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

Abstract

The invention provides a technology capable of improving the quality of a film formed on a substrate. The present invention comprises: (a) a step in which a starting material gas containing a first element and an organic ligand is supplied to a substrate; (b) a step for supplying a treatment gas to the substrate to reduce the amount of by-products present on the surface of the substrate; (c) supplying a first reaction gas to the substrate; and (d) forming a film containing the first element on the substrate by performing (a), (b) and (c) a predetermined number of times.

Description

Technical Field

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

[0002] As one of the steps in the process of manufacturing a semiconductor device, there is a case where a process of forming a film on a substrate is performed (for example, refer to Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2008-124184 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention provides a technology capable of improving the quality of a film formed on a substrate.

[0008] Solutions for solving problems

[0009] According to one embodiment of the present invention, a technology is provided, which has the following steps:

[0010] (a) supplying a raw material gas containing a first element and an organic ligand to a substrate;

[0011] (b) supplying a treatment gas to the substrate to reduce the amount of by-products present on the surface of the substrate;

[0012] (c) supplying a first reaction gas to the substrate; and

[0013] (d) A step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the substrate.

[0014] Effects of the Invention

[0015] According to the present invention, the quality of a film formed on a substrate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a longitudinal sectional view showing a schematic structure of a vertical processing furnace of a substrate processing apparatus according to one embodiment of the present invention.

[0017] Figure 2 yes Figure 1 AA line schematic cross-sectional view.

[0018] Figure 3It is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment of the present invention, and is a diagram showing a control system of the controller in a block diagram.

[0019] Figure 4 It is a diagram showing a substrate processing flow in one embodiment of the present invention.

[0020] Figure 5 It is a diagram showing a substrate processing sequence in one embodiment of the present invention.

[0021] Figure 6 (a) to Figure 6 (f) are diagrams each showing a modified example of the substrate processing sequence in one embodiment of the present invention.

[0022] Figure 7 It is a diagram showing a modified example of the substrate processing sequence in one embodiment of the present invention. DETAILED DESCRIPTION

[0023] Hereinafter, one embodiment of the present invention will be mainly described with reference to Figures 1 to 5 In addition, the drawings used in the following description are schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings may not be consistent with the actual object. In addition, the dimensional relationship of each element, the ratio of each element, etc. may not be consistent between multiple drawings.

[0024] (1) Configuration of substrate processing apparatus

[0025] The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating unit (heating mechanism, heating system). The heater 207 is cylindrical and is supported by a heater base (not shown) as a holding plate and is installed vertically.

[0026] On the inner side of the heater 207, an outer tube 203 constituting a processing container is arranged in a concentric manner with the heater 207. The outer tube 203 is also called an external reaction tube (outer tube). The outer tube 203 is made of heat-resistant materials such as quartz (SiO2) and silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (inlet flange) 209 is arranged in a concentric manner with the outer tube 203. The manifold 209 is made of metal such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. An O-ring 220a as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported by the heater base, so that the outer tube 203 is installed vertically.

[0027] Inside the outer tube 203, an inner tube 204 constituting a reaction vessel is provided. The inner tube 204 is also referred to as an inner tube. The inner tube 204 is made of a heat-resistant material such as SiO2 or SiC, and is formed into a cylindrical shape with a closed upper end and an open lower end. The processing vessel is mainly composed of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing vessel (inside the inner tube 204).

[0028] The processing chamber 201 is configured to accommodate wafers 200 as substrates in a horizontal posture and arranged in multiple stages in the vertical direction using a wafer boat 217 to be described later.

[0029] In the processing chamber 201, nozzles 410, 420, 430, 440 are provided to penetrate the side wall of the manifold 209 and the inner tube 204. Gas supply pipes 310, 320, 330, 340 are connected to the nozzles 410, 420, 430, 440, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned form.

[0030] The gas supply pipes 310, 320, 330, 340 are provided with flow controllers (flow control units) or mass flow controllers (MFCs) 312, 322, 332, 342 in order from the upstream side. In addition, the gas supply pipes 310, 320, 330, 340 are provided with valves 314, 324, 334, 344, which are on-off valves. The gas supply pipes 510, 520, 530, 540 for supplying inert gas are connected to the downstream side of the valves 314, 324, 334, 344 of the gas supply pipes 310, 320, 330, 340, respectively. The gas supply pipes 510, 520, 530, 540 are provided with MFCs 512, 522, 532, 542 and valves 514, 524, 534, 544 in order from the upstream side.

[0031] Nozzles 410, 420, 430, 440 are connected to the front ends of the gas supply pipes 310, 320, 330, 340, respectively. The nozzles 410, 420, 430, 440 are configured as L-shaped nozzles, and their horizontal portions are arranged to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, 430, 440 are arranged inside the channel-shaped (groove-shaped) preparation chamber 201a, and are arranged to face upward (above the arrangement direction of the wafers 200) along the inner wall of the inner tube 204 in the preparation chamber 201a, and the preparation chamber 201a is formed to protrude radially outward from the inner tube 204 and extend in the vertical direction.

[0032] The nozzles 410, 420, 430, 440 are arranged to extend from the lower area of ​​the processing chamber 201 to the upper area of ​​the processing chamber 201, and a plurality of gas supply holes 410a, 420a, 430a, 440a are respectively arranged at positions opposite to the wafer 200. Thus, the processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a, 440a of the nozzles 410, 420, 430, 440, respectively. The gas supply holes 410a, 420a, 430a, 440a are arranged in plurality from the lower part to the upper part of the inner tube 204, and each has the same opening area, and is further arranged at the same opening spacing. However, the gas supply holes 410a, 420a, 430a, 440a are not limited to the above-mentioned form. For example, the opening area may be gradually increased from the lower part to the upper part of the inner tube 204. Thus, the flow rate of gas supplied from the gas supply holes 410a, 420a, 430a, and 440a can be made more uniform.

[0033] The gas supply holes 410a, 420a, 430a, 440a of the nozzles 410, 420, 430, 440 are provided in a plurality of height positions from the lower part to the upper part of the wafer boat 217 described later. Therefore, the processing gas supplied from the gas supply holes 410a, 420a, 430a, 440a of the nozzles 410, 420, 430, 440 to the processing chamber 201 is supplied to the entire area of ​​the wafers 200 stored from the lower part to the upper part of the wafer boat 217. Although the nozzles 410, 420, 430, 440 only need to be provided to extend from the lower area to the upper area of ​​the processing chamber 201, it is preferred that they be provided to extend to the vicinity of the top wall of the wafer boat 217.

[0034] From the gas supply pipe 310, the first processing gas is supplied into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410. In the present invention, the first processing gas is also referred to as a modified gas, a modifier, an adsorption inhibitor, and an adsorption inhibitor gas. In addition, the first processing gas is also referred to as a first modifier and a first modified gas.

[0035] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, a modifier, an adsorption inhibitor, etc. may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0036] The second process gas is supplied from the gas supply pipe 320 into the process chamber 201 via the MFC 322, the valve 324 and the nozzle 420. In the present invention, the second process gas is also referred to as raw material gas, gas containing the first element, gas containing the first element and ligands, and gas containing the first element and organic ligands.

[0037] From the gas supply pipe 330, the third process gas is supplied into the process chamber 201 via the MFC 332, the valve 334, and the nozzle 430. In the present invention, the third process gas is used as a reaction gas that reacts with the raw material gas. In the present invention, the third process gas is also referred to as a treatment gas, a second modifier, a second modified gas, and a reducing gas (first reducing gas). In the present invention, the treatment gas is also referred to as a second reaction gas.

[0038] From the gas supply pipe 340, the fourth process gas is supplied into the process chamber 201 via the MFC 342, the valve 344, and the nozzle 440. In the present invention, the fourth process gas is also referred to as a reactant serving as the first reaction gas, a reaction gas, a gas containing a second element (a gas containing a second element), a third modifier, and a third modified gas.

[0039] The inert gas is supplied from the gas supply pipes 510 , 520 , 530 , 540 into the processing chamber 201 via the MFCs 512 , 522 , 532 , 542 , the valves 514 , 524 , 534 , 544 , and the nozzles 410 , 420 , 430 , 440 , respectively.

[0040] Although the process gas supply system is mainly composed of the gas supply pipes 310, 320, 330, 340, the MFCs 312, 322, 332, 342, the valves 314, 324, 334, 344, and the nozzles 410, 420, 430, 440, only the nozzles 410, 420, 430, 440 may be considered as the process gas supply system. The process gas supply system may also be simply referred to as the gas supply system. When the first process gas is caused to flow from the gas supply pipe 310, the first process gas supply system is mainly composed of the gas supply pipe 310, the MFC 312, and the valve 314, but the nozzle 410 may also be considered to be included in the first process gas supply system. The first process gas supply system may also be referred to as the modifier supply system. In addition, when the second process gas is caused to flow from the gas supply pipe 320, the second process gas supply system is mainly composed of the gas supply pipe 320, the MFC 322, and the valve 324, but the nozzle 420 may be included in the second process gas supply system. The second process gas supply system may also be referred to as a raw gas supply system. In addition, when the third process gas is caused to flow from the gas supply pipe 330, the third process gas supply system is mainly composed of the gas supply pipe 330, the MFC 332, and the valve 334, but the nozzle 430 may be included in the third process gas supply system. The third process gas supply system may also be referred to as a disposal gas supply system or a second reaction gas supply system. In addition, when the fourth process gas is caused to flow from the gas supply pipe 340, the fourth process gas supply system is mainly composed of the gas supply pipe 340, the MFC 342, and the valve 344, but the nozzle 440 may be included in the fourth process gas supply system. The fourth process gas supply system may also be referred to as a reactant supply system or a first reaction gas supply system. In addition, the inert gas supply system is mainly composed of gas supply pipes 510 , 520 , 530 , 540 , MFCs 512 , 522 , 532 , 542 , and valves 514 , 524 , 534 , 544 .

[0041] The gas supply method in this embodiment is to transfer the gas through the nozzles 410, 420, 430, 440 arranged in the preparation chamber 201a, wherein the preparation chamber 201a is a preparation chamber 201a located in a circular ring-shaped longitudinally extending space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200. Then, the gas is ejected into the inner tube 204 from the plurality of gas supply holes 410a, 420a, 430a, 440a provided at the positions of the nozzles 410, 420, 430, 440 facing the wafers. More specifically, the processing gas and the like are ejected in a direction parallel to the surface of the wafer 200 by the gas supply holes 410a of the nozzle 410, the gas supply holes 420a of the nozzle 420, the gas supply holes 430a of the nozzle 430, and the gas supply holes 440a of the nozzle 440.

[0042] The exhaust hole (exhaust port) 204a is a through hole formed in the side wall of the inner tube 204 and at a position opposite to the nozzles 410, 420, 430, 440, for example, a slit-shaped through hole opened in a vertical direction. The gas supplied from the gas supply holes 410a, 420a, 430a, 440a of the nozzles 410, 420, 430, 440 into the processing chamber 201 and flowing on the surface of the wafer 200 flows into the exhaust path 206 through the exhaust hole 204a, wherein the exhaust path 206 is formed by the gap formed between the inner tube 204 and the outer tube 203. Then, the gas flowing into the exhaust path 206 flows into the exhaust pipe 231 and is discharged toward the outside of the processing furnace 202.

[0043] The exhaust hole 204a is provided at a position opposite to the plurality of wafers 200, and the gas supplied from the gas supply holes 410a, 420a, 430a, and 440a to the vicinity of the wafers 200 in the processing chamber 201 flows in a horizontal direction and then flows through the exhaust hole 204a toward the exhaust path 206. The exhaust hole 204a is not limited to a through hole formed in a slit shape, and may be formed using a plurality of holes.

[0044] The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is connected in order from the upstream side to a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum exhaust device. The APC valve 243 opens and closes the valve while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust and vacuum exhaust stop in the processing chamber 201. Furthermore, the valve opening is adjusted while the vacuum pump 246 is in operation, thereby enabling the pressure in the processing chamber 201 to be adjusted. The exhaust system is mainly composed of the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. It is also conceivable to include the vacuum pump 246 in the exhaust system.

[0045] Below the manifold 209, a sealing cover 219 is provided as a furnace port cover body that can hermetically seal the lower end opening of the manifold 209. The sealing cover 219 is configured to be abutted against the lower end of the manifold 209 from the lower side in the vertical direction. The sealing cover 219 is made of metal such as SUS, for example, and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b is provided as a sealing member that abuts against the lower end of the manifold 209. On the opposite side of the processing chamber 201 in the sealing cover 219, a rotating mechanism 267 is provided to rotate the wafer boat 217 that accommodates the wafer 200. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism vertically provided outside the outer tube 203. The boat elevator 115 is configured to raise and lower the sealing cap 219, thereby enabling the boat 217 to be moved in and out of the processing chamber 201. The boat elevator 115 is configured as a transport device (transport system) that transports the boat 217 and the wafers 200 stored in the boat 217 in and out of the processing chamber 201.

[0046] The wafer boat 217 as a substrate support is configured to arrange multiple wafers, for example, 25 to 200 wafers 200, at intervals in the vertical direction in a horizontal posture and in a state where the centers are aligned with each other. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the lower part of the wafer boat 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in a horizontal posture in multiple stages (not shown). With this structure, it becomes difficult for the heat from the heater 207 to be transferred to the sealing cover 219 side. However, the present embodiment is not limited to the above-mentioned form. For example, instead of providing the heat insulation plate 218 at the lower part of the wafer boat 217, an insulation cylinder formed as a cylindrical member made of a heat-resistant material such as quartz or SiC may be provided.

[0047] like Figure 2 As shown in FIG. 1 , a temperature sensor 263 as a temperature detector is provided in the inner tube 204, and the amount of current supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby making the temperature in the processing chamber 201 a desired temperature distribution. The temperature sensor 263 is configured in an L shape similarly to the nozzles 410, 420, 430, and 440, and is provided along the inner wall of the inner tube 204.

[0048] like Figure 3 As shown, the control unit (control unit), i.e., the controller 121, is constituted by a computer, and is provided with a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus. An input / output device 122 configured as a touch panel, etc. is connected to the controller 121, for example. In addition, the substrate processing device may be configured to have one control unit or to have multiple control units. That is, for the control for performing the processing sequence described later, one control unit may be used to perform the control, or multiple control units may be used to perform the control. In addition, the multiple control units may be configured as a control system that is mutually connected using a wired or wireless communication network, or the control system as a whole may be used to perform the control for performing the processing sequence described later. When the term "control unit" is used in this specification, it includes not only one control unit but also a plurality of control units and a control system composed of a plurality of control units.

[0049] The storage device 121c is constituted by, for example, a flash memory, a HDD (Hard Disk Drive), etc. In the storage device 121c, a control program for controlling the operation of the substrate processing device, a process recipe recording the steps and conditions of the semiconductor device manufacturing method described later, etc. can be readable. The process recipe is a combination of the controller 121 to execute each process (step) in the semiconductor device manufacturing method described later and obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc. are integrated and also referred to as a program. When the term program is used in this specification, there are cases where only the process recipe alone is included, only the control program alone is included, or a combination of the process recipe and the control program is included. RAM 121b is configured as a memory area (work area) that temporarily holds programs, data, etc. read out by CPU 121a.

[0050] The I / O port 121d is connected to the above-mentioned MFCs 312, 322, 332, 342, 512, 522, 532, 542, valves 314, 324, 334, 344, 514, 524, 534, 544, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, wafer boat elevator 115, etc.

[0051] The CPU 121 a is configured to read out and execute a control program from the storage device 121 c , and to read out a recipe or the like from the storage device 121 c in response to input of an operation command from the input / output device 122 or the like. CPU 121a is configured to control the following contents according to the contents of the read recipe: flow adjustment actions of various gases performed according to MFC 312, 322, 332, 342, 512, 522, 532, 542, opening and closing actions of valves 314, 324, 334, 344, 514, 524, 534, 544, opening and closing actions of APC valve 243 and pressure adjustment actions of APC valve 243 based on pressure sensor 245, temperature adjustment actions of heater 207 based on temperature sensor 263, start and stop of vacuum pump 246, rotation and rotation speed adjustment actions of wafer boat 217 performed by rotating mechanism 267, lifting and lowering actions of wafer boat 217 performed by wafer boat elevator 115, storage actions of wafer 200 toward wafer boat 217, etc.

[0052] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a magnetic tape, a floppy disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO (magneto-optical disc), a semiconductor memory such as a USB memory or a memory card) 123 on a computer. The storage device 121c or the external storage device 123 is constructed as a computer-readable storage medium storing a program. Hereinafter, they are integrated and simply referred to as storage media. In this specification, the storage medium may include only the storage device 121c monomer, only the external storage device 123 monomer, or both. The program may be provided to the computer without using the external storage device 123, but using communication means such as the Internet or a dedicated line.

[0053] (2) Substrate processing step (substrate processing method)

[0054] As one example of a process for manufacturing a semiconductor device, a first element-containing film containing a first element is formed on a wafer 200 using Figure 4 and Figure 5 In this process, the processing furnace 202 of the substrate processing apparatus 10 described above is used to perform the process. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121 .

[0055] In the substrate processing step (semiconductor device manufacturing step) of this embodiment, there are:

[0056] (a) A process of supplying a raw material gas containing a first element and an organic ligand to the wafer 200;

[0057] (b) supplying a treatment gas to the wafer 200 to reduce the amount of by-products present on the surface of the wafer 200;

[0058] (c) a step of supplying a reactant to the wafer 200; and

[0059] (d) A step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the wafer 200 .

[0060] The term "wafer" used in this specification may refer to the wafer itself, or to a stack of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may refer to the surface of the wafer itself, or to the surface of a predetermined layer, etc. formed on the wafer. In this specification, "forming a predetermined layer on the wafer" means directly forming a predetermined layer on the surface of the wafer itself, or forming a predetermined layer on a layer, etc. formed on the wafer. In this specification, the term "substrate" is used in the same meaning as the term "wafer".

[0061] [Wafer loading (wafer loading)]

[0062] When multiple wafers 200 are loaded into the wafer boat 217 (wafer loading), as shown in FIG. Figure 1 As shown, the wafer boat 217 supporting the plurality of wafers 200 is lifted by the wafer boat elevator 115 and carried into the processing chamber 201 of the processing container (wafer boat introduction), and is stored in the processing container. In this state, the sealing cap 219 is in a state of sealing the lower end opening of the outer tube 203 via the O-ring 220.

[0063] [Pressure adjustment and temperature adjustment]

[0064] The vacuum pump 246 is used to perform vacuum exhaust so that the space in the processing chamber 201, i.e., the space where the wafer 200 is located, becomes the required pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is feedback controlled (pressure adjusted) based on the measured pressure information. The vacuum pump 246 is maintained in a state of always being in operation at least until the processing of the wafer 200 is completed. In addition, the processing chamber 201 is heated by the heater 207 to reach the required temperature. At this time, the amount of current flowing toward the heater 207 is feedback controlled (temperature adjusted) based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has the required temperature distribution. The heating in the processing chamber 201 performed by the heater 207 is continuously performed at least until the processing of the wafer 200 is completed.

[0065] [Step A: Supply of Modifying Agent]

[0066] like Figure 5As shown by the dotted line, the valve 314 may be opened to perform step A of flowing the modifier into the gas supply pipe 310. The modifier whose flow rate is adjusted by the MFC 312 is supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410, and is exhausted from the exhaust pipe 231. At this time, the modifier is supplied to the wafer 200 (modifier supply). The modifier is sometimes supplied in a state diluted by a diluent gas such as an inert gas.

[0067] The modifier is supplied to the wafer 200 under the conditions described below, so that the surface of the wafer 200 physically adsorbs the modifier, and an adsorption layer containing the modifier physically adsorbed on the surface of the wafer 200 can be formed on the wafer 200. As a result of the formation of the adsorption layer, among the adsorption sites existing on the surface of the wafer 200, a part of the adsorption sites are covered by the adsorption layer, and another part of the adsorption sites are not covered by the adsorption layer and are exposed. Here, the so-called adsorption sites existing on the surface of the wafer 200 include, for example, a hydroxyl group (OH group) that blocks the surface of the wafer 200. In addition, the modifier includes an organic compound as described below, and therefore, at least a part of the surface of the adsorption layer can be blocked by a hydrocarbon group or the like.

[0068] The thickness of the adsorption layer is preferably set to a thickness less than 1 molecular layer. That is, the adsorption layer preferably contains the adsorbed modifier in a manner that discontinuously covers the surface of the wafer 200. As a result, among the adsorption sites (OH groups) present on the surface of the wafer 200, a portion of the adsorption sites can be set to a reliably exposed state. However, in this stage, the modifier can be pre-physical adsorbed on the surface of the wafer 200 in a manner that sets the thickness of the adsorption layer to a thickness of more than 1 molecular layer (that is, the surface of the wafer 200 is pre-covered with a continuous layer), and a portion of the modifier contained in the adsorption layer is removed from the surface of the wafer 200, thereby forming an adsorption layer with a thickness less than 1 molecular layer.

[0069] Furthermore, in this step, an adsorption layer is formed at least on the surface near the opening (particularly the side wall near the opening) of the inner surface of the concave structure formed on the surface of the wafer 200. Furthermore, more preferably, as described later, in this step, an adsorption layer is also formed on the bottom surface and the side wall of the inner surface of the concave structure.

[0070] After the adsorption layer is formed on the wafer 200 , the valve 314 is closed to stop supplying the modifying agent into the processing chamber 201 .

[0071] After the supply of the modifying agent to the wafer 200 is completed (after it is stopped), the Figure 5 As shown by the dotted line, the process chamber 201 is exhausted while the supply of the modifying agent into the process chamber 201 is stopped, and step E is performed to remove the gas remaining in the process chamber 201 from the process chamber 201.

[0072] In addition, if Figure 5 As shown, in step E, preferably, valves 514 to 544 are opened to supply inert gas into the processing chamber 201 through the nozzles 410 to 440. That is, in step E, it is preferred that the processing chamber 201 is exhausted while the inert gas is supplied to the wafer 200. In addition, in step E, it is preferred that the steps of exhausting the processing chamber 201 while the inert gas is supplied to the wafer 200 and the step of exhausting the processing chamber 201 while the supply of the inert gas is stopped may be performed. In addition, it is preferred that a purge cycle is performed multiple times in step E, and the purge cycle includes (performed non-simultaneously) the step of exhausting the processing chamber 201 while the inert gas is supplied to the wafer 200 and the step of exhausting the processing chamber 201 while the supply of the inert gas is stopped. These contents are also the same in the following description.

[0073] The treatment conditions in the supply of the modifier in step A can be exemplified as follows:

[0074] Modifier supply flow rate (excluding dilution gas): 0.01 to 10 g / min, more preferably 0.1 to 5 g / min;

[0075] Dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm;

[0076] Modifier supply time: 1 to 600 seconds, more preferably 10 to 300 seconds;

[0077] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm;

[0078] Processing temperature: 200-500°C, more preferably 200-350°C;

[0079] Treatment pressure: 100-10000Pa, more preferably 100-1000Pa.

[0080] In addition, the description of a numerical range such as "100 to 100,000 sccm" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "100 to 100,000 sccm" means "above 100 sccm and below 100,000 sccm". The same applies to other numerical ranges. In addition, the so-called flow rate of 0 sccm means that the supply of the substance is not implemented.

[0081] In addition, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. These contents also apply to the following description.

[0082] The modifier can use a gas containing an organic compound. The gas containing an organic compound can use a gas containing at least any one of an ether compound, a ketone compound, an amine compound, an organic hydrazine compound, etc. The gas containing an ether compound can use a gas containing at least any one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. The gas containing a ketone compound can use a gas containing at least any one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. The gas containing an amine compound can use a gas containing at least any one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, and triethylamine, and methylethylamine compounds such as dimethylethylamine and methyldiethylamine. The gas containing an organic hydrazine compound can use a gas containing at least any one of methylhydrazine gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine. The modifier can use one or more of these gases. In addition, as the modifier, it is preferable to use a gas that is difficult to chemically adsorb on the surface of the wafer 200. In order to form an adsorption layer including a modifier that is physically adsorbed on the surface of the wafer 200, for example, a gas that does not substantially chemically react with the adsorption sites (OH groups) on the surface of the wafer 200 can be appropriately used.

[0083] The inert gas may be a rare gas such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), or xenon (Xe). The inert gas may be one or more of these gases. This also applies to each step described later.

[0084] [Step B: Raw material gas supply]

[0085] After step A is completed, the source gas is supplied to the wafer 200 in the processing chamber 201 , that is, to the wafer 200 having the adsorption layer formed on the surface thereof.

[0086] Specifically, valve 324 is opened to allow the raw material gas to flow into the gas supply pipe 320. The raw material gas is flow-regulated by MFC 322, and is supplied into the processing chamber 201 through nozzle 420, and is exhausted from exhaust hole 204a. At this time, the raw material gas is supplied to the wafer 200 (raw material gas supply). The raw material gas is sometimes supplied in a state diluted by a diluent gas such as an inert gas. In addition, valves 514 to 544 may be opened at this time to supply an inert gas into the processing chamber 201 through nozzles 410 to 440, respectively.

[0087] The raw material gas is supplied to the wafer 200 under the conditions described below, so that the raw material gas can react with the surface of the wafer 200. As described below, the raw material gas contains molecules having a first element and a ligand bonded to the first element (hereinafter also referred to as raw material molecules). When the raw material gas reaches the surface of the wafer 200, it reacts with the exposed surface of the wafer 200 that is not covered by the modified layer, that is, it reacts with the adsorption site (OH group) exposed on the surface of the wafer 200. In the course of this reaction, the ligand is separated from the first element (main element) contained in the raw material gas, and the first element having unbound species due to the separation of the ligand is chemically adsorbed (bonded) to the surface of the wafer 200. By virtue of the progress of this reaction, a first layer containing the first element is formed on the wafer 200, that is, on the exposed surface (exposed portion) of the wafer 200 that is not covered by the adsorption layer.

[0088] In addition, when the first layer is formed, a predetermined first by-product is generated. The first by-product sometimes contains a ligand (also referred to as a ligand monomer) that is detached from the first element by reacting the raw material gas with the adsorption site exposed on the surface of the wafer 200. In addition, for example, the first by-product sometimes also contains a molecule in which a part of the ligand has been detached from a molecule having the first element and a ligand bound to the first element. In addition, a molecule in which a part of the ligand has been detached from a molecule having the first element and a ligand bound to the first element is sometimes generated by, for example, thermal decomposition of the raw material gas supplied to the processing chamber 201.

[0089] As described later, the first by-product sometimes contains an organic ligand (organic matter), and it is not expected that the first by-product is adsorbed (attached) to the surface of the film formed on the wafer 200, or the first by-product remains in the film. The adsorption of the first by-product on the film surface or the first by-product remaining in the film is the main reason for the increase in the thickness of the film. Therefore, the adsorption amount or residual amount of the first by-product becomes uneven within the wafer surface and within the inner surface (inner wall) of the concave structure on the wafer, which is the main reason for the deterioration of the uniformity of the film thickness of the film formed on the wafer 200 within the wafer surface and the step coverage (step coverage stepcoverage) of the film formed within the inner surface of the concave structure. In addition, the first by-product remaining in the film will increase the impurities caused by the first by-product in the film, which becomes the main reason for the reduction in film quality. Here, the increase in the thickness of the film can be considered to be caused by the following factors. The first by-product (ligand) present on the wafer 200 after the first layer is formed reacts with the reactant (reaction gas), thereby producing a second by-product. When the second byproduct remains on the wafer 200, the second byproduct reacts with the raw gas in the next cycle of raw gas supply to form an unexpected layer (film). The second byproduct may include hydrogen (H) and oxygen (O). This second byproduct is as shown in the chemical formula R1 X -O-R2 YThe substance shown in the formula is a substance that generates at least one of the substances. Here, R1 and R2 respectively contain at least one of H, nitrogen (N), halogen, and organic ligands. x and y are integers greater than 0. Examples of organic ligands are C1-C5 alkyl groups, amine groups, and the like. Examples of such second by-products include H2O, OH-groups, O-groups, amides, esters, aldehydes, carboxylic acids, ketones, and the like. In addition, although the chemical formula may include ether compounds, it may also include substances other than ether compounds as described above. Examples of substances other than ether compounds include H2O, OH-groups, and the like. Such second by-products may be produced by the reaction of hydrocarbon groups as ligands (especially organic ligands) contained in the raw gas with oxygen-containing gas as a reactant. The second by-product is easily produced when the raw gas contains at least one of hydrocarbon groups and amino groups as organic ligands. Furthermore, it is more likely to be produced when the raw gas contains both hydrocarbon groups and amino groups. Still further, it is more likely to be produced when the raw gas contains alkylamino groups. Since at least one of the hydrocarbon group and the amino group reacts with the reactant to produce a second by-product, when using a modifier containing at least one of the hydrocarbon group and the amino group, the modifier existing on the wafer 200 after the raw material gas is supplied sometimes reacts with the reactant to produce a second by-product. In addition, the second by-product may also have the following situations, for example: when H2O is produced, H2O is difficult to be separated from the wafer 200 by purification, etc., and when the film forming process is cyclically processed, H2O remains in the next cycle, and the H2O existing on the wafer 200 reacts unexpectedly with the raw material gas supplied in the next cycle. In addition, when a film forming process using a modifier is used, such a second by-product reacts unexpectedly with the modifier, and there is a situation where the effect of the modifier is difficult to obtain.

[0090] With regard to this problem, according to the present invention, the amount of the first byproduct generated when the first layer is formed is reduced in the step C described later. Thus, the generation of the second byproduct generated by the reaction of the first byproduct with the reactant can be suppressed. As a result, the following situation can be suppressed, that is, the film formed on the wafer 200 cannot be controlled and the film thickness increases unevenly due to the reaction of the second byproduct with the raw material gas supplied in the next cycle.

[0091] After the formation of the first layer on the wafer 200 is completed, the valve 324 is closed to stop the supply of the raw material gas into the processing chamber 201 .

[0092] After the supply of the raw material gas to the wafer 200 is completed (after it is stopped), it is preferable to Figure 5 As shown, in a state where the supply of the source gas into the processing chamber 201 is stopped, the processing chamber 201 is exhausted to remove the gas remaining in the processing chamber 201 from the processing chamber 201 in step E.

[0093] By performing step E, the ambient gas can be removed from the processing chamber 201, wherein the ambient gas contains the raw material gas that has not reacted or helped to form the first layer, the first by-product, etc. remaining in the processing chamber 201.

[0094] In addition, by performing step E, the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200, can be separated from the surface of the wafer 200. As a result, the modifier can be suppressed from remaining in the film formed on the wafer 200, and the film can be made into a film with a low concentration of impurities caused by the modifier.

[0095] Furthermore, by performing step E, the first by-product attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, that is, together with the modifier physically adsorbed on the surface of the wafer 200. As a result, the first by-product can be suppressed from remaining in the film formed on the wafer 200, and the film can be made into a film with excellent film thickness uniformity and step coverage within the wafer surface and a low concentration of impurities caused by the first by-product.

[0096] By performing step E as described above, a portion of the modifying agent physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above-mentioned various effects can be obtained more reliably.

[0097] The processing conditions for supplying the raw material gas in step B can be exemplified as follows:

[0098] Raw material gas supply flow rate (excluding dilution gas): 0.1 to 10 g / min, more preferably 0.5 to 5 g / min;

[0099] Dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm;

[0100] Raw material gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds;

[0101] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm.

[0102] The other conditions can be the same as those in the process of supplying the modifying agent in step A.

[0103] The treatment conditions in step E after step B can be set to be the same as the treatment conditions in step E after step A.

[0104] The raw material gas can use a gas containing molecules having a first element and a ligand bonded to the first element. The first element can be a metal element, preferably a transition metal element, more preferably a Group 4 element such as zirconium (Zr), hafnium (Hf), titanium (Ti). In addition, the first element can be an element such as aluminum (Al), gallium (Ga), indium (In) of the 13th group element. In addition, silicon (Si), germanium (Ge) of the 14th group element can be listed. In addition, the ligand bonded to the first element can be an organic ligand, preferably a hydrocarbon group containing at least one of an alkyl group such as a methyl, ethyl, propyl, butyl, a cyclopentadienyl group, a cyclohexadienyl group, a cycloheptatrienyl group, etc. In addition, the ligand bonded to the first element can be an amino group, an alkylamino group, etc.

[0105] The raw material gas containing Zr as the first element can use, for example, a gas containing at least any one of tetrakis(ethylmethylamino)zirconium (Zr[N(CH3)C2H5]4), tetrakis(diethylamino)zirconium (Zr[N(C2H5)2]4), tetrakis(dimethylamino)zirconium (Zr[N(CH3)2]4), Zr(MMP)4, Zr(O-tBu)4, tris(dimethylamino)cyclopentadienyl zirconium ((C5H5)Zr[N(CH3)2]3), and tris(dimethylamino)cyclopentadienyl zirconium (ZrCp(N(CH3)2)3). The raw material gas can use one or more of them.

[0106] In addition, the raw material gas containing Hf as the first element can use, for example, a gas containing at least any one of tetrakis(ethylmethylamino)hafnium (Hf[N(CH3)C2H5]4), tetrakis(diethylamino)hafnium (Hf[N(C2H5)2]4), tetrakis(dimethylamino)hafnium (Hf[N(CH3)2]4), Hf(O-tBu)4, Hf(MMP)4, tris(dimethylamino)cyclopentadienylhafnium ((C5H5)Hf[N(CH3)2]3), and tris(dimethylamino)cyclopentadienylhafnium (HfCp(N(CH3)2)3). The raw material gas can use one or more of them.

[0107] In addition, the raw material gas containing Ti as the first element can use, for example, a gas containing at least any one of tetrakis(ethylmethylamino)titanium (Ti[N(CH3)C2H5]4), tetrakis(diethylamino)titanium (Ti[N(C2H5)2]4), tetrakis(dimethylamino)titanium (Ti[N(CH3)2]4), Ti(O-tBu)4, Ti(MMP)4, tris(dimethylamino)cyclopentadienyltitanium ((C5H5)Ti[N(CH3)2]3), and tris(dimethylamino)cyclopentadienyltitanium (TiCp(N(CH3)2)3). The raw material gas can use one or more of them.

[0108] In addition, the raw material gas containing Si as the first element may include aminosilane gases such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4, abbreviated as: 4DMAS) gas, tris(dimethylamino)silane (Si[N(CH3)2]3H, abbreviated as: 3DMAS) gas, bis(diethylamino)silane (Si[N(C2H5)2]2H2, abbreviated as: BDEAS) gas, bis(tert-butylamino)silane (SiH2[NH(C4H9)]2, abbreviated as: BTBAS) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2], abbreviated as: DIPAS) gas.

[0109] [Step C: Treatment gas supply]

[0110] After step B is completed, a treatment gas is supplied to the wafer 200 in the processing chamber 201 , that is, to the wafer 200 on which the first layer containing the first element is formed.

[0111] Specifically, valve 334 is opened to allow treatment gas to flow into gas supply pipe 330. Treatment gas is flow-regulated by MFC 332, supplied into processing chamber 201 through nozzle 430, and exhausted from exhaust hole 204a. At this time, treatment gas is supplied to wafer 200 (treatment gas supply). Treatment gas is sometimes supplied in a diluted state using a diluent gas such as an inert gas. In addition, valves 514 to 544 may be opened at this time to supply inert gas into processing chamber 201 through nozzles 410 to 440, respectively.

[0112] By supplying the processing gas to the wafer 200 under the conditions described below, the processing gas reacts with the first by-product present on the wafer 200 , thereby removing at least a portion of the first by-product.

[0113] After the supply of the treatment gas to the wafer 200 is completed (after it is stopped), it is preferable to Figure 5 As shown, in a state where the supply of the processing gas into the processing chamber 201 is stopped, the processing chamber 201 is exhausted to remove the gas remaining in the processing chamber 201 from the processing chamber 201 in step E.

[0114] By performing step E, the ambient gas can be removed from the processing chamber 201, wherein the ambient gas includes unreacted treatment gas remaining in the processing chamber 201, reaction products generated by the reaction between the treatment gas and the first by-product, and the like.

[0115] Furthermore, by performing step E, the modifier adsorbed (physical adsorbed) on the wafer 200 after step C can be removed from the surface of the wafer 200. As a result, the reaction between the reactant supplied in step D performed thereafter and the modifier can be suppressed.

[0116] The processing conditions in the treatment gas supply of step C can be exemplified as follows:

[0117] Treatment gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm;

[0118] Treatment gas supply time: 10 to 600 seconds, more preferably 30 to 300 seconds;

[0119] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm.

[0120] The other conditions can be the same as those in the process of supplying the modifying agent in step A.

[0121] The treatment conditions in step E after step C can be set to be the same as the treatment conditions in step E after step A.

[0122] The treatment gas may be, for example, a gas that does not contain oxygen (O). In addition, the treatment gas may be, for example, a gas that contains nitrogen (N). The gas containing N may be, for example, at least one of ammonia (NH3), diazene (N2H2) gas, triazene (N3H3) gas, hydrazine (N2H4) gas, etc. In addition, the treatment gas may be, for example, hydrogen (H2), deutrium (D2) gas, activated H2 gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monoborane (BH3) gas, diborane (B2H6) gas, phosphine (PH3) gas, hydrogen chloride (HCl) gas, hydrogen fluoride (HF) gas, hydrogen bromide (HBr) gas, hydrogen iodide (HI) gas, etc. At least one of the gas may be used. In addition, these gases are also referred to as hydrogen-containing gases and reducing gases.

[0123] In addition, the supply of the treatment gas is preferably performed in a state where there is no plasma (also referred to as non-plasma or plasma-free). By supplying the treatment gas without using plasma, it is possible to suppress the generation of a compound in which the element contained in the treatment gas is combined with the first element in the first layer. That is, the reaction can be performed mainly with the first byproduct.

[0124] [Step D: Reactant Supply]

[0125] After step C is completed, a reactant is supplied to the wafer 200 in the processing chamber 201 , that is, to the wafer 200 having the first layer containing the first element formed on the surface thereof.

[0126] Specifically, valve 344 is opened, and reactants flow into gas supply pipe 340. The reactants are flow-regulated by MFC 342, and are supplied into processing chamber 201 through nozzle 440, and are exhausted from exhaust hole 204a. At this time, reactants are supplied to wafer 200 (reactant supply). Reactants are sometimes supplied in a state diluted by a diluent gas such as an inert gas. In addition, valves 514 to 544 may be opened at this time, and inert gases may be supplied into processing chamber 201 through nozzles 410 to 440, respectively.

[0127] By supplying an oxidant as a reactant to the wafer 200 under the conditions described below, for example, and reacting the oxidant with the first layer, the first layer can be modified (oxidized) into a second layer containing the first element and O. That is, the second layer containing no N but the first element and O can be formed.

[0128] In addition, when the second layer is formed, a second byproduct is sometimes generated. The second byproduct is generated by the reaction of the first byproduct and the reactant. However, by performing the above step C, the amount of the first byproduct is reduced, and therefore, the amount of the second byproduct generated is also reduced.

[0129] After the formation of the second layer on the wafer 200 is completed, the valve 344 is closed to stop the supply of the reactants into the processing chamber 201 .

[0130] After the supply of reactants to the wafer 200 is completed (after stopping), it is preferred that Figure 5 As shown, in a state where the supply of reactants into the process chamber 201 is stopped, the process chamber 201 is evacuated, and step E is performed to remove the gas remaining in the process chamber 201 from the process chamber 201 .

[0131] By performing step E, the ambient gas may be removed from the process chamber 201 , wherein the ambient gas contains reactants, second by-products, etc., which remain in the process chamber 201 and are not reacted or have helped to form the second layer.

[0132] Furthermore, by performing step E, the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200, can be detached from the surface of the wafer 200. As a result, the modifier can be suppressed from remaining in the film formed on the wafer 200, and the film can be made into a film with a low concentration of impurities caused by the modifier.

[0133] Furthermore, by performing step E, the first byproduct and the second byproduct attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, that is, together with the modifier physically adsorbed on the surface of the wafer 200. As a result, the first byproduct and the second byproduct can be suppressed from remaining in the film formed on the wafer 200, and the film can be made excellent in film thickness uniformity or step coverage within the wafer surface and in which the concentration of impurities caused by these factors is low.

[0134] By performing step E as described above, a portion of the modifying agent physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above-mentioned various effects can be obtained more reliably.

[0135] The processing conditions in the supply of the reactants in step D can be exemplified as follows:

[0136] Reactant supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm;

[0137] Reactant supply time: 10 to 600 seconds, more preferably 30 to 300 seconds;

[0138] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm.

[0139] The other conditions can be the same as those in the process of supplying the modifying agent in step A.

[0140] The treatment conditions in step E can be set to be the same as the treatment conditions in step E after step A.

[0141] The reactant may use a gas containing O, i.e., an oxidant (oxidizing gas). For example, an oxidant may use a gas containing oxygen (O) and hydrogen (H). For example, a gas containing O and H may use water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) + oxygen (O2), H2 gas + ozone (O3) gas, etc. In addition, in addition to a gas containing O and H, an oxidant may use a gas containing oxygen (O). For example, an O-containing gas may use O2 gas, activated O2 gas, O3 gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc. In addition, a gas containing O and H is also a gas containing O. The oxidant may use one or more of these gases.

[0142] In addition, in this specification, the combined description of two gases such as "H2 gas + O2 gas" means a mixed gas of H2 gas and O2 gas. When supplying the mixed gas, the two gases can be mixed in the supply pipe (pre-mixed) and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 from different supply pipes and mixed in the processing chamber 201 (post-mixed).

[0143] [Scheduled number of implementations X]

[0144] The above steps B and C are performed a predetermined number of times (X times, X is an integer greater than or equal to 1 or 2), so that a first layer containing the first element can be formed on the wafer 200, that is, on the surface of the wafer 200 including the inner surface of the concave structure formed on the surface of the wafer 200. The above cycle is preferably repeated multiple times.

[0145] [Scheduled number of implementations Y]

[0146] The above steps A to E are performed a predetermined number of times (Y times, Y is an integer greater than or equal to 1 or 2), so that a film containing the first element (e.g., an oxide film containing the first element) can be formed on the wafer 200, that is, on the surface of the wafer 200 including the inner surface of the concave structure formed on the surface of the wafer 200. The above cycle is preferably repeated a plurality of times. That is, it is preferred that the thickness of the second layer formed in each cycle is thinner than the desired thickness, and the above cycle is repeated a plurality of times until the thickness of the film (e.g., oxide film) formed by laminating the second layer reaches the desired thickness.

[0147] [Scheduled number of implementations Z]

[0148] The above steps A, B, and C are performed a predetermined number of times (Z times, where Z is an integer greater than or equal to 1 or 2), so that a first layer containing the first element can be formed on the wafer 200, that is, on the surface of the wafer 200 including the inner surface of the concave structure formed on the surface of the wafer 200. The above cycle is preferably repeated a plurality of times.

[0149] (Post-purification and atmospheric pressure recovery)

[0150] After the film formation on the wafer 200 is completed, an inert gas as a purge gas is supplied from each of the nozzles 410 to 440 into the processing chamber 201, and is exhausted from the exhaust hole 204a. Thus, the processing chamber 201 is purged, and the gas, reaction byproducts, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purification). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure restoration).

[0151] (Wafer boat export and wafer unloading)

[0152] Thereafter, the sealing cover 219 is lowered by the wafer boat elevator 115, thereby opening the lower end of the outer tube 203. Next, the processed wafer 200 is carried out from the lower end of the outer tube 203 (wafer boat is led out) to the outside of the outer tube 203 while being supported by the wafer boat 217. Thereafter, the processed wafer 200 is taken out of the wafer boat 217 (also referred to as wafer unloading).

[0153] (3) Effects of this embodiment

[0154] According to the present embodiment, one or more of the following effects can be obtained.

[0155] (a) Step C is performed on the wafer 200 to which step B has been performed, thereby reducing the amount of the first byproduct present on the wafer 200. Thus, the amount of the second byproduct generated by the reaction between the first byproduct and the reactant can be reduced. As a result, the second byproduct present on the wafer 200 can be inhibited from unexpectedly reacting with the raw material gas supplied next. That is, the uniformity of the film thickness within the surface of the wafer 200 can be improved. When a recess is formed on the surface of the wafer 200, the step coverage of the film formed in the recess can be improved.

[0156] (b) Step C is performed on the wafer 200 on which step B has been performed, thereby reducing the amount of the modifier (adsorption layer) present on the wafer 200. By reducing the amount of the adsorption layer, the reaction between the adsorption layer and the reactant supplied in step D can be suppressed. When a material having at least one of a hydrocarbon group, an amino group, and an alkylamino group is used as a modifier and an oxygen-containing gas is used as a reactant, a second by-product (H2O, OH-group, etc.) is sometimes generated. Even in this case, by performing step C, the adsorption layer can be reduced, and thus the reaction between the adsorption layer and the reactant can be suppressed.

[0157] (c) Step C is performed on the wafer 200 that has been subjected to step A and step B. In addition to at least one of the effects of (a) and (b) above, the amount of second byproducts generated by the reaction between the adsorption layer formed on the wafer 200 in step A and the reactant can be reduced. As a result, the second byproducts on the wafer 200 can be inhibited from reacting unexpectedly with the modifier supplied next. In the film forming process of step A, the second byproducts (at least one of H2O, OH-group, etc.) react with the modifier, and although there is a possibility that the original effect of the modifier is reduced, the effect of the modifier can be obtained by performing step C.

[0158] (d) By performing step B and step C X times (X is preferably multiple times), the ligand (especially organic ligand) bound to the first element adsorbed on the wafer 200 can be removed. Since the ligand bound to the first element adsorbed on the wafer 200 becomes a steric hindrance, the first element cannot be adsorbed at the site where the first element can be adsorbed on the wafer 200. By performing the predetermined number of times X, the steric hindrance can be reduced, and the adsorption of the first element toward the wafer 200 can be promoted.

[0159] (e) By performing steps A to C Z times (Z is preferably multiple times), the effect of (d) can be obtained with respect to the region of the wafer 200 where the modifier is difficult to adsorb. Here, the region of the wafer 200 where the modifier is difficult to adsorb is, for example, the bottom side of a recess formed in the wafer 200.

[0160] (f) When, for example, a raw material gas containing a methylamino group [N(CH3)a group, where a is an integer greater than or equal to 1] is used as a ligand of the raw material gas, and, for example, NH3 gas is used as a treatment gas, the ligand can be decomposed by the following reaction. Decomposition products generated in the decomposition can be exhausted from the processing chamber 201.

[0161] [N(CH3)a]+bNH3→cN2+dC2H6+eCH3+fCH4+gH2

[0162] Here, a to g are integers greater than 0. In addition, although an example using methylamino group and NH3 gas is shown here, the present invention is not limited thereto, and similar reactions can be generated when it is changed to other configurations of the present invention.

[0163] (4) Other Implementation Methods

[0164] The embodiments of the present invention have been specifically described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

[0165] For example, Figure 6 (a) to Figure 6 (f) is a modified example of the substrate processing sequence in one embodiment of the present invention. Figure 5 In the timing sequence, a mode of performing step B→step E→step C is shown, but in these modified examples, a mode in which step E is not performed between step B and step C. Figure 6 (a) is a mode in which step C is performed during step B. In other words, step C is started after step B is started, and step B is ended after step C is ended. Figure 6(b) is a mode in which step B is performed during step C. In other words, step B is started after step C is started, and step C is ended after step B is ended. Figure 6 (c) is a mode in which step C is started during step B and step C is ended after step B is ended. Figure 6 (d) is a mode in which step B and step C are started at the same time, and step B is ended after step C is ended. Figure 6 (e) is a mode in which step C is started after step B is started, and steps B and C are ended at the same time. Figure 6 (f) is a mode in which step C is performed instead of step E after step B. In these variations, the same effects as those of the above-mentioned embodiments can still be obtained. In addition, in this variation, further as in these modes, step B and step C are performed in the processing chamber 201 in a manner that the raw gas and at least a portion of the treatment gas are mixed, thereby allowing the ligand contained in the raw gas to be removed by the treatment gas in the gas phase, and allowing the first element contained in the raw gas to be adsorbed on the wafer 200. In addition, since the ligand contained in the raw gas can be removed in the gas phase, even if there is a second by-product on the wafer 200, the gas phase reaction (CVD (Chemical Vapor Deposition) reaction) of the second by-product and the raw gas can be suppressed. In addition, since step E is not performed between step B and step C, the time of the film forming process can be shortened. That is, the manufacturing productivity of semiconductor devices can be improved.

[0166] In addition, for example Figure 7 The substrate processing timing is shown in Figure 2. Figure 7 In Figure 5 In the sequence shown, the mode of step C is performed after step D. In addition, in this sequence, if Figure 7As shown by the dotted line, it is not necessary to perform step A and step C between step B and step D. In this variant, the same effect as the above embodiment can still be obtained. In addition, in this variant, in step D, a second byproduct (H2O, OH-base, etc.) is generated, and the second byproduct is adsorbed on the wafer 200. The second byproduct can be removed by supplying the treatment gas of step C to the wafer 200. As a result, the reaction of the second byproduct with the raw gas can be suppressed. When a modifier is used, the reaction of the second byproduct with the modifier can also be suppressed. In addition, after step D, by performing step C (supplying hydrogen-containing gas), the OH-terminus on the surface of the wafer 200 can be set to H-terminus. In addition, in step C, when NH3 gas is supplied, the OH-terminus can be replaced by NH-terminus. As a result, the second byproduct exposed to the wafer 200 can be reduced, and at least one of the reaction of the second byproduct with the raw gas and the reaction of the second byproduct with the modifier can be reduced. In addition, it can also be considered that in step C after step D, H-termined and NH-termined are formed on the OH-termined on the wafer 200 or the H2O adsorbed on the wafer 200, thereby reducing the OH- and H2O exposed on the surface of the wafer 200. That is, the molecules of the treatment gas supplied in step C and a part of the treatment gas molecules are in a state of covering at least a part of the second byproduct existing on the surface of the wafer 200.

[0167] In addition, if Figure 7 As shown, step C after step D may be performed N times (N is an integer greater than 1). By performing step C after step D multiple times, the amount of the second by-product present on the wafer 200 can be reduced. Preferably, the step is performed when a recess is formed on the wafer 200. In order to uniformly form a film in the recess, it is necessary to form an adsorption layer using a modifier on the upper side of the bottom side of the recess. However, when the second by-product is also present on the bottom side of the recess, the second by-product present on the bottom side of the recess may easily react with the modifier (the modifier is adsorbed on the second by-product). In this state, the modifier is sometimes adsorbed on the bottom side of the recess, and an adsorption layer is also formed on the bottom side of the recess. As a result, it becomes difficult to obtain the step coverage improvement effect of the adsorption layer. For this problem, using a method such as Figure 7 By performing step C N times after step D as shown, the second by-product present on the bottom side of the recess can be removed.

[0168] also, Figure 7Step C after step D shown, in other words, step C is performed before step B. That is, it means that the treatment gas is supplied before the raw material gas is supplied. By supplying the treatment gas before supplying the raw material gas, the surface of the wafer 200 can be modified to a state where the raw material gas is difficult to adsorb. That is, the treatment gas can achieve the effect of hindering the adsorption of the raw material gas on the wafer 200. For example, by using NH3 as the treatment gas, the surface of the wafer 200 can be terminated with NH-groups. At least one of the hydrocarbon groups, amino groups, and alkylamino groups contained in the raw material gas has the characteristic of being difficult to combine (adsorb) with the NH-group. Thereby, the adsorption of the raw material gas on the wafer 200 can be suppressed. When a recess is formed on the surface of the wafer 200, by forming an NH-group termination on the upper part of the recess, the adsorption of the raw material gas toward the upper side of the recess can be suppressed. As a result, the uniformity (step coverage) of the film formed in the recess can be improved.

[0169] In addition, in the above embodiment, although an example of performing step A is shown, the present invention is not limited to this. Figure 5 As shown by the dotted line in FIG. 1 , step A and step E after step A are not performed. Even if step A is not performed, the amount of the first by-product caused by the source gas supplied to the wafer 200 in step B can be reduced in step C.

[0170] In addition, in the above embodiment, although the example of film formation using a batch-type vertical device that processes multiple substrates at a time, that is, a substrate processing device, is described, the present invention is not limited to this, and it can still be appropriately applied when a film is formed using a single-wafer substrate processing device that processes one or more substrates at a time. In addition, in the above method, the example of film formation using a substrate processing device with a hot wall type processing furnace is described. The present invention is not limited to the above method, and it can still be appropriately applied when a film is formed using a substrate processing device with a cold wall type processing furnace.

[0171] When these substrate processing apparatuses are used, each process can still be performed using the same processing steps and processing conditions as the above-mentioned method or modified example, and the same effects as the above-mentioned method or modified example can be obtained.

[0172] In addition, in the above-mentioned method, an example of performing the above-mentioned processing sequence in the same processing chamber (in-situ) of the same substrate processing device has been described. However, the present invention is not limited to the above-mentioned method, and for example, any step and any other step of the above-mentioned processing sequence may be performed in different processing chambers (ex-situ) of different processing devices, or may be performed in different processing chambers of the same substrate processing device.

[0173] The process recipes (programs recording processing steps, processing conditions, etc.) used for the formation of these various thin films are preferably prepared individually (preparing multiple) according to the content of the substrate processing (film type, composition ratio, film quality, film thickness, processing steps, processing conditions, etc. of the formed thin film). Moreover, it is preferred that when the substrate processing is started, an appropriate process recipe is appropriately selected from multiple process recipes according to the content of the substrate processing. Specifically, it is preferred that multiple process recipes prepared individually according to the content of the substrate processing are pre-stored (installed) in the storage device 121c possessed by the substrate processing device via an electrical communication line or a storage medium (external storage device 123) storing the process recipes. Next, it is preferred that when the substrate processing is started, the CPU 121a possessed by the substrate processing device appropriately selects an appropriate process recipe from the multiple process recipes stored in the storage device 121c according to the content of the substrate processing. With this configuration, thin films of various film types, composition ratios, film qualities, and film thicknesses can be formed universally and with good reproducibility using a single substrate processing device. In addition, it is possible to reduce the operator's operational burden (the burden of inputting processing steps, processing conditions, etc.), and to quickly start substrate processing while avoiding operational errors.

[0174] In addition, the present invention can also be implemented by, for example, changing the process recipe of an existing substrate processing device. When changing the process recipe, the process recipe of the present invention can be installed in the existing substrate processing device via an electrical communication line or a storage medium storing the process recipe, or the input and output device of the existing substrate processing device can be operated to change the process recipe itself to the process recipe of the present invention.

[0175] Furthermore, the present invention can be used, for example, in a word line portion of a NAND flash memory or DRAM having a three-dimensional structure.

[0176] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing steps and processing conditions in this case may be, for example, the same as those of the above-mentioned aspects and modifications.

[0177] Explanation of symbols

[0178] 200—Wafer (substrate).

Claims

1. A substrate processing method, characterized in that: have: (a) supplying a raw material gas containing a first element and an organic ligand to a substrate; (b) supplying a treatment gas to the substrate to reduce the amount of by-products present on the surface of the substrate; (c) supplying a first reaction gas to the substrate; and (d) A step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the substrate.

2. The substrate processing method according to claim 1, characterized in that: The organic ligand contains at least one of a hydrocarbon group and an amino group.

3. The substrate processing method according to claim 1, characterized in that: The above-mentioned organic ligand contains a hydrocarbon group and an amino group.

4. The substrate processing method according to claim 1, characterized in that: The above-mentioned organic ligand contains an alkylamino group.

5. The substrate processing method according to any one of claims 1 to 4, characterized in that: The first reaction gas is a gas containing oxygen. In (b), a second reaction gas not containing oxygen element is supplied.

6. The substrate processing method according to claim 5, characterized in that: The second reaction gas is a reducing gas.

7. The substrate processing method according to claim 5, characterized in that: The first reaction gas contains at least one of O2, O3, H2O, H2O2, and activated O2. The second reaction gas contains at least one of NH3, N2H4, H2, activated H2, D2, SiH4, Si2H6, Si3H8, BH3, B2H6, and PH3.

8. The substrate processing method according to claim 5, characterized in that: The second reaction gas is a gas containing nitrogen. In (c), a film containing no nitrogen element and containing the first element and oxygen element is formed on the substrate.

9. The substrate processing method according to claim 5, characterized in that: (b) is carried out under non-plasma conditions.

10. The substrate processing method according to claim 1, characterized in that: In (d), after (a) and (b) are performed a predetermined number of times, (c) is performed.

11. The substrate processing method according to claim 1, characterized in that: In (d), (b) is performed after (c).

12. The substrate processing method according to claim 10, characterized in that: In (d), (b) is performed after (c).

13. The substrate processing method according to claim 1, characterized in that: (a) and (b) are partially executed in parallel.

14. The substrate processing method according to claim 1, characterized in that: In (b), the organic ligand present on the substrate is decomposed.

15. A method for manufacturing a semiconductor device, characterized in that: have: (a) supplying a raw material gas containing a first element and an organic ligand to a substrate; (b) supplying a treatment gas to the substrate to reduce the amount of by-products present on the surface of the substrate; (c) supplying a first reaction gas to the substrate; and (d) A step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the substrate.

16. A program, characterized in that The computer enables the substrate processing device to perform the following steps: (a) supplying a raw material gas containing a first element and an organic ligand to a substrate; (b) supplying a treatment gas to the substrate to reduce the amount of by-products present on the surface of the substrate; (c) supplying a first reaction gas to the substrate; and (d) A step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the substrate.

17. A substrate processing device, characterized in that: have: a raw material gas supply system for supplying a raw material gas containing a first element and an organic ligand to the substrate; a treatment gas supply system for supplying treatment gas to the substrate; A first reaction gas supply system for supplying a first reaction gas to the substrate; and a control unit configured to control the raw material gas supply system, the treatment gas supply system, and the first reaction gas supply system to perform the following processes: (a) a process of supplying the raw material gas to the substrate; (b) a process of supplying the treatment gas to the substrate to reduce the amount of byproducts present on the surface of the substrate; (c) a process of supplying the first reaction gas to the substrate; and (d) performing (a), (b), and (c) a predetermined number of times to form a film containing the first element on the substrate.

Images