Nozzles 223 and 224 are provided between the partition plates 226 and between the partition plates 226 and the frame 227. The downstream rectifier section 215 has a frame 231 and a partition plate 232. The gas exhaust structure 213 is mainly composed of a frame 241, an exhaust pipe connection 242, and an exhaust port 244.

[0029] A transfer chamber 217 is formed at the lower part of the reaction tube 210. The following operations are performed inside the transfer chamber 217: the transfer of substrate S through a substrate loading inlet (not shown) between the inside and outside of the transfer chamber 217 by a transfer robot (not shown), and the loading and unloading of substrate S relative to the substrate support 300 (hereinafter, there may also be a case simply referred to as a crystal boat) inside the transfer chamber 217.

[0030] The vertical drive mechanism 400 causes the substrate support 300 and the partition plate support 310 to move vertically between the reaction tube 210 and the transfer chamber 217. Figure 1 This indicates that the substrate support 300 and the partition plate support 310 are raised by the vertical drive mechanism 400 and stored in the reaction tube 210. The vertical drive mechanism 400 includes a rotation drive mechanism 430 that rotates the substrate support 300 and the partition plate support 310 together, and a boat lifting mechanism 420 that drives the substrate support 300 relative to the partition plate support 310 in the vertical direction. The rotation drive mechanism 430 and the boat lifting mechanism 420 are fixed to a base flange 401, which serves as a cover. The base flange 401 is supported by a base plate 402 via a side plate 403. An O-ring 446 for vacuum sealing is provided on the upper surface of the base flange 401. The support member 440, which is fixed to the partition plate support 310, and the support member 441, which is fixed to the substrate support 300, are connected by a vacuum bellows 443.

[0031] On the substrate support 300, a plurality of substrates S are mounted at predetermined intervals in the vertical direction. In the partition plate support 310, a plurality of partition plates 314 are disposed directly below the substrates S, and are disposed on either or both of the upper and lower portions of the substrates S. In the substrate processing steps described later, it is preferable to align the heights of the partition plates 314, 226, and 232. This facilitates the formation of a horizontal gas flow from the partition plate 226, the substrate S, to the partition plate 232, where the flow in the vertical direction is suppressed, thus allowing for uniform processing of each substrate S.

[0032] In addition, Figure 1 The example shown is an example of five substrates S supported by a substrate support 300. However, the present invention is not limited to this. The substrate support 300 may also be configured to support approximately 5 to 50 substrates S. Furthermore, the expression of a numerical range such as "5 to 50 substrates" in this specification means that the lower and upper limits are included within that range. Therefore, for example, "5 to 50 substrates" means "more than 5 substrates and less than 50 substrates". The same applies to other numerical ranges.

[0033] like Figure 2 As described in (A), the gas supply pipe 251 is provided in sequence from upstream: a first gas source 252, a flow controller (flow control unit) i.e., a mass flow controller (MFC) 253, an on / off valve i.e., a valve 275, a storage unit for storing gas inside i.e., a tank 259, a pressure measuring device (pressure measuring unit) i.e., a sensor 301 for measuring the pressure inside the tank 259, and a valve 254.

[0034] The tank 259 is equipped with a temperature measuring device (temperature measuring unit), i.e., a sensor 448, which measures the temperature of the tank 259 and / or the gas stored within it. Furthermore, the tank 259 is equipped with a temperature controller (temperature control unit), i.e., a heater 447, which regulates the temperature of the tank 259 and / or the gas stored within it. Alternatively, the tank 259 can be omitted, and the diameter of the gas supply pipe 251 between the upstream valve 275 and the downstream valve 254 of the tank 259 can be increased, or it can be made spiral-shaped to increase its capacity, and it can be used as a storage unit. By opening and closing the upstream valve 275 and the downstream valve 254 of the tank 259, the gas supplied from the gas supply pipe 251 can be temporarily stored (filled) in the tank 259, or the gas stored in the tank 259 can be supplied to the processing chamber 201.

[0035] The first gas source 252 is a gas source used to supply the first gas (also called the raw material gas). Alternatively, the first gas source 252 can also be a vaporizer that generates the first gas by vaporizing a liquid or solid. The following explanation will use the case where a gas obtained by vaporizing a liquid or solid is used as the first gas.

[0036] The first gas supply system 250 (also called the raw material gas supply system) is mainly composed of a gas supply pipe 251, an MFC 253, a valve 275, a tank 259, a sensor 301, and a valve 254. A first gas source 252 may also be included in the first gas supply system 250. Furthermore, a sensor 448 and a heater 447 may also be included in the first gas supply system 250. Additionally, heaters (not shown) other than heater 447 may be provided in various parts of the first gas supply system 250 to adjust the temperature of the first gas supply system 250. This is an example of a gas supply system that stores the first gas in the tank 259 and supplies the first gas stored in the tank 259 to the substrate S.

[0037] In the gas supply pipe 251, a gas exhaust pipe 302 is connected between the sensor 301 and the valve 254. This gas exhaust pipe 302 is used to discharge the gas in the tank 259 towards the outside of the processing chamber 201 instead of supplying it towards the processing chamber 201. A valve 303 is provided in the gas exhaust pipe 302. The first gas exhaust system (also called the raw material gas exhaust system) is mainly composed of the gas exhaust pipe 302 and the valve 303. The first gas exhaust system can also be included in the first gas supply system 250.

[0038] In the gas supply pipe 251, a gas supply pipe 255 is connected between the valve 275 and the tank 259. An inert gas source 256, an MFC 257, and a valve 258 are sequentially arranged upstream of the gas supply pipe 255. Inert gas is supplied from the inert gas source 256. The first inert gas supply system is mainly composed of the gas supply pipe 255, the MFC 257, and the valve 258. Alternatively, the inert gas source 256 can be included in the first inert gas supply system. Alternatively, the first inert gas supply system can be included in the first gas supply system 250.

[0039] like Figure 2 As described in (B), a second gas source 262, an MFC 263, and a valve 264 are sequentially arranged from upstream in the gas supply pipe 261. The second gas source 262 is used to supply the second gas (also called the reaction gas). The second gas supply system 260 (also called the reaction gas supply system) is mainly composed of the gas supply pipe 261, the MFC 263, and the valve 264. Alternatively, the second gas source 262 can be included in the second gas supply system 260.

[0040] In gas supply pipe 261, downstream of valve 264, gas supply pipe 265 is connected. In gas supply pipe 265, from upstream, an inert gas source 266, an MFC 267, and a valve 268 are sequentially arranged. Inert gas is supplied from inert gas source 266. The second inert gas supply system is mainly composed of gas supply pipe 265, MFC 267, and valve 268. Alternatively, inert gas source 266 can be included in the second inert gas supply system. Alternatively, the second inert gas supply system can be included in the second gas supply system 260.

[0041] like Figure 2 As described in (C), a vacuum pump 284, serving as a vacuum exhaust device, is connected to the exhaust pipe 281 via valve 282 and an APC (Auto Pressure Controller) valve 283, which acts as a pressure regulator (pressure adjustment unit). This configuration enables vacuum exhaust to bring the pressure within the reaction tube 210 to a predetermined pressure (vacuum level). The exhaust pipe 281 is connected to the exhaust pipe connection 242. The exhaust pipe 281, valve 282, and APC valve 283 are collectively referred to as the exhaust system 280. The exhaust system 280 is also called the processing chamber exhaust system. Alternatively, the vacuum pump 284 may be included within the exhaust system 280.

[0042] Next, use Figure 3 To explain the control unit (control unit), i.e., the controller. The substrate processing apparatus 10 has a controller 600 that controls the operation of each part of the substrate processing apparatus 10.

[0043] exist Figure 3 The diagram shows a schematic of the controller 600. The controller 600 is configured as a computer, which includes a CPU (Central Processing Unit) 601, RAM (Random Access Memory) 602, a storage device 603 as a storage unit, and an I / O port 604. The RAM 602, storage device 603, and I / O port 604 are configured to exchange data with the CPU 601 via an internal bus 605.

[0044] The storage device 603 is configured, for example, by flash memory or HDD (Hard Disk Drive). Within the storage device 603, control programs that control the operation of the substrate processing apparatus 10, process recipes that describe the substrate processing procedures and conditions, etc., are readablely recorded and stored. Furthermore, the process recipe is a combination of processes in the substrate processing steps described later, executed by the controller 600 in a manner that achieves a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc., will be collectively referred to and simply as a program (program product). Additionally, when the term "program" is used in this specification, it may include only the process recipe unit, only the control program unit, or both. Furthermore, the RAM 602 is configured as a memory area (working area) that temporarily holds programs, data, etc., read by the CPU 601.

[0045] I / O port 604 is connected to the aforementioned up-down drive mechanism 400, heaters 211 and 447, APC valve 283, vacuum pump 284, MFC 253, 257, 263 and 267, valves 254, 258, 264, 268, 275, 282 and 303, sensors 301 and 448, rotary drive mechanism 430, etc.

[0046] CPU 601 is configured to read and execute control programs from storage device 603, and to read process recipes from storage device 603 based on inputs such as operation instructions from input / output device 681. Furthermore, the CPU601 is configured to control the following actions based on the read process recipe: lifting and lowering of the substrate support 300 by the up-down drive mechanism 400; heating by the heater 211; opening adjustment of the APC valve 283; starting and stopping of the vacuum pump 284; flow rate adjustment of various gases by the MFCs 253, 257, 263, and 267; opening and closing of valves 254, 258, 264, 268, 275, 282, and 303; pressure measurement within the tank 259 by the sensor 301; temperature measurement of the tank 259 and / or the gas stored in the tank 259 by the sensor 448; temperature control of the tank 259 and / or the gas stored in the tank 259 by the heater 447; and rotation and speed adjustment of the substrate support 300 by the rotation drive mechanism 430. MFC253, 257, 263, 267, valves 254, 258, 264, 268, 275, 282, 303, APC valve 283, and vacuum pump 284 can be used as a gas control unit, which is configured to control the supply and exhaust of gas into the processing chamber 201.

[0047] The controller 600 can use an external storage device (e.g., a hard disk, a DVD, a magneto-optical disk, a USB flash drive, or a semiconductor memory) 682 that records and stores the aforementioned program to install the program onto a computer, thereby constituting the controller 600 of this type. Furthermore, the method for supplying the program to the computer is not limited to supplying it via the external storage device 682. For example, a communication unit such as the Internet or a dedicated line can be used to supply the program without using the external storage device 682. Furthermore, the storage device 603 and the external storage device 682 constitute a computer-readable recording medium containing the program. Hereinafter, these will be collectively and simply referred to as a recording medium. Additionally, in this specification, the term "recording medium" may refer only to the storage device 603, only to the external storage device 682, or both.

[0048] (2) Substrate processing process

[0049] Next, as a step in the manufacturing process of a semiconductor device (assembly), for the substrate processing step in which a thin film is formed on a substrate S using a substrate processing apparatus 10 with the above-described structure, the following steps are performed: Figure 4 and Figure 7 (A) to Figure 7 Let's explain using (D) in the text.

[0050] like Figure 4 As shown, grooves or holes are formed on the surface of the substrate S. In the following description, the opening 701 of the recess 700 will be referred to as the opening 701, and the depth 702 of the recess 700 will be referred to as the depth 702.

[0051] In the substrate processing process, such as Figure 7 As shown in (A), the following steps are performed: preparation step S0, substrate loading step S1, pressure and temperature adjustment step S2, processing step S3, pressure and temperature adjustment step S4, and substrate unloading step S5. Furthermore, in the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 600. Since the preparation step S0 can be omitted, the following description begins with the substrate loading step S1, while the description of the preparation step S0 will follow.

[0052] In this specification, the term "substrate" may refer to the substrate itself or to a laminate of the substrate and a specified layer, film, etc., formed on its surface. The term "surface of the substrate" may refer to the surface of the substrate itself or to the surface of a specified layer, etc., formed on the substrate. The phrase "forming a specified layer on the substrate" may indicate that the specified layer is formed directly on the surface of the substrate itself or that the specified layer is formed on top of a layer, etc., formed on the substrate. The term "wafer" used in this specification has the same meaning as the term "substrate."

[0053] (Substrate handling process S1)

[0054] In the transfer chamber 217, multiple substrates S are loaded into the substrate support 300 (wafer loading). Subsequently, the substrate support 300 is raised by the up-down drive mechanism 400, thereby moving the substrates S into the reaction tube 210, i.e., the processing chamber 201 (crystal boat loading).

[0055] (Pressure and temperature adjustment process S2)

[0056] The opening degree of APC valve 283 is adjusted and exhaust is performed in the processing chamber 201 by vacuum pump 284 to bring the pressure in the processing chamber 201 to the required level (pressure adjustment). Furthermore, the output of heater 211 is controlled to bring the temperature in the processing chamber 201 or the substrate S to the required level (temperature adjustment). That is, the pressure and temperature adjustment step S2 is a step of adjusting at least one of the temperature and pressure in the processing chamber 201. In addition, the substrate support 300 (and the substrate S) and the partition plate support 310 are rotated by the rotary drive mechanism 430. Furthermore, the tank 259 is heated by heater 447 to bring the tank 259 or the gas inside the tank 259 to the required temperature (tank temperature adjustment).

[0057] At this time, the temperature of the first gas supply system 250 is controlled so that the temperature of the first gas supplied from the first gas source 252 to the tank 259 is lower than the temperature of the tank 259 or the temperature of the first gas inside the tank 259. This suppresses the generation of particulate matter within the tank 259 due to partial liquefaction or solidification of the first gas. These actions are performed continuously, at least until the processing of the substrate S is completed.

[0058] (Processing step S3)

[0059] Next, as Figure 7As shown in (B), the processing cycle is performed a predetermined number of times (n times, where n is an integer of 1 or 2 or more). This processing cycle includes a first gas supply step S31, a purge gas supply step S32, a second gas supply step S33, and a purge gas supply step S34. In the following description, the case of processing step S3 being performed under predetermined conditions will be used as an example. The predetermined conditions satisfy the temperature condition of setting the temperature of the substrate S (and inside the processing chamber 201) to be above the decomposition temperature of the first gas, as well as the first to third conditions described later. In processing step S3, as... Figure 7 As shown in (B), the first gas supply process S31, the purging gas supply process S32, the second gas supply process S33, and the purging gas supply process S34 are performed.

[0060] [First gas supply process S31]

[0061] like Figure 7 As shown in (C), in the first gas supply step S31, the first gas is stored in the tank 259 in the storage step S311, and the first gas stored in the tank 259 is supplied to the processing chamber 201 (or the substrate S) in the supply step S312. As a result, a layer (first layer) containing the first element of the first substance is formed on the surface of the substrate S. In the first gas supply step S31, as... Figure 7 As shown in (C), the storage process S311 and the supply process S312 are carried out.

[0062] <Storage process S311>

[0063] Storage step S311 is the process of storing the first gas in tank 259. With valves 254, 258, 303, 264, and 268 closed, valve 275 is opened, thereby initiating the storage of the first gas into tank 259. Then, after a predetermined time has elapsed, valve 275 is closed, thereby ending storage step S311.

[0064] Furthermore, the storage step S311 in the first processing cycle can be partially performed simultaneously with the substrate loading step S1 and the pressure and temperature adjustment step S2. Additionally, when multiple processing cycles are performed, for the storage step S311 in subsequent processing cycles, at least one of the purge gas supply step S32, the second gas supply step S33, and the purge gas supply step S34 can be performed simultaneously with the storage step S311. This can improve production output.

[0065] <Supply Process S312>

[0066] In the supply process S312, a first gas is supplied to the substrate S under specified conditions. Specifically, with valves 258, 275, 303, 264, and 268 closed, valve 254 is opened, supplying (flowing) at least a portion of the first gas stored (filled) in the tank 259. This allows at least a portion of the first gas to be supplied to the substrate S in the processing chamber 201 at once. By supplying the first gas to the substrate S, a layer (first layer) containing a first element can be formed on the surface of the substrate S. At a predetermined time point after the start of the first gas supply, valve 254 is closed, thereby ending the supply process S312.

[0067] Here, the supply process S312 is preferably performed such that a predetermined amount X of the first gas remains in the tank 259 at the end of the supply process S312. The predetermined amount X can be set, for example, to any value from 0.1% to 99% of the amount of the first gas (predetermined amount Y) stored in the tank 259 at the beginning of the supply process S312. In this case, the supply process S312 can also be ended at the point when the pressure in the tank 259, as measured by the sensor 301, drops to a predetermined pressure. Furthermore, the amount of the first gas remaining in the tank 259 at the end of the supply process S312 can be controlled by adjusting the predetermined pressure.

[0068] Furthermore, in the supply process S312, valve 258 can be opened to supply inert gas into gas supply pipe 251 via gas supply pipe 255. Additionally, to prevent the first gas from entering gas supply pipe 261, valves 268 and 264 can also be opened to supply inert gas into gas supply pipe 261. Furthermore, for reasons described later, it is preferable to keep valve 282 and APC valve 283 open in the supply process S312. This increases the flow rate of the first gas in processing chamber 201, thus suppressing the decomposition of the first gas. Therefore, the second period T2 can be extended.

[0069] [Purge gas supply process S32]

[0070] In the purging gas supply process S32, the processing chamber 201 is purged. Specifically, with valves 275, 303, and 264 closed, valves 254, 258, and 268 are opened to supply inert gas as purging gas into the processing chamber 201, and exhaust gas is carried out by vacuum pump 284.

[0071] [Second gas supply process S33]

[0072] In the second gas supply process S33, with valves 254, 258, 275, 303, and 268 closed, valve 264 is opened, and after a predetermined time, valve 264 is closed. Thus, the second gas, whose flow rate has been adjusted by MFC 263, is exhausted after being supplied to the substrate S in the processing chamber 201. By supplying the second gas to the substrate S, the first layer on the substrate S can be modified into the second layer. At this time, valves 282 and APC valve 283 are open. Alternatively, valve 268 can be opened, allowing inert gas to flow into the gas supply pipe 261 via gas supply pipe 265. Furthermore, valves 258 and 254 can also be opened, allowing inert gas to flow into the gas supply pipe 251.

[0073] [Purge gas supply process S34]

[0074] In the purging gas supply process S34, the processing chamber 201 is purged using the same process as the purging gas supply process S32 described above.

[0075] [Number of times stipulated for implementation]

[0076] The processing cycle of performing the first gas supply step S31, the purge gas supply step S32, the second gas supply step S33, and the purge gas supply step S34 is performed a predetermined number of times (n times, where n is an integer of 1 or 2 or more). As a result, a film of a predetermined thickness containing, for example, a first element from the first gas and an element from the second gas is formed on the substrate S with a recess 700 on its surface.

[0077] (Pressure and temperature adjustment process S4)

[0078] An inert gas, used as a purging gas, is supplied into the processing chamber 201 and exhausted from the exhaust pipe 281. This removes any remaining gases and reaction byproducts from the processing chamber 201. Then, the ambient gas in the processing chamber 201 is replaced with the inert gas, and the pressure inside the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration). Furthermore, the output of the heater 211 is controlled to maintain the desired temperature inside the processing chamber 201 (temperature adjustment).

[0079] (Substrate removal process S5)

[0080] The base flange 401 is lowered by the up-down driving mechanism 400, opening the lower end of the reaction tube 210. Then, the processed substrate S is moved to the transfer chamber 217 (crystal boat removal) while supported by the substrate support 300. The processed substrate S is removed from the substrate support 300 in the transfer chamber 217 (wafer removal).

[0081] The following is about Figure 5(A) will be explained in detail.

[0082] exist Figure 5 The curve shown in (A) schematically represents the amount of the first substance formed at the opening 701 (opening adsorption amount A) when the first gas is supplied to the substrate S under the specified conditions of the first condition described later. top (Time changes) Figure 5 The horizontal axis of (A) in the diagram represents the elapsed time t from the start time t0 of the first gas supply. Figure 5 The vertical axis (A) in the figure represents the amount A of the first substance formed at the opening 701 in each cycle. top The following is about... Figure 5 The first period T1, the second period T2, and the third period T3 shown in (A) will be explained.

[0083] The first period T1 is the period after the first gas is supplied. During the first period T1, a large number of adsorption sites (hereinafter simply referred to as adsorption sites) exist on the surface of the substrate S, which can adsorb molecules of the first gas. Therefore, during the first period T1, A top It increases over time. Furthermore, during the first period T1, the decomposition rate of the first gas within the processing chamber 201 is low (e.g., a low decomposition rate including 0%), therefore, most of the first gas adsorbed on the substrate S remains undecomposed. Here, the decomposition rate of the first gas refers to the amount of first gas decomposed in the processing chamber 201 relative to the total amount of first gas supplied to the processing chamber 201.

[0084] The second period T2 is the period following the first period T1. During the second period T2, most of the adsorption sites on the substrate S are adsorbed with the first gas. Furthermore, during the second period T2, the first gas supplied to the processing chamber 201 and the first gas adsorbed on the substrate S are not decomposed; therefore, the adsorption of the first gas onto the substrate S is hindered. Thus, during the second period T2, A can be... top Gradually approaching a specific value (specified value A).

[0085] Period 3 (T3) follows period 2 (T2). During period 3 (T3), the decomposition (thermal decomposition) of the first gas occurs. Because the substances generated from the decomposition of the first gas (the decomposition products of the first gas) are more reactive than the undecomposed first gas, the adsorption of the decomposition products of the first gas onto the substrate S is less hindered by the first gas already adsorbed on the substrate S. Therefore, during period 3 (T3), A... top It increases over time.

[0086] As described above, during period T1, A top Increase, in period T2, Atop Gradually approaching the specified value, during the third period T3, A top Addendum. In this specification, the processing conditions that produce these phenomena are referred to as Condition 1.

[0087] In the supply process S312, under the specified conditions of temperature and the first condition described above, the first gas is supplied to the substrate S. Then, in the supply process S312, the supply of the first gas ends during the second period T2 (specifically, at time t1 after a predetermined time has elapsed since the start of the first gas supply). Figure 5 The solid line A shown in (A) top2 In the supply process S312, A represents... top In contrast, in Figure 5 The dashed line A shown in (A) top1 A represents the situation where the supply of gas 1 is not terminated during period T2 and continues during period T3. top Furthermore, in Figure 5 In (A), the period from time t0 to time t1 is represented by the dashed line A. top1 With solid line A top2 They overlap.

[0088] Next, regarding Figure 5 (B) will be explained in detail.

[0089] exist Figure 5 The curve shown in (B) schematically represents the amount of the first substance (deep adsorption amount A) formed in the depth 702 when the first gas is supplied to the substrate S under the specified conditions of the second and third conditions described later. btm (Time changes) Figure 5 The horizontal axis of (B) is the elapsed time t from the start time t0 of the first gas supply. Figure 5 The vertical axis of (B) represents the amount A of the first substance formed in depth 702 during each cycle. btm In addition, Figure 5 (A) of A in top and Figure 5 (B) of A btm The time scale is set to be consistent. Furthermore, in Figure 5 In (B) of the text, the following are shown respectively: Figure 5 In (A), the first period T1, the second period T2, and the third period T3 are discussed. The following discussion focuses on... Figure 5 The fourth period T4 and the fifth period T5 shown in (B) are explained.

[0090] The fourth period, T4, is the period after the supply of the first gas begins. During the fourth period, T4, a large number of adsorption sites for the first gas exist on the surface of the substrate S. Therefore, during the fourth period, A... btm It increases over time. Furthermore, in period T4, the first gas reaches the opening 701 more easily than the deeper portion 702. Therefore, A in period T4... btm Compared to A in period T1 of the first period top The increasing curve becomes flat. Therefore, period 4, T4, ends only after period 1, T1, has ended.

[0091] The fifth period T5 is the period following the fourth period T4. In the fifth period T5, most of the adsorption sites on the substrate S are adsorbed with the first gas. Furthermore, in the fifth period T5, the first gas supplied to the processing chamber 201 and the first gas adsorbed on the substrate S are not decomposed; therefore, the adsorption of the first gas onto the substrate S is hindered. Thus, in the fifth period T5, A can be... btm Gradually approaching a specific value (defined value A). For example... Figure 5 As shown in (B), period 5, T5, begins after period 2, T2, and before period 2, T2, ends. That is, period 2, T2, and period 5, T5, overlap by at least a portion. Figure 5 As shown in (B), there is a period when the second period T2 and the fifth period T5 overlap, namely the sixth period T6, that is, there is a period when A... top and A btm During the 6th period T6, any value gradually approaches the specified value A, thereby reducing A. top With A btm The difference in membrane thickness between the opening 701 and the depth 702 can be reduced, thereby improving the step coverage.

[0092] As mentioned above, in period 4 T4, A btm Increase, in period T5, A btm It gradually approaches the specified value. Furthermore, after the start of period 2 (T2), period 5 (T5) begins. In this specification, the processing conditions that produce these phenomena are referred to as condition 2.

[0093] Furthermore, as described above, the fifth period T5 begins before the end of the second period T2. In this specification, the processing condition that causes this phenomenon will be referred to as the third condition.

[0094] In the supply process S312, it is preferable to supply the first gas to the substrate S under conditions that, in addition to the aforementioned temperature conditions and the first condition, the second condition or the third condition is also met. Furthermore, in the supply process S312, it is more preferable to terminate the supply of the first gas to the substrate S during the sixth period T6, which is the period overlapping the second period T2 and the fifth period T5. Figure 5 The solid line A shown in (B) btm2 In the supply process S312, A represents... btm That is, A when the supply of the first gas ends in period T6 of period 6. btm In contrast, in Figure 5 The dashed line A shown in (B) btm1 A represents the situation where the supply of gas 1 continues without stopping during period T6 (period 6). btm Furthermore, in Figure 5 (B) represents the period from time t0 to time t1, represented by the dashed line A. btm1 With solid line A btm2 overlapping.

[0095] Furthermore, the greater the ratio (width-to-height ratio) of the depth to the width of the recess 700, the more difficult it is for the first gas to reach the deep portion 702. Therefore, the time difference between the start of the second period T2 and the start of the fifth period T5 tends to increase, making it difficult to satisfy the second condition. For example, when the width-to-height ratio of the recess 700 is 400 or higher, the time difference between the start of the second period T2 and the start of the fifth period T5 tends to increase.

[0096] Here, we consider a substrate S with a high aspect ratio recess 700 on its surface, where the temperature of the substrate S is above the decomposition temperature of the first gas, and the processing step S3 is performed. In this case, it is preferable to set the processing conditions and supply time t1 in processing step S3 such that a film with near-100% stepped coverage is formed within the recess 700. In this case, it can be said that there is almost no difference in film thickness between the opening 701 and the depth 702. Therefore, the processing conditions can satisfy either the first condition or the second condition, and the supply time t1 at which the supply of the first gas to the substrate S ends in either the second period T2 or the sixth period T6 can be controlled. Therefore, a film with good properties and stepped coverage can be formed.

[0097] Furthermore, during period T6, due to A top and A btm By gradually approaching the specified value A, the difference in film thickness between the opening 701 and the depth 702 can be reduced. Therefore, the supply of the first gas is terminated during the sixth period T6, thereby further improving the step coverage.

[0098] The following uses Figure 6 (A) Figure 6 (B) Figure 6 Section (C) describes the processing conditions in the supply process S312.

[0099] Figure 6 (A) in the figure represents the change in the decomposition rate of the first gas in the processing chamber 201 after the first gas is supplied. Figure 6 The horizontal axis of (A) in the figure represents the elapsed time t from the start of the first gas supply. Figure 6 The vertical axis of (A) represents the decomposition rate D of the first gas in the processing chamber 201. Figure 6 (B) in the figure represents the change in the flow rate of the first gas in the processing chamber 201 after the first gas is supplied. Figure 6 The horizontal axis of (B) in the diagram represents the elapsed time t from the start of the first gas supply. Figure 6 The vertical axis of (B) in the figure represents the flow velocity V of the first gas in the processing chamber 201. Figure 6 (C) in the figure represents the pressure change in the processing chamber 201 after the first gas is supplied. Figure 6 The horizontal axis of (C) in the figure represents the elapsed time t from the start of the first gas supply. Figure 6 The vertical axis of (C) represents the pressure (partial pressure of the first gas) P inside the processing chamber 201.

[0100] In the supply process S312, at least a portion of the first gas stored in the tank 259 is supplied to the processing chamber 201. This allows the maximum supply amount to exceed the maximum exhaust amount.

[0101] As described above, the supply process S312 is performed at a temperature above the decomposition temperature of the first gas, where the temperature of the substrate S (and the processing chamber 201) is set. Therefore, as Figure 6 As shown in (A), the decomposition rate of the first gas in the processing chamber 201 increases with time. At this time, it is preferable to... Figure 6 As shown in (A), during the period from the start of the supply of the first gas until a predetermined time has elapsed, the state of the first gas having a low decomposition rate is maintained in the processing chamber 201 for a sufficient time (the predetermined time). This extends the second period T2 and the fifth period T5, resulting in the extension of the sixth period T6. This improves the step coverage.

[0102] In the supply process S312, it is preferable to include at least a portion of the period from the start of supplying the first gas toward the substrate S to the end, such as... Figure 6As shown in (A), the decomposition rate D is set to 0%. This allows for further extension of periods T2 and T5, which in turn allows for further extension of period T6. This further improves the ladder coverage.

[0103] like Figure 6 As shown in (B), in the supply process S312, the flow rate V decreases as time passes from the start of the supply of the first gas. The lower the flow rate V, the longer the first gas supplied to the processing chamber at a certain moment remains in the processing chamber 201 (hereinafter referred to as the residence time), and therefore, the decomposition rate D tends to increase. Therefore, as... Figure 6 As shown in (B), it is preferable to maintain the state of higher flow velocity V for a sufficient time (a predetermined time) and to maintain the period of shorter residence time for a sufficient time. This allows for a further extension of the second period T2 and the fifth period T5, which in turn allows for a further extension of the sixth period T6. This further improves the step coverage.

[0104] In the supply process S312, it is preferable to exhaust gas from the processing chamber 201 to shorten the residence time of the first gas. Furthermore, it is preferable that the APC valve 283 is in a high opening state, more preferably in a fully open state. This increases the flow rate of the first gas within the processing chamber 201, thereby further suppressing the decomposition of the first gas.

[0105] Furthermore, within the processing chamber 201, when the partial pressure of the first gas is high, the first gas can easily reach the deep chamber 702. For example... Figure 6 As shown in (C), in the supply process S312, it is preferable to maintain a high partial pressure of the first gas for a predetermined period starting from the start of the supply of the first gas. Therefore, since the time from the start of the supply of the first gas to the start of the fifth period T5 can be shortened, the sixth period T6 can be adequately maintained. As a result, the step coverage can be further improved.

[0106] In the supply process S312, it is preferable that the maximum value of the amount of the first gas supplied to the processing chamber 201 per unit time (hereinafter referred to as the maximum supply amount) is greater than the maximum value of the amount of gas discharged from the processing chamber 201 per unit time (hereinafter referred to as the maximum discharge amount). As a result, it is easier to maintain a high partial pressure of the first gas in the processing chamber 201.

[0107] like Figure 6As shown in (C), in the supply process S312, it is preferable to make the pressure P reach a maximum value during the period from the start of supplying the first gas to the end. Furthermore, it is preferable to make the pressure P at the end of the supply of the first gas more than half of the maximum value and less than the maximum value. Therefore, within the processing chamber 201, since the decomposition rate of the first gas can be maintained at a low level, the step coverage can be further improved.

[0108] In the aforementioned substrate processing step, the thickness THK of the film formed at the opening 701 top-n The thickness THK of the film formed at the opening 701 during one processing cycle top Proportional. Furthermore, THK top-n With the above A top It is directly proportional. Therefore, under certain condition X, the elapsed time t is directly proportional to THK. top-n The curve graph (hereinafter referred to as the first curve graph) and Figure 5 (A) of A in top1 The curves become the same shape. Therefore, as time t increases, the curves in the first phase sequentially pass through THK. top-n Increased period, THK top-n The period gradually approaching the specified value, and THK top-n In the case of an extended period, it can be confirmed that condition X satisfies the first condition. Furthermore, based on the first curve, the supply process S312 can be terminated in the second period T2.

[0109] The time t and the thickness THK of the film formed in depth 702 during the above-mentioned substrate processing process. btm-n The curve graph (hereinafter referred to as the second curve graph) is the same as the first curve graph. That is, by confirming the shape of the second curve graph, it can be confirmed whether condition X satisfies the second condition or satisfies both the second and third conditions. Furthermore, based on the first and second curve graphs, the supply process S312 can be terminated in the sixth period T6.

[0110] In summary, such as Figure 7 (A) and Figure 7As shown in (D), the preparation step S0 can also be performed after the graph creation step S01 and the condition setting step S02, followed by the supply step S312. The graph creation step S01 creates a first graph, and the condition setting step S02 sets the processing conditions for the supply step S312 that meet specified conditions and the time from the start of the supply step S312 to its end, based on the first graph. Alternatively, the first graph and the second graph can be created in the graph creation step S01, and the processing conditions for the supply step S312 that meet specified conditions and the time from the start of the supply step S312 to its end can be set in the condition setting step S02 based on the first graph and the second graph.

[0111] Specifically, the curve-setting process S01 can also include the following steps, using test conditions as the specified conditions. This process includes: step S011, which involves supplying a first gas to a test substrate (hereinafter referred to as the test substrate) having a test recess (hereinafter referred to as the test recess) on its surface under test conditions, thereby forming a film on the test recess; step S012, which involves creating a first curve, which is a curve showing the time elapsed since the start of step S011 (i.e., the first elapsed time) versus the thickness of the film formed at the opening of the test recess; and step S013, which involves confirming, based on the first curve, that the test conditions meet the first condition. Furthermore, the condition-setting process S02 can also include the following step S021, which involves setting the time from the start of the supply process S312 to its end based on the first curve, so that the supply process S312 ends during the aforementioned second period.

[0112] Furthermore, in the curve generation process S01, the following steps can be performed: Step S014, which is a process of generating a second curve showing the relationship between the first elapsed time and the thickness of the film formed deep in the test recess; Step S015, which is a process of confirming, based on the first and second curves, that the test conditions further meet the second condition. Furthermore, in the curve generation process S01, the following step S016 can be performed, which is a process of confirming, based on the first and second curves, that the test conditions further meet the third condition. Moreover, as a condition setting process S02, the following step S022 can be performed, which is a process of setting the time from the start (a1) to the end based on the first and second curves, so that the supply process S312 ends during the sixth period.

[0113] Here, it can also be considered that in the supply process S312, the surface of the opening 701 is supplied with approximately the same amount of the first gas as the surface of the substrate without recesses (hereinafter referred to as a flat substrate). Therefore, the same effect can be obtained even when a flat substrate is used as a test substrate in the preparation process S0. Since a flat substrate is cheaper than a substrate with recesses formed on its surface, the cost of the preparation process S0 can be reduced by using a flat substrate.

[0114] The shape and opening direction of the test recess formed on the surface of the test substrate and the recess 700 formed on the surface of the substrate S may be different. For example, the aspect ratio of the test recess and the recess 700 may also be different. Furthermore, for example, the test recess may be open in the horizontal direction, while the recess 700 may be open in the vertical direction. Even in these cases, at least some of the above-mentioned effects can still be achieved.

[0115] The number of test recesses formed on one test substrate can also be less than the number of recesses 700 formed on one substrate S. In this case, since the cost of the test substrate can be reduced, the cost of the preparation step S0 can be reduced. Furthermore, it is preferable that the aspect ratio of the test recess is greater than that of the recess 700. In this case, the actual A can be more easily and accurately controlled in the preparation step S0. top and A btm Changes over time.

[0116] (3) The effect of this method

[0117] According to this method, one or more of the following effects can be obtained.

[0118] (a) The supply process S312 is performed under specified conditions, and the supply process S312 is ended in the second period T2. These specified conditions satisfy the first condition described above, and the temperature of the substrate S is set to a temperature condition above the decomposition temperature of the first gas. This improves at least one of the film's properties and its step coverage. This will be explained below.

[0119] By performing the supply process S312 under the aforementioned temperature conditions, the properties of the film can be improved. Impurities from the ligands of the first element in the molecular structure of the first gas can be removed from the substrate S. This improves the properties of the film formed on the substrate S. Furthermore, it suppresses the resistance to the reaction between the substrate S surface and various gases caused by these impurities. This improves productivity.

[0120] Furthermore, under the first condition described above, the supply process S312 is performed, and the supply process S312 (specifically, the supply of the first gas is terminated) is ended in the second period T2. This improves the step coverage. The reason is that in the second period T2, A can be... top As the gas gradually approaches the predetermined value A, it is possible to suppress the increase in film thickness at the opening 701 while promoting the increase in film thickness at the depth 702. Therefore, by ending the supply of the first gas in the second period T2, the step coverage can be improved. Furthermore, in the first period T1, the first gas is less likely to reach the depth 702 than at the opening 701; therefore, the increase in film thickness at the depth 702 will occur later than the increase in film thickness at the opening 701. Moreover, in the third period T3, the decomposition of the first gas is underway, which will promote the increase in film thickness at the opening 701. Therefore, it is difficult to improve the step coverage when the supply of the first gas is ended in the first period T1 or the third period T3.

[0121] Generally, when the temperature of the substrate S is set above the thermal decomposition temperature of the first gas, it is easy to supply the decomposition products of the first gas at the opening 701. Therefore, due to A top It is easy to increase, therefore, it is difficult to improve the step coverage. According to the technology of the present invention, even when the temperature of the substrate S is set above the thermal decomposition temperature of the first gas, the step coverage can still be improved. That is, it is possible to simultaneously improve the film properties and / or productivity, as well as the step coverage.

[0122] (b) Furthermore, by performing the supply process S312 under the specified conditions of the second condition described above, the difference between the film thickness of the opening 701 and the film thickness of the depth 702 can be reduced, thereby further improving the step coverage.

[0123] (c) Furthermore, by performing the supply process S312 under the specified conditions of the third condition described above, the difference between the film thickness of the opening 701 and the film thickness of the depth 702 can be further reduced, thereby further improving the step coverage.

[0124] (d) During the sixth period T6, which overlaps with the second period T2 and the fifth period T5, the supply of the first gas to the substrate S is terminated. This allows the supply process S312 to be terminated while maintaining a small difference between the film thickness of the opening 701 and the film thickness of the depth 702. This further improves the step coverage.

[0125] (e) During at least a portion of the supply time from the start of supplying the first gas toward the substrate S to the end of the supply time, the decomposition rate of the first gas in the processing chamber 201 is set to 0%, thereby extending the second period T2 and thus ensuring the sixth period T6 sufficiently. As a result, the step coverage can be further improved.

[0126] Furthermore, when the supply process S312 is performed under conditions where the sixth period does not exist, A will always be the end of the supply of the first gas, regardless of when the supply ends. btm top The relationship. Furthermore, when the supply of the first gas ends before the start of the sixth period, it becomes A. btm <A≈A top The relationship, when the supply of the first gas ends after the end of the 6th period, becomes A. btm =A top The relationship is that, in these cases, ladder coverage is prone to decrease.

[0127] (f) The above cycle includes a first gas supply step S31 in which the first gas is stored in the tank 259. In the supply step S312, at least a portion of the first gas stored in the tank 259 in the first gas supply step S31 is supplied to the substrate S. As a result, the step coverage can be further improved.

[0128] (g) In the supply process S312, the pressure in the processing chamber 201 is maximized from the start to the end of the supply of the first gas, thereby maintaining the decomposition rate of the first gas at a low level within the processing chamber 201. This further improves the step coverage.

[0129] (h) In the supply process S312, the pressure in the processing chamber 201 at the point when the supply of the first gas ends is set to more than half of the maximum value and less than the maximum value. As a result, the decomposition rate of the first gas can be maintained at a low level in the processing chamber 201. This further improves the step coverage.

[0130] While the implementation method of this invention has been specifically described above, the invention is not limited thereto and various modifications can be made without departing from its spirit.

[0131] As the first gas, for example, a gas containing a specified element (the first element) such as tungsten (W), titanium (Ti), molybdenum (Mo), tantalum (Ta), cobalt (Co), yttrium (Y), ruthenium (Ru), hafnium (Hf), zirconium (Zr), aluminum (Al), and silicon (Si) can be used. More than one of these gases can be used as the first gas. A gas activated by plasma or the like can also be used as the first gas.​​

[0132] As a gas containing a specified element, for example, a halogen-based gas containing both the specified element and a halogen element can be used. Examples of halogen-based gases containing specified elements include tungsten hexachloride (WCl6), tungsten hexafluoride (WF6), titanium tetrachloride (TiCl4), titanium tetrafluoride (TiF4), molybdenum pentachloride (MoCl5), molybdenum pentafluoride (MoF5), molybdenum dichlorodioxide (MoO2Cl2), molybdenum tetrachlorodioxide (MoOCl4), tantalum pentachloride (TaCl5), tantalum pentafluoride (TaF5), cobalt difluoride (CoF2), cobalt difluoride (CoCl2), yttrium trifluoride (YF3), yttrium trichloride (YCl3), ruthenium trichloride (RuCl3), and fluorine trifluoride. Gases containing ruthenium chloride (RuF3), hafnium tetrachloride (HfCl4), hafnium tetrafluoride (HfF4), zirconium tetrachloride (ZrCl4), zirconium tetrafluoride (ZrF4), aluminum trichloride (AlCl3), aluminum trifluoride (AlF3), dichlorosilane (SiH2Cl2), 1,2-dichlorodisilazane (Si2H4Cl2), 1,1,1-trichlorodisilazane (Si2H3Cl3), 1,1,2-trichlorodisilazane (Si2H3Cl3), pentachlorodisilazane (Si2HCl5), hexachlorodisilazane (Si2Cl6), and tetrafluorosilane (SiF4) are permitted. Furthermore, gases containing specified elements, such as monosilane (SiH4), disilazane (Si2H6), trisilane (Si3H8), and tetrasilane (Si4H6), can also be used. 10 Gases such as ) and others. As gases containing specified elements, one or more of these gases may be used.

[0133] Furthermore, as a gas containing a specified element, an organic system containing a specified element, for example, can be used, which has a specified element and an organic ligand. Examples of organic systems containing a specified element include hexa(dimethylamino)ditungsten (W₂[N(CH₃)₂]₆), bis(tert-butylimino)bis(dimethylamino)tungsten ((t-C₄H₉NH)₂W=(Nt-C₄H₉)₂), tetra(ethylmethylamino)titanium (Ti[N(C₂H₅)(CH₃)]₄), bis(ethylcyclopentadienyl)ruthenium (Ru(EtCp)₂), bis(cyclopentadienyl)ruthenium (Ru(Cp)₂), tetra(ethylmethylamino)hafnium (Hf[N(Me)Et]₄), and tetra(diethylamino)hafnium (Hf[N(Et)Cp)₂). Gases containing the specified elements, such as tetra(dimethylamino)hafnium (Hf[N(Me)2]4), tri(dimethylamino)cyclopentadienylhafnium ((Cp)Hf[N(Me)2]3), tetra(ethylmethylamino)zirconium (Zr[N(Me)Cp]4), tetra(diethylamino)zirconium (Zr[N(Et)2]4), tetra(dimethylamino)zirconium (Zr[N(Me)2]4), tri(dimethylamino)cyclopentadienylzirconium ((Cp)Zr[N(Me)2]3), trimethylaluminum (Al(CH3)3), and tri(dimethylamino)silane (Si[N(CH3)2]3H), may be used. One or more of these gases may be used as the gas containing the specified element.

[0134] When a gas containing atoms of two or more specified elements in its molecular structure is used as the first gas, the thermal decomposition of the first gas easily produces products containing the specified elements and with high reactivity. This tends to increase the film thickness near the opening 701, thus potentially reducing the step coverage. According to the technology of the present invention, even in such cases, the step coverage can be improved. For example, gases containing atoms of two or more specified elements can be used, such as those containing Si2H4Cl2, Si2H3Cl3, Si2HCl5, Si2Cl6, Si2H6, Si3H8, or Si4H4Cl2. 10 One or more of the following gases: W2[N(CH3)2]6.

[0135] As the second gas, for example, a gas including reducing gas, oxidizing gas, nitriding gas, sulfiding gas, selenizing gas, tellurizing gas, etc., can be used. One or more of these gases can be used as the second gas. A gas activated by plasma or the like can also be used as the second gas. For example, when the first gas is a gas containing a specified element and the second gas is a reducing gas, a film composed of a single specified element can be formed on the substrate S. Furthermore, for example, when the first gas is a gas containing a specified element and the second gas is any one of an oxidizing gas, nitriding gas, sulfiding gas, selenizing gas, or tellurizing gas, an oxide film, a nitriding film, a sulfiding film, a selenizing film, or a tellurizing film of a specified element can be formed on the substrate S.

[0136] As a reducing gas, one or more gases can be used, such as hydrogen (H2), deuterium (D2), borane (BH3), diborane (B2H6), carbon monoxide (CO), ammonia (NH3), monosilane (SiH4), disilane (Si2H6), trisilane (Si3H8), monogermanane (GeH4), and digermanane (Ge2H6). As an oxidizing gas, one or more gases can be used, such as oxygen (O2), ozone (O3), water vapor (H2O), a mixture of H2 and O2, hydrogen peroxide (H2O2), and nitrous oxide (N2O). As a nitriding gas, one or more hydrogen nitride gases can be used, such as ammonia (NH3), diazepine (N2H2), hydrazine (N2H4), and N3H8. For example, gases containing thioalkylene (H₂S), dithionane (H₂S₂), ammonium sulfide ((NH₄)₂S), dimethyl sulfide ((CH₃)₂S), etc., can be used as sulfiding gases. One or more of these gases can be used as sulfiding gases. For example, gases containing selenoalkylene (H₂Se), diselenoalkylene (H₂Se₂), dimethylselenide ((CH₃)₂Se), etc., can be used as selenoalkylene (H₂Se). One or more of these gases can be used as selenoalkylene (H₂Te), ditellurane (H₂Te₂), dimethyltelluride ((CH₃)₂Te), etc., can be used as sulfiding gases. One or more of these gases can be used as sulfiding gases.

[0137] As an inert gas, rare gases such as helium (He), argon (Ar), neon (Ne), and xenon (Xe) or nitrogen (N2) can be used. More than one of these gases can be used as an inert gas.

[0138] In the above-described manner, an example is taken where the first gas and the second gas are used in processing step S3 to form a film on the substrate S. However, the technology of the present invention is not limited thereto. For example, the technology of the present invention can be applied even when using three or more gases. Furthermore, for example, the technology of the present invention can be applied even when the second gas supply step S33 and the purge gas supply step S34 are omitted.

[0139] In the above-described method, an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time has been described. However, the present invention is not limited to the above-described method; for example, it can also be appropriately applied when forming a film using a single-sheet substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described method, an example of forming a film using a substrate processing apparatus with a hot-wall type processing furnace has been described. The present invention is not limited to the above-described method; it can also be appropriately applied when forming a film using a substrate processing apparatus with a cold-wall type processing furnace, and the same effects as the above-described method or its variations can be obtained.

[0140] The above methods and variations can be appropriately combined and used. The processing procedures and conditions can, for example, be set to be the same as those in the above methods and variations.

[0141] Explanation of reference numerals in the attached figures

[0142] S: substrate, 700: recess, 701 opening.

Claims

1. A substrate processing method, characterized in that, have: Step (a) involves performing the cycle of step (a1) a predetermined number of times to form a film containing a predetermined substance of the first element on a substrate. Step (a1) involves supplying a first gas to the substrate having recesses on its surface under predetermined conditions, and forming a first substance containing the first element on the surface of the substrate. The above-mentioned conditions must satisfy both the temperature condition and condition 1. This temperature condition is achieved by setting the temperature of the substrate above the decomposition temperature of the first gas. The first condition is that, during a first period after the supply of the first gas begins, the amount of the first substance adsorbed at the opening of the recess (i.e., the opening adsorption amount) is increased; during a second period following the first period, the opening adsorption amount is gradually brought closer to a predetermined value; and during a third period following the second period, the opening adsorption amount is increased. (a1) Ends during the second period mentioned above.

2. The substrate processing method according to claim 1, characterized in that, The above-mentioned conditions also meet condition 2. The second condition is that during the fourth period after the supply of the first gas begins, the amount of the first substance adsorbed in the depth of the recess, i.e., the deep adsorption amount, is increased. During the fifth period after the fourth period, the deep adsorption amount is gradually brought close to the specified value. The fifth period begins after the start of the second period.

3. The substrate processing method according to claim 2, characterized in that, The above-mentioned conditions also meet condition 3. The third condition is that the fifth period begins before the end of the second period.

4. The substrate processing method according to claim 3, characterized in that, In (a1), during the sixth period, which overlaps with the second period and the fifth period, the supply of the first gas toward the substrate is terminated.

5. The substrate processing method according to any one of claims 1 to 4, characterized in that, In (a1), during at least a portion of the supply time from the start to the end of the supply of the first gas toward the substrate, i.e., the supply time, the decomposition rate of the first gas in the space where the substrate exists is set to 0.

6. The substrate processing method according to any one of claims 1 to 4, characterized in that, The above cycle also includes: step (a0), storing the first gas in a storage unit. In (a1), at least a portion of the first gas stored in the storage section in (a0) is supplied to the substrate.

7. The substrate processing method according to any one of claims 1 to 4, characterized in that, In (a1), during the period from the start of supplying the first gas to the end, the pressure in the space where the substrate exists is maximized.

8. The substrate processing method according to claim 7, characterized in that, In (a1), the pressure in the space at the time when the supply of the first gas ends is set to be more than half of the maximum value and less than the maximum value.

9. The substrate processing method according to any one of claims 1 to 4, characterized in that, The above cycle also includes: step (b), supplying the substrate with a second gas that modifies the first substance.

10. The substrate processing method according to any one of claims 1 to 4, characterized in that, The first gas mentioned above is a gas containing atoms of two or more specified elements in its molecular structure.

11. The substrate processing method according to claim 4, characterized in that, The above-described substrate processing method further includes step (c) comprising the following steps: (c1) Step: Under test conditions, the first gas is supplied to a test substrate having a test recess on its surface, and the film is formed on the test recess. (c2) Step 1: Create a first curve graph, which is a curve graph of the time elapsed since (c1), i.e. the first elapsed time, and the thickness of the film formed at the opening of the above-mentioned test recess. (c3) Step 1: Based on the first graph above, confirm whether the above test conditions meet the first condition. The above-mentioned test conditions shall be used as the conditions specified above.

12. The substrate processing method according to claim 11, characterized in that, The above-described substrate processing method further includes a step (d1) in which a time from the start (a1) to the end is set according to the first graph, so that (a1) ends during the second period.

13. The substrate processing method according to claim 11, characterized in that, Process (c) also includes the following processes: (c4) Step, the step of making a second curve, which is the relationship between the first elapsed time and the thickness of the film formed in the depth of the test recess. (c5) Step: Based on the first curve and the second curve mentioned above, confirm whether the above test conditions still meet the second condition mentioned above.

14. The substrate processing method according to claim 13, characterized in that, Process (c) also includes the following processes: (c6) Step: Based on the first curve and the second curve mentioned above, confirm whether the test conditions also meet the third condition mentioned above.

15. The substrate processing method according to claim 14, characterized in that, The above-described substrate processing method further includes: step (d2), which sets the time from the start (a1) to the end based on the first curve and the second curve, such that (a1) ends during the sixth period.

16. The substrate processing method according to any one of claims 1 to 4, characterized in that, The above-described substrate processing method further includes a step (e) comprising the following steps: (e1) In the test conditions, the first gas is supplied to the test substrate and the film is formed on the test substrate; (e2) Step, the first curve is obtained, which is the relationship between the time elapsed since (e1), i.e. the first elapsed time, and the thickness of the film formed on the test substrate. (e3) Step: Based on the first curve above, confirm whether the above test conditions meet the first condition above. The above-mentioned test conditions shall be used as the conditions specified above.

17. The substrate processing method according to claim 16, characterized in that, The above-described substrate processing method further includes: step (f), which sets the time from the start (a1) to the end according to the first curve, such that (a1) ends during the second period.

18. A method for manufacturing a semiconductor device, characterized in that, The manufacturing method includes: step (a), which involves performing a cycle including step (a1) a predetermined number of times to form a film containing a predetermined substance of the first element on a substrate, wherein step (a1) involves supplying a first gas to the substrate having recesses on its surface under predetermined conditions, and forming a first substance containing the first element on the surface of the substrate. The above-mentioned conditions must satisfy both the temperature condition and condition 1. This temperature condition is achieved by setting the temperature of the substrate above the decomposition temperature of the first gas. The first condition is that, during a first period after the supply of the first gas begins, the amount of the first substance adsorbed at the opening of the recess (i.e., the opening adsorption amount) is increased; during a second period following the first period, the opening adsorption amount is gradually brought closer to a predetermined value; and during a third period following the second period, the opening adsorption amount is increased. (a1) Ends during the second period mentioned above.

19. A substrate processing apparatus, characterized in that, have: A first gas supply system supplies a first gas to a substrate having a recess on its surface; A temperature control unit that controls the temperature of the aforementioned substrate; The control unit is configured to control the first gas supply system and the temperature control unit to perform a process comprising performing a cycle including process (a1) a predetermined number of times and forming a film containing a predetermined substance of the first element on the substrate. Process (a1) involves supplying the first gas to the substrate under predetermined conditions and forming a first substance containing the first element on the surface of the substrate. The above-mentioned conditions must satisfy both the temperature condition and condition 1. This temperature condition is achieved by setting the temperature of the substrate above the decomposition temperature of the first gas. The first condition is that, during a first period after the supply of the first gas begins, the amount of the first substance adsorbed at the opening of the recess (i.e., the opening adsorption amount) is increased; during a second period following the first period, the opening adsorption amount is gradually brought closer to a predetermined value; and during a third period following the second period, the opening adsorption amount is increased. (a1) Ends during the second period mentioned above.

20. A program, characterized in that, The program uses a computer to cause the substrate processing device to perform the following process. The process comprises: process (a), in which a cycle including process (a1) is performed a predetermined number of times to form a film containing a predetermined substance of the first element on a substrate; process (a1) involves supplying a first gas to the substrate having recesses on its surface under predetermined conditions, and forming a first substance containing the first element on the surface of the substrate. The above-mentioned conditions must satisfy both the temperature condition and condition 1. This temperature condition is achieved by setting the temperature of the substrate above the decomposition temperature of the first gas. The first condition is that, during a first period after the supply of the first gas begins, the amount of the first substance adsorbed at the opening of the recess (i.e., the opening adsorption amount) is increased; during a second period following the first period, the opening adsorption amount is gradually brought closer to a predetermined value; and during a third period following the second period, the opening adsorption amount is increased. (a1) Ends during the second period mentioned above.

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