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

Abstract

The present invention relates to a substrate processing method, a semiconductor device manufacturing method, a program product, and a substrate processing apparatus. Provided is a technique capable of controlling a film thickness distribution in a recess in processing in which a film is formed in the recess. By performing a cycle including the following processes a prescribed number of times, a film containing a prescribed element is formed in the recess: (a) a process of forming an adsorption barrier layer on a surface in the recess by supplying a first treatment agent to a substrate having a recess; (b) a process of forming a first layer containing the prescribed element and a first halogen element on the surface in the recess by supplying a second treatment agent containing the prescribed element and the first halogen element to the substrate after the process of (a); (c) a process of modifying the first layer to a second layer by supplying a third treatment agent that reacts with the first layer to the substrate; and (d) a process of causing at least a part of the first halogen element to desorb from a surface of the second layer by supplying a fourth treatment agent that is plasma-excited to the substrate.

Description

Technical Field

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

[0002] As a step in the manufacturing process of semiconductor devices, a process of forming a film on a substrate is sometimes performed (see, for example, Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2010-50425 Summary of the Invention

[0004] The problem that the invention aims to solve The present invention provides a technique for controlling the thickness distribution of the film within a recess during the process of forming a film within a recess.

[0005] Methods for solving problems According to one aspect of the present invention, the following technology can be provided: A film containing specified elements is formed within the recess by performing a predetermined number of cycles including the following steps: (a) A process of forming an adsorption barrier layer that prevents the adsorption of a second treatment agent on the surface of the aforementioned recess by supplying a first treatment agent to a substrate having a recess. (b) After starting (a), a process of forming a first layer containing the specified element and the first halogen element on the surface of the aforementioned recess by supplying the aforementioned second treatment agent containing the specified element and the first halogen element to the aforementioned substrate; (c) A process of modifying the first layer into a second layer by supplying the aforementioned substrate with a third processing agent that reacts with the aforementioned first layer; and (d) A process in which at least a portion of the first halogen element is removed from the surface of the second layer by supplying the aforementioned substrate with a plasma-excited fourth processing agent.

[0006] Invention Effects According to the present invention, the thickness distribution of the film within the recess can be controlled during the process of forming the film within the recess. Attached Figure Description

[0007] Figure 1 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that can be suitably used in one aspect of the present invention, showing the portion of the processing furnace 202 in a longitudinal cross-sectional view.

[0008] Figure 2This is a schematic diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in one embodiment of the present invention. Figure 1 The AA-line cross-sectional view shows part of the processing furnace 202.

[0009] Figure 3 (a) is a perspective view of electrodes 300-1 and 300-2, which can be suitably used in one aspect of the present invention, being disposed on electrode fixture 301. Figure 3 (b) is a diagram showing the positional relationship of the heater 207, electrode holder 301, electrodes 300-1, 300-2, protrusion 310 for fixing electrodes 300-1, 300-2, and reaction tube 203, which can be suitably used in one aspect of the invention.

[0010] Figure 4 This is a schematic configuration diagram of the controller 121 of a substrate processing apparatus that can be suitably used in one aspect of the invention, and is a block diagram illustrating the control system of the controller 121.

[0011] Figure 5 This is a diagram illustrating an example of the processing sequence in one aspect of the present invention.

[0012] Figure 6 (a) is an enlarged cross-sectional view of the wafer 200 after step A. Figure 6 (b) is an enlarged cross-sectional view of the wafer 200 after step B. Figure 6 (c) is an enlarged cross-sectional view of the wafer 200 after step C. Figure 6 (d) is an enlarged cross-sectional view of the wafer 200 after step D.

[0013] Figure 7 This is a diagram illustrating an example of the processing sequence in Modification 1 of the present invention.

[0014] Figure 8 This is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in Variation 4 of the present invention, and is a horizontal cross-sectional view of the processing furnace portion.

[0015] Explanation of reference numerals in the attached figures 200 chips Detailed Implementation

[0016] <One aspect of the invention> The following is mainly based on Figures 1-5 , Figure 6 (a) in Figure 6Section (d) describes one aspect of the present invention. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements may not be consistent between different drawings.

[0017] (1) Composition of substrate processing device like Figure 1 As shown, the processing furnace 202 has a heater 207 that functions as a temperature regulator (heating unit). The heater 207 also functions as an activation mechanism (thermal activation unit) that activates (excites) the gas by heat.

[0018] An electrode holder 301 (described later) is disposed inside the heater 207. Furthermore, an electrode 300 (described later) for the plasma generation section is disposed inside the electrode holder 301. A reaction tube 203 is disposed concentrically with the heater 207 inside the electrode 300. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape that is closed at the top and open at the bottom. A manifold 209 is disposed below the reaction tube 203. An O-ring 220a, serving as a sealing component, is provided between the manifold 209 and the reaction tube 203. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing container. The processing chamber 201 is configured to accommodate multiple wafers 200 used as substrates. It should be noted that the processing container is not limited to the above configuration, and sometimes only the reaction tube 203 is referred to as the processing container.

[0019] (Gas Supply Department) Inside the processing chamber 201, nozzles 249a and 249b, serving as first and second supply units, are respectively installed through the side wall of the manifold 209. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively. In this way, by providing two nozzles 249a and 249b and two gas supply pipes 232a and 232b in the processing container, various gases can be supplied into the processing chamber 201.

[0020] On gas supply pipes 232a and 232b, mass flow controllers (MFCs) 241a and 241b, serving as flow controllers (flow control units), and valves 243a and 243b, serving as on / off valves, are sequentially installed from the upstream side of the airflow. Gas supply pipes 232c and 232e are connected downstream of valve 243a on gas supply pipe 232a. Gas supply pipes 232d and 232f are connected downstream of valve 243b on gas supply pipe 232b. On gas supply pipes 232c to 232f, MFCs 241c to 241f and valves 243c to 243f are sequentially installed from the upstream side of the airflow.

[0021] like Figure 1 , Figure 2 As shown, nozzles 249a and 249b are respectively arranged upright from the lower part of the inner wall of the reaction tube 203 along the upward direction of the wafer 200 in the space between the inner wall of the reaction tube 203 and the wafer 200. Gas supply holes 250a and 250b for supplying gas are respectively provided on the sides of nozzles 249a and 249b. When viewed from above, gas supply holes 250a and 250b are opened opposite (facing) the exhaust port 231a and are capable of supplying gas to the wafer 200. Multiple gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

[0022] The first treatment agent is supplied into the treatment chamber 201 from the gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a.

[0023] The third treatment agent is supplied from the gas supply pipe 232b through MFC 241b, valve 243b, and nozzle 249b into the treatment chamber 201.

[0024] The second treatment agent is supplied into the treatment chamber 201 from the gas supply pipe 232c via MFC 241c, valve 243c, gas supply pipe 232a, and nozzle 249a.

[0025] The fourth treatment agent is supplied from gas supply pipe 232d through MFC 241d, valve 243d, gas supply pipe 232b, and nozzle 249b into the treatment chamber 201.

[0026] Inactive gases are supplied to the treatment chamber 201 from gas supply pipes 232e and 232f via MFCs 241e and 241f, valves 243e and 243f, gas supply pipes 232a and 232c, and nozzles 249a and 249b, respectively. The inactive gases function as purge gases, carrier gases, and dilution gases.

[0027] The first treatment agent supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The third treatment agent supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The second treatment agent supply system mainly consists of gas supply pipe 232c, MFC 241c, and valve 243c. The fourth treatment agent supply system mainly consists of gas supply pipe 232d, MFC 241d, and valve 243d. The inactive gas supply system mainly consists of gas supply pipes 232e and 232f, MFC 241e and 241f, and valves 243e and 243f. The first to fourth treatment agent supply systems are collectively referred to as the treatment agent supply system. Alternatively, the nozzles connected to the gas supply pipes constituting each of the above supply systems can be included in their respective supply systems.

[0028] (Substrate support) like Figure 1 As shown, the crystal boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example, 25 to 200 wafers 200, in a horizontal orientation and with their centers aligned in a straight line along the vertical direction, in a multi-layered arrangement, i.e., arranged at intervals. At the lower part of the crystal boat 217, a heat-insulating plate 218, made of a heat-resistant material such as quartz or SiC, is supported in multiple layers.

[0029] (Plasma Generation Unit) Next, use Figures 1-3 (a) Figure 3 Section (b) describes the plasma generation unit.

[0030] An electrode 300 for plasma generation is disposed on the outside of the reaction tube 203, i.e., on the outside (outer periphery) of the processing container (processing chamber 201). By applying electricity to the electrode 300, the gas can be plasmaized and excited inside the reaction tube 203, i.e., inside the processing container (processing chamber 201), that is, the gas is excited into a plasma state. Hereinafter, the process of exciting the gas into a plasma state will sometimes be referred to as plasma excitation. The electrode 300 is configured to generate capacitively coupled plasma (CCP) inside the reaction tube 203, i.e., the processing container (processing chamber 201), by applying high-frequency electricity (RF electricity).

[0031] Specifically, such as Figure 2 As shown, an electrode 300 and an electrode fixing member 301 for fixing the electrode 300 are disposed between the heater 207 and the reaction tube 203. The electrode fixing member 301 is disposed inside the heater 207, the electrode 300 is disposed inside the electrode fixing member 301, and the reaction tube 203 is disposed inside the electrode 300.

[0032] In addition, such as Figure 1 , Figure 2 As shown, the electrode 300 and electrode holder 301 are respectively arranged in a ring-shaped space between the inner wall of the heater 207 and the outer wall of the reaction tube 203, extending from the lower to the upper part of the outer wall of the reaction tube 203 in the arrangement direction of the wafer 200. The electrode 300 is arranged parallel to the nozzles 249a and 249b. The electrode 300 and electrode holder 301 are arranged and configured in a concentric circle with the reaction tube 203 and the heater 207 in a non-contact manner when viewed from above.

[0033] like Figure 2 As shown, multiple electrodes 300 are provided, and these electrodes 300 are fixedly disposed on the inner wall of the electrode fixing member 301. More specifically, a protrusion 310 for hooking the electrode 300 is provided on the inner wall surface of the electrode fixing member 301, and a through hole, i.e., an opening 305, is provided on the electrode 300 for the protrusion 310 to be inserted through. It should be noted that... Figure 2 The diagram shows an example where nine electrodes 300 are fixed to one electrode holder 301, and this structure (unit) consists of two sets. Figure 3 (a) Figure 3 Example of a structure (unit) for fixing eight electrodes 300-1, 300-2 to one electrode fixture 301 is shown in (b).

[0034] like Figure 2 and Figure 3 As shown in (a), electrode 300 includes a first electrode 300-1 and a second electrode 300-2. The first electrode 300-1 is connected to a high-frequency power supply (RF power supply) 320 via a matching connector 325 and is subjected to an arbitrary potential. The second electrode 300-2 is connected to ground and becomes a reference potential (0V). The first electrode 300-1 is also referred to as the Hot electrode, and the second electrode 300-2 is referred to as the Ground electrode. The first electrode 300-1 and the second electrode 300-2 are each configured as a rectangular plate-shaped component when viewed from the front. Figure 2 , Figure 3 (a) Figure 3 Example (b) shows an example with four first electrodes 300-1 and four second electrodes 300-2. Plasma is generated in the region between the first electrodes 300-1 and the second electrodes 300-2 by applying RF power from RF power supply 320 via matching unit 325 to the region between the first electrodes 300-1 and the second electrodes 300-2. This region is also referred to as the plasma generation region. Figure 2As shown, the electrodes 300 (first electrode 300-1, second electrode 300-2) are configured to extend in the length direction along the loading direction in which the plurality of wafers 200 are loaded, and are positioned on an arc when viewed from above. Furthermore, the electrodes 300 are configured to be fixed between the reaction tube 203 and the heater 207 to the inner wall of the electrode holder 301, which is positioned in a generally arc shape when viewed from above, in a manner that runs along the outer wall of the reaction tube 203.

[0035] Plasma 302 is generated within the reaction tube 203 by inputting a high frequency, for example, between 25 MHz and 35 MHz, from the RF power supply 320 to the electrode 300 via the matching unit 325. Using the plasma 302 generated in this way, active species for substrate processing can be supplied to the surface of the wafer 200 from the surrounding area of ​​the wafer 200.

[0036] The plasma generation section (plasma excitation section) is mainly composed of electrodes 300, which excites (activates) the gas into a plasma state. It can also be considered that the plasma generation section includes electrode fixing member 301, matching device 325, and RF power supply 320.

[0037] (Exhaust section) like Figure 1 As shown, an exhaust pipe 231 for venting the atmosphere inside the processing chamber 201 is provided in the reaction tube 203. A vacuum pump 246, serving as a vacuum venting device, is connected to the exhaust pipe 231 via a pressure sensor 245 (pressure detector, pressure sensing unit) and an APC (Auto Pressure Controller) valve 244 (pressure regulating unit). The APC valve 244 is configured to allow vacuum venting and cessation of vacuum venting within the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted by regulating the valve opening based on the pressure information detected by the pressure sensor 245. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be considered as being included in the exhaust system.

[0038] (Peripheral devices) A sealing cap 219, serving as a furnace opening cover, is provided below the manifold 209 to airtightly seal the lower opening of the manifold 209. The sealing cap 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. An O-ring 220b, serving as a sealing member, is provided on the upper surface of the sealing cap 219, abutting against the lower end of the manifold 209.

[0039] A rotation mechanism 267 for rotating the crystal boat 217 is provided on the opposite side of the sealing cover 219 from the processing chamber 201. The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. The sealing cover 219 is configured to move vertically upwards and downwards via a crystal boat lift 115, which is vertically provided outside the reaction tube 203 and serves as a lifting mechanism. The crystal boat lift 115 is configured to move the crystal boat 217 in and out of the processing chamber 201 by moving the sealing cover 219 upwards and downwards.

[0040] The crystal boat elevator 115 is configured as a conveying device (conveying mechanism) for transporting the crystal boat 217, i.e. the wafer 200, to and from the processing chamber 201.

[0041] A temperature sensor 263, which serves as a temperature detector, is installed inside the reaction tube 203. By adjusting the energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature within the processing chamber 201 is adjusted to achieve the desired temperature distribution.

[0042] (Control device) Next, use Figure 4 The control device should be described. For example... Figure 4 As shown, the controller 121, serving as the control unit (control device), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121.

[0043] The storage device 121c is configured such as flash memory, HDD (Hard Disk Drive), or SSD (Solid State Drive). The storage device 121c records and stores in a readable manner a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions (described later). The process flow is formed by the controller 121 causing the substrate processing apparatus to execute each step of the substrate processing (described later) in a way that yields a predetermined result, and functions as a program. Hereinafter, the process flow, control program, etc., will be generally referred to as a program (program product). Furthermore, the process flow will be referred to simply as a process. When the term "program" is used in this specification, there may be cases where only the process flow is included, cases where only the control program is included, or cases where both are included. RAM 121b is configured as a memory area that temporarily holds programs, data, etc., read by the CPU 121a.

[0044] I / O port 121d is connected to the aforementioned MFC 241a~241f, valves 243a~243f, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, crystal boat lift 115, RF power supply 320, etc.

[0045] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on inputs such as operation commands from input / output device 122. CPU 121a is configured to perform the following according to the read processes: flow regulation of various gases based on MFC 241a to 241f, opening and closing of valves 243a to 243f, opening and closing of APC valve 244, pressure regulation based on pressure sensor 245 and using APC valve 244, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation of crystal boat 217 based on rotation mechanism 267, lifting and lowering of crystal boat 217 based on crystal boat lift 115, and control of power supply to RF power supply 320.

[0046] The controller 121 can be configured to install the aforementioned program, recorded and stored in the external storage device 123, into the computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, a USB flash drive, or a semiconductor storage device such as an SSD. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium. Hereinafter, they will also be generally referred to simply as recording media. When the term "recording medium" is used in this specification, there may be a case where only the storage device 121c is included, a case where only the external storage device 123 is included, or a case where both are included. It should be noted that the program can also be provided to the computer using a communication unit such as the Internet or a dedicated line, without using the external storage device 123.

[0047] (2) Substrate processing process Main use Figure 5 , Figure 6 (a) in Figure 6 (d) describes a method for processing a substrate using the aforementioned substrate processing apparatus as a step in the manufacturing process of a semiconductor device, namely, an example of a processing sequence for forming a film on the surface of the wafer 200, which serves as the substrate. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0048] In this method, an example using a wafer 200 with recesses such as grooves, slots, and holes formed on its surface as three-dimensional structures will be described. It should be noted that, in this specification, the term "recess" is not limited to shapes with a bottom surface; for example, it sometimes includes structures such as gaps or through holes that do not have a bottom surface. In the case of structures without a bottom surface, "bottom side" sometimes refers to the direction (side) from each opening toward the inside of the structure when viewed from two or more openings.

[0049] In this processing sequence, a film containing a specified element is formed within the concave portion by repeating the following steps a specified number of times (n times, where n is an integer of 1 or 2 or higher): (a) Step A: By supplying a first processing agent to a wafer 200 having a recess, an adsorption barrier layer is formed on the surface within the recess to prevent the adsorption of a second processing agent. (b) After starting step A, step B is to form a first layer containing the specified element and the first halogen element on the surface of the recess by supplying a second processing agent containing the specified element and the first halogen element to the wafer 200; (c) Step C, which modifies the first layer into a second layer by supplying the wafer 200 with a third processing agent that reacts with the first layer; and (d) Step D, in which at least a portion of the first halogen element is removed from the surface of the second layer by supplying the wafer 200 with a plasma-excited fourth processing agent.

[0050] In the following examples, such as Figure 5 As shown, the cases in steps A and B where the first and second treatment agents are not subjected to plasma excitation (i.e., steps A and B are performed in a non-plasma atmosphere) will be explained, and the cases in steps C and D where the third and fourth treatment agents are subjected to plasma excitation will be explained.

[0051] In addition, the following examples illustrate cases where the first processing agent contains a specified element and a second halogen element, and the specified element contained in the first processing agent and the specified element contained in the second processing agent are the same element.

[0052] For convenience, the above processing order is sometimes represented as follows in this specification. The same expression is also used in the following descriptions of other methods, variations, etc.

[0053] (First treatment agent → purge → Second treatment agent → purge → plasma excitation → Third treatment agent → plasma excitation → Fourth treatment agent → purge) × n Figure 5 In this diagram, the implementation periods for steps A, B, C, and D are denoted as A, B, C, and D, respectively. The implementation period for purging is represented by P. Figure 7 The same applies to China.

[0054] The term "wafer" as used in this specification can refer to the wafer itself, or to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" as used in this specification can refer to the surface of the wafer itself, or to the surface of a specified layer, etc., formed on the wafer. In this specification, when described as "forming a specified layer on the wafer," it can mean forming the specified layer directly on the surface of the wafer itself, or forming the specified layer on top of a layer, etc., formed on the wafer. In this specification, the use of "substrate" is also synonymous with the use of "wafer."

[0055] As used in this specification, the terms "agent" and "substance" include at least one of gaseous and liquid substances. Liquid substances include mist substances. That is, the first to fourth treatment agents may contain gaseous substances, mist substances, or other liquid substances, or both.

[0056] As used in this specification, the term "layer" includes at least one of continuous layers and discontinuous layers. For example, the adsorption barrier layer, the first layer, and the second layer described later may include continuous layers, discontinuous layers, or both.

[0057] In this specification, when describing the adsorption and reaction of the first to fourth treatment agents onto the surface of the wafer, it includes not only the adsorption and reaction of the agents onto the wafer surface in their undecomposed state, but also the adsorption and reaction of the intermediates generated by their decomposition and ligand release onto the wafer surface.

[0058] (Wafer filling and crystal boat loading) When loading multiple wafers 200 into the crystal boat 217, open the lower opening of the manifold 209. Then, as... Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat elevator 115 and moved into a processing chamber 201. In this way, the wafers 200 are prepared in the processing chamber 201.

[0059] (Pressure and temperature regulation) After the crystal boat is loaded, vacuum venting (pressure reduction venting) is performed by vacuum pump 246 to bring the processing chamber 201 to the desired pressure (vacuum level). Additionally, the wafer 200 inside the processing chamber 201 is heated by heater 207 to the desired processing temperature. Furthermore, rotation of the wafer 200 is initiated based on rotation mechanism 267. Venting in the processing chamber 201, heating of the wafer 200, and rotation are all performed continuously until the processing of the wafer 200 is completed.

[0060] (Film-forming treatment) Then, execute steps A through D in sequence.

[0061] [Step A] In step A, a first processing agent containing a specified element and a second halogen element is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 243a is opened to allow the first processing agent to flow into the gas supply pipe 232a. The first processing agent is supplied to the processing chamber 201 via nozzle 249a and vented through exhaust port 231a by MFC 241a for flow regulation. At this time, the first processing agent is supplied to the wafer 200 (first processing agent supply). At this time, valves 243e and 243f may also be opened to supply inactive gas into the processing chamber 201 via nozzles 249a and 249b, respectively.

[0062] Examples of processing conditions for supplying the first processing agent in this step include: Processing temperature: 300–700℃, preferably 400–650℃ Processing pressure: 100–4000 Pa, preferably 100–1000 Pa First treatment agent supply flow rate: 0.1–3 slm The first treatment agent supply time is 1 to 100 seconds, preferably 1 to 30 seconds. Inactive gas supply flow rate (per gas supply pipe): 0-10 slm.

[0063] It should be noted that the numerical range "300~700℃" in this specification refers to the lower and upper limits being included within that range. Therefore, for example, "300~700℃" means "above 300℃ and below 700℃". The same applies to other numerical ranges. Furthermore, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201, in other words, the pressure of the space where the wafer 200 exists (being processed). Additionally, the processing time refers to the duration of the processing. Also, when the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied. These same principles apply in the following descriptions.

[0064] By supplying the first processing agent to the wafer 200 under the aforementioned processing conditions, at least one of the partial structures of the first processing agent and its molecules (hereinafter also referred to as the first processing agent, etc.) can be adsorbed onto a first adsorption site on the surface of a first region (specifically, the region on the opening side of the recess) that is part of the recess (see...). Figure 6 (a)). By adsorbing the first treatment agent or the like onto the first adsorption site on the surface of the first region, a layer (hereinafter also referred to as the A layer) containing a specified element and atomically capped by a second halogen element in a state of being bonded to the specified element (hereinafter also referred to as the second halogen capping) can be formed in that region. Specifically, under the above-described treatment conditions, a portion of the bond between the specified element in the first treatment agent and the second halogen element is broken, causing atoms of the specified element having unbonded bonds to adsorb onto the first adsorption site on the surface of the first region, thereby forming the A layer.

[0065] In layer A, the adsorption of at least one of the components of the second treatment agent supplied in step B (hereinafter also referred to as the second treatment agent, etc.) is suppressed (hindered) by a second halogen end-capping formed on the surface. In other words, layer A constitutes an adsorption barrier layer that prevents the adsorption of the second treatment agent, etc., on layer A. Further, in other words, layer A constitutes an adsorption barrier layer that prevents the second treatment agent, etc., from adsorbing onto a first adsorption site on the surface where the first treatment agent, etc., is adsorbed, existing in the first region.

[0066] It should be noted that, in this method, as a pretreatment step, it is preferable to pre-flow the wafer 200 with, for example, the third treatment agent used in step C described later. During pre-flow, by supplying, for example, a nitriding agent containing nitrogen (N) and hydrogen (H) as the third treatment agent, NH capping, serving as the first adsorption site, can be formed on the surface of the wafer 200. Therefore, in this step and step B described later, the first and second treatment agents can be readily adsorbed. The pre-flow step can, for example, be the same as the step C described later, performed in a non-plasma atmosphere.

[0067] As the first processing agent, a substance containing a specified element and a second halogen element may be used. If the specified element is Si, a halosilane may be used as the first processing agent. As the second halogen element, at least one of chlorine (Cl), fluorine (F), bromine (Br), and iodine (I) may be used.

[0068] As the first processing agent, gases containing chlorosilanes such as tetrachlorosilane (SiCl4), monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), hexachlorodisilane (Si2Cl6), octachlorotrisilane (Si3Cl8), monochlorodisilane (Si2H5Cl), dichlorodisilane (Si2H4Cl2), trichlorodisilane (Si2H3Cl3), tetrachlorodisilane (Si2H2Cl4), monochlorotrisilane (Si3H5Cl), and dichlorotrisilane (Si3H4Cl2) can be used.

[0069] In addition to chlorosilanes, gases containing fluorosilanes such as tetrafluorosilane (SiF4) and difluorosilane (SiH2F2), bromosilanes such as tetrabromosilane (SiBr4) and dibromosilane (SiH2Br2), and iodosilanes such as tetraiodosilane (SiI4) and diiodosilane (SiH2I2) can also be used as the first processing agent.

[0070] As a first processing agent, a gas containing a compound is preferably used, which is a compound of the above-mentioned halosilanes having a molecular structure in which atoms of a second halogen element are bonded to all the bonds of the atoms of a specified element (Si) (e.g., SiCl4, SiF4, SiBr4, SiI4).

[0071] One or more of these can be used as the first treatment agent.

[0072] As inert gases, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. One or more of these can be used as inert gases. This also applies to the steps described later.

[0073] After forming an adsorption barrier layer on the surface within the recess of wafer 200, valve 243a is closed to stop supplying the first processing agent into processing chamber 201. Then, a vacuum is applied to processing chamber 201 to remove any gaseous substances remaining within it. At this time, valves 243e and 243f are opened, and inactive gas is supplied into processing chamber 201 via nozzles 249a and 249b. The inactive gas supplied from nozzles 249a and 249b acts as a purging gas, thereby purging processing chamber 201.

[0074] [Step B] After step A is completed, a raw material containing a specified element and a first halogen element is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the adsorption barrier layer is formed on the inner surface of the recess, as a second processing agent.

[0075] Specifically, valve 243c is opened, allowing the second processing agent to flow into the gas supply pipe 232c. The flow rate of the second processing agent is regulated using MFC 241c, and it is supplied into the processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this time, the second processing agent is supplied to the wafer 200 (second processing agent supply). At this time, valves 243e and 243f can also be opened to supply inactive gas into the processing chamber 201 via nozzles 249a and 249b, respectively.

[0076] Examples of processing conditions for supplying the second processing agent in this step include: Second treatment agent supply flow rate: 0.1–3 slm The second treatment agent is supplied for 1 to 100 seconds, preferably 1 to 30 seconds.

[0077] Other processing conditions can be the same as those when the first processing agent is supplied in step A.

[0078] By supplying the second processing agent to the wafer 200 under the aforementioned processing conditions, the second processing agent can be adsorbed onto the first adsorption site on the surface of the second region (specifically, the region on the bottom side of the recess), which is another part of the recess (see...). Figure 6 (b)). By adsorbing the second treatment agent or the like onto the first adsorption site on the surface of the second region, a first layer containing a specified element and a first halogen element can be formed in that region. Specifically, under the above-described treatment conditions, at least one of the bonds between the specified elements in the second treatment agent (e.g., Si-Si bonds) and the bonds between the specified element and the first halogen element (e.g., Si-Cl bonds) is broken, causing atoms of the specified element with unbonded bonds to adsorb onto the first adsorption site in the second region, thereby forming a first layer containing the specified element and the first halogen element.

[0079] It should be noted that the first region where the adsorption barrier layer is formed and the second region where the first layer is formed sometimes overlap at least partially in the surface within the recess. In other words, sometimes the first layer is formed at at least a portion of the first adsorption sites remaining in the gaps of the discontinuously formed adsorption barrier layers (see...). Figure 6 (b) in the middle.

[0080] As the second processing agent, a substance comprising a specified element and a first halogen element can be used. For example, a halosilane comprising Si, which is the main element (i.e., the specified element) constituting the film formed on wafer 200, can be used. As the first halogen element, at least one element selected from Cl, F, Br, and I can be used. The second halogen element in the second processing agent and the first halogen element in the first processing agent can be the same element or different elements.

[0081] As the second processing agent, one or more of the substances (halosilanes) listed as the first processing agent may be used. However, the first processing agent and the second processing agent are substances with different molecular structures.

[0082] As a second processing agent, it is preferable to use, for example, compounds of the halosilanes described above that have molecular structures having bonds between atoms (Si) of a specified element (e.g., Si2Cl6, Si3Cl8, Si2H5Cl, Si2H4Cl2).

[0083] Furthermore, it is preferable to use a compound with a molecular structure in which atoms of the second halogen element are bonded to all the bonds of the atoms of the specified element (Si) (e.g., SiCl4) as the first treatment agent, and a compound with a molecular structure containing bonds between atoms of the specified element (Si) (e.g., Si2Cl6) as the second treatment agent. In this case, the ratio of the number of atoms of the second halogen element contained in the adsorption barrier layer to the number of atoms of the specified element (e.g., 4 / 1) is greater than the ratio of the number of atoms of the first halogen element contained in the first layer to the number of atoms of the specified element (e.g., 6 / 2).

[0084] After the first layer is formed on the surface within the recess of the wafer 200, valve 243c is closed to stop the supply of the second processing agent to the processing chamber 201. Then, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps as the purging in step A.

[0085] [Step C] After step B is completed, the reactant, which is the third processing agent, is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the first layer is formed on the inner surface of the recess.

[0086] Specifically, valve 243b is opened, allowing the third processing agent to flow into the gas supply pipe 232b. The flow rate of the third processing agent is regulated by MFC 241b and supplied into the processing chamber 201 via nozzle 249b (third processing agent supply). At this time, high-frequency power is supplied (applied) to the electrode 300 from the RF power supply 320. The third processing agent supplied into the processing chamber 201 is excited by plasma inside the processing chamber 201, generating active species (excited species). At this time, the third processing agent containing the active species is supplied to the wafer 200. At this time, valves 243e and 243f can also be opened to supply inactive gas into the processing chamber 201 via nozzles 249a and 249b, respectively.

[0087] Examples of processing conditions for supplying the third processing agent in this step include: Processing pressure: 2–100 Pa, preferably 20–70 Pa The third treatment agent supply flow rate is 0.1–10 slm. The third treatment agent supply time is 10–600 seconds, preferably 10–60 seconds. RF power: 100-1000W RF frequency: 25MHz~35MHz.

[0088] Other processing conditions can be the same as those when the first processing agent is supplied in step A.

[0089] By supplying the third processing agent to the wafer 200 under the aforementioned processing conditions, the first layer and the A layer (i.e., the adsorption barrier layer) formed on the surface within the recess react with the third processing agent and are modified into a second layer. As a result, a second layer is formed on the surface within the recess. (See...) Figure 6 (c) That is, the second layer is composed of the layer formed by the reaction of the first layer with the third treatment agent and the layer A (adsorption barrier layer) formed by the reaction of the third treatment agent. It should be noted that in this specification, the layer formed by the reaction of the first layer with the third treatment agent is sometimes specifically referred to as the second layer.

[0090] For example, as a third treatment agent, by supplying the nitriding agent described later, the first and second halogen elements contained in the first and A layers are removed, and NH capping as the first adsorption site can be formed on the surface of the second layer. However, at this time, a portion of the first and second halogen elements contained in the first and A layers cannot be completely removed, thus remaining on the surface of the second layer (see...). Figure 6 (c) Figure 6(c) shows an example where Cl remains as the first halogen element). In the second layer, the adsorption of the first treatment agent supplied in step A of the next cycle can be promoted by the first adsorption sites formed on its surface. On the other hand, the adsorption of the first treatment agent is hindered by at least one of the first halogen element and the second halogen element remaining on its surface.

[0091] As a third processing agent, a nitriding agent can be used, for example. As a nitriding agent, a gas containing substances containing N and H can be used, for example. As substances containing N and H, hydrogen nitride-based substances such as ammonia (NH3), diazoxide (N2H2), hydrazine (N2H4), and N3H8 can be used, for example.

[0092] In addition to these, gases containing N, carbon (C), and hydrogen (H) can also be used as the third processing agent. Examples of substances containing N, C, and H include ethylamines such as monoethylamine (C2H5NH2), diethylamine ((C2H5)2NH), and triethylamine ((C2H5)3N), amines such as monomethylamine (CH3NH2), dimethylamine ((CH3)2NH), and trimethylamine ((CH3)3N), and organohydrazines such as monomethylhydrazine ((CH3)HN2H2), dimethylhydrazine ((CH3)2N2H2), and trimethylhydrazine ((CH3)2N2(CH3)H).

[0093] As a third processing agent, one or more of these can be used. As a third processing agent, for example, in the case of using a nitriding agent, as an active species generated by plasma excitation, a free radical containing N (e.g., Ions containing N. As a third treatment agent, for example, when using a substance containing both N and H, free radicals containing N and H (e.g., [missing information]) can be used as active species generated by plasma excitation. Ions containing NH. It should be noted that... This represents a free radical. The same applies in the following explanation.

[0094] After the second layer is formed on the surface within the recess of the wafer 200, valve 243b is closed to stop the supply of the third processing agent to the processing chamber 201. Then, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps as the purging in step A.

[0095] [Step D] After step C is completed, the fourth processing agent is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the second layer is formed on the inner surface of the recess. The fourth processing agent is excited by plasma.

[0096] Specifically, valve 243d is opened, allowing the fourth processing agent to flow into the gas supply pipe 232d. The flow rate of the fourth processing agent is regulated by MFC 241d and supplied into the processing chamber 201 via nozzle 249b (fourth processing agent supply). At this time, high-frequency power is supplied (applied) to the electrode 300 from the RF power supply 320. The fourth processing agent supplied into the processing chamber 201 is excited by plasma inside the processing chamber 201, generating active species. At this time, the fourth processing agent containing active species is supplied to the wafer 200. At this time, valves 243e and 243f can also be opened to supply inactive gas into the processing chamber 201 via nozzles 249a and 249b, respectively.

[0097] Examples of processing conditions for supplying the fourth processing agent in this step include: Processing pressure: 2–100 Pa, preferably 20–70 Pa The fourth treatment agent supply flow rate is 0.1–10 slm. The fourth treatment agent supply time is 5 to 450 seconds, preferably 0.5 to 30 seconds. RF power: 100-1000W RF frequency: 25MHz~35MHz.

[0098] Other processing conditions can be the same as those when the third processing agent is supplied in step C.

[0099] By supplying the fourth processing agent to the wafer 200 under the aforementioned processing conditions, at least a portion of the first halogen element and the second halogen element can be detached from the surface of the second layer (see [link]). Figure 6 (d)). It should be noted that, in the following, at least one of the first halogen element and the second halogen element will sometimes be referred to simply as "halogen element".

[0100] By removing at least a portion of the first halogen element and the second halogen element from the surface of the second layer, the first adsorption site formed at the portion (site) where the first halogen element or the second halogen element is removed can function as an adsorption site for the first treatment agent, etc. This can also be considered as forming or increasing the number of first adsorption sites capable of adsorbing the first treatment agent, etc., by removing at least a portion of the first halogen element and the second halogen element from the surface of the second layer.

[0101] By supplying the fourth processing agent to the wafer 200 under the aforementioned processing conditions, at least a portion of the first and second halogen elements can be detached from the surface of the second layer in such a way that the density of the first and second halogen elements at the opening side of the recess (including the density where at least one of the first and second halogen elements exists) is smaller than that at the bottom side of the recess. In other words, at least one of the first and second halogen elements remaining at the opening side of the recess can be selectively (preferably) removed compared to at least one of the first and second halogen elements remaining at the bottom side of the recess (see [link]). Figure 6 (d)). At this time, by adjusting at least one of the above processing conditions—the magnitude of the RF power, the processing pressure, or the supply time of the fourth processing agent—the density distribution of the first and second halogen elements within the recess can be adjusted. For example, the shorter the supply time of the fourth processing agent, the more effectively the first halogen element on the opening side of the recess can be removed.

[0102] As a fourth processing agent, a gas containing a substance with hydrogen (H) can be used, for example. The substance containing H can be, for example, H2 or other substances composed solely of the hydrogen element.

[0103] As a fourth processing agent, it can also replace the H-containing substance to supply a gas containing a deuterium (D)-containing substance, or supply a gas containing a deuterium (D)-containing substance in addition to the H-containing substance. As the D-containing substance, for example, a substance composed of only the D element, such as D2, can be used.

[0104] As a fourth processing agent, for example, in the case of using a substance containing H, as an active species generated by plasma excitation, a free radical containing H (e.g., The fourth treatment agent preferably contains H-containing ions. The lifetime of the active species generated by plasma excitation is shorter than the lifetime of the active species contained in the plasma-excited third treatment agent. Examples of combinations of active species with such a lifetime relationship include, for instance, free radicals containing N and H generated by plasma excitation of the N- and H-containing substance used as the third treatment agent (e.g., N- and H-containing ions). Compared to these, shorter-lived free radicals (e.g., those containing H but lacking N) generated by plasma excitation of H-containing substances used as the fourth treatment agent are also available. In this way, by supplying live species with relatively short lifespans (e.g.) The fourth treatment agent deactivates the active species on the opening side before reaching the bottom side of the recess, thus enabling the local removal of at least one of the first halogen element and the second halogen element on the opening side of the recess.

[0105] After at least a portion of the first and second halogen elements are removed from the surface of the second layer, valve 243d is closed to stop the supply of the fourth treatment agent to the treatment chamber 201. Then, gaseous substances and the like remaining in the treatment chamber 201 are removed from the treatment chamber 201 by the same treatment steps as the purging in step A.

[0106] [Number of times stipulated for implementation] By performing steps A, B, C, and D sequentially n times (where n is an integer of 1 or 2 or more) non-simultaneously (or in other words, alternately or intermittently), a film containing a specified element can be formed within the recess of the wafer 200. The film formed within the recess of the wafer 200 can form an inner space of the recess that communicates with the outer space of the recess. For example, using the second processing agent containing Si and the third processing agent containing N, a silicon nitride film (SiN film) can be formed within the recess. Alternatively, using the third processing agent containing N and C, a silicon carbon nitride film (SiCN film) can be formed within the recess. The above cycle is preferably repeated at least twice until the film thickness formed by stacking the second layer reaches the desired thickness.

[0107] (Post-purge and atmospheric pressure recovery) After the film-forming process is completed, inert gases are supplied as purge gases into the treatment chamber 201 through nozzles 249a and 249b, and exhausted through exhaust port 231a. This purges the treatment chamber 201, removing residual gases and reaction products. Then, the atmosphere in the treatment chamber 201 is replaced with an inert gas, and the pressure inside the treatment chamber 201 returns to atmospheric pressure.

[0108] (Crystal boat unloading and wafer removal) Then, the sealing cover 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the crystal boat 217, is then moved from the lower end of the manifold 209 to the outside of the reaction tube 203. After the processed wafer 200 is moved to the outside of the reaction tube 203, it is removed from the crystal boat 217.

[0109] (3) The effects of this method According to this method, one or more of the following effects can be obtained.

[0110] (a) In step A, by supplying the first processing agent to the wafer 200 having the recess, the film thickness distribution within the recess can be controlled. Specifically, in step A, when the first processing agent is supplied to form an adsorption barrier layer that hinders the adsorption of the second processing agent, the first processing agent is adjusted to adsorb on the opening side (near the opening) of the recess. As a result, in step B, the second processing agent can be more easily adsorbed on the bottom side compared to the opening side of the recess. As a result, for example, the step coverage of the formed film can be improved.

[0111] In step D, a fourth treatment agent excited by plasma is supplied, causing at least a portion of the first halogen element and the second halogen element (which hinder the adsorption of the first treatment agent) to detach from the surface of the second layer, thereby enabling the first treatment agent to be adsorbed onto the surface within the recess in step A of the next cycle.

[0112] In step D, a fourth treatment agent excited by plasma is supplied. The plasma-excited fourth treatment agent has a shorter lifetime compared to the unexcited fourth treatment agent. By supplying a short-lived active species generated through plasma excitation of the fourth treatment agent, the probability of the fourth treatment agent reaching the bottom side of the recess is reduced, allowing the fourth treatment agent to primarily reach the opening side of the recess. This enables at least one of the first and second halogen elements remaining on the opening side of the recess to preferentially detach. Consequently, in step A of the next cycle, the first treatment agent can be effectively adsorbed onto the opening side of the recess.

[0113] (b) By performing two or more cycles including steps A to D, the adsorption of the first treatment agent after the second cycle can be particularly promoted, thereby improving the controllability of the film thickness distribution within the recess. Specifically, for example, the step coverage of the film can be improved.

[0114] (c) By including the second halogen element in the first treatment agent, an adsorption barrier layer capped by the second halogen can be formed in step A. The second halogen capping formed on the surface of the adsorption barrier layer prevents the adsorption of the second treatment agent, etc., in step B, thereby improving the controllability of the film thickness distribution within the recess. Specifically, for example, it can improve the step coverage of the film.

[0115] (d) By including the specified element in the first treatment agent, the adsorption capacity (adsorption ease) to the surface inside the recess can be improved in step A. In addition, by forming an adsorption barrier layer containing the specified element, the adsorption barrier layer (layer A) can be modified together with the first layer to form the second layer in step C, thereby improving the film deposition rate.

[0116] (e) By making the ratio of the number of atoms of the second halogen element contained in the adsorption barrier layer to the number of atoms of the specified element greater than the ratio of the number of atoms of the first halogen element contained in the first layer to the number of atoms of the specified element, the adsorption barrier effect of the second treatment agent, etc., brought about by the first treatment agent can be improved.

[0117] Furthermore, this can further enhance the locality of the adsorption barrier effect at the opening side of the recess brought about by step D. This will be explained below.

[0118] As described above, compared to the adsorption inhibition effect of the second treatment agent, etc., caused by the first halogen element remaining in the second layer in step C, the adsorption inhibition effect of the second treatment agent, etc., caused by the second halogen end-capping formed on the surface of the adsorption inhibition layer in step A is higher. Therefore, after removing the first halogen element remaining in the second layer (formed on the opening side of the recess) in step D, compared to performing step A without performing step D, forming an adsorption inhibition layer in the part where the first halogen element has been removed in step A of the next cycle can relatively enhance the adsorption inhibition effect of that part.

[0119] (f) By including a compound having a molecular structure in which the second halogen atom is bonded to all the bonding bonds of the specified element atoms, the adsorption barrier effect of the second halogen atom on the surface of the recess can be improved when the first treatment agent is adsorbed on the surface of the recess.

[0120] (g) By including the second treatment agent in a compound with a molecular structure having bonds between atoms of a specified element (e.g., Si), the Si-Si bonds are broken by thermal energy, thus facilitating thermal decomposition. As a result, the unbonded bonds of highly reactive Si are adsorbed onto the surface within the recess, thereby increasing the adsorption rate (deposition rate).

[0121] (h) In step D, at least one of the first and second halogen elements can be detached from the surface of the second layer in such a way that the density of the first and second halogen elements at the opening side of the recess is smaller than the density of the first and second halogen elements at the bottom side of the recess. Therefore, in step A of the next cycle, the first treatment agent, etc., can be preferentially adsorbed on the opening side of the recess to form an adsorption barrier layer, thereby improving the adsorption inhibition effect of the second treatment agent, etc., at the opening side and increasing the step coverage of the membrane.

[0122] (i) By making the third processing agent contain N and H, the first layer is nitrided and at least a portion of the first halogen element contained in the first layer is removed.

[0123] (j) By including at least one of H2 or D2 (i.e., a substance consisting solely of H or solely of D) in the fourth treatment agent, the first halogen element remaining on the surface of the second layer can be efficiently removed. Furthermore, by using a substance containing at least one of H2 or D2 with a relatively short lifetime of active species as the fourth treatment agent, the active species (e.g., The halogen is deactivated on the opening side before reaching the bottom side of the recess, thus enabling the local removal of at least one of the first halogen element and the second halogen element on the opening side of the recess.

[0124] (k) In step A, the first treatment agent or the like is adsorbed onto a first adsorption site on the surface of a first region that is part of the recess. In step B, the second treatment agent or the like is adsorbed onto a first adsorption site on the surface of a second region that is another part of the recess. By adjusting the area where the first treatment agent is adsorbed, the area where the second treatment agent is adsorbed can be controlled. This allows for adjustment of the thickness distribution of the formed film.

[0125] (l) In step D, by detaching at least a portion of the first halogen element and the second halogen element from the surface of the second layer, a first adsorption site capable of adsorbing the first treatment agent, etc., can be formed or increased on the surface within the recess. Thus, adsorption sites (first adsorption sites) for the first treatment agent supplied in step A of the next cycle can be formed in the desired area, thereby facilitating easy control of the film thickness distribution. Specifically, for example, the step coverage of the film can be improved.

[0126] (m) In step D, by adjusting at least one of the magnitude of the RF power, the processing pressure, or the supply time of the fourth processing agent as processing conditions when supplying the fourth processing agent, the density distribution of the first and second halogen elements within the recess can be adjusted. In this way, by adjusting the removal range of the first halogen element within the recess, the adsorption distribution of the first processing agent in step A of the next cycle can be controlled. As a result, the film thickness distribution within the recess can be adjusted, and in particular, the step coverage can be improved.

[0127] (n) In step C, by supplying the third processing agent to the wafer 200 in a plasma-excited state, the desorption of the first halogen element contained in the first layer can be promoted. As a result, the adsorption of the first processing agent supplied in step A of the next cycle can be further promoted, and the adsorption suppression effect of the second processing agent, etc., can be improved.

[0128] (o) Steps C and D are performed separately, with step D performed after step C. This allows step C to be performed with the entire surface within the recess of the first layer being capped by atoms of at least one of the first and second halogen elements (hereinafter also referred to as halogen capping), thus enabling uniform modification of the surface within the recess. In contrast, if step C is performed with the halogen capping on the opening side of the recess partially removed by step D, the nitriding caused by the reaction between NH3 (as a third treatment agent) and Cl (as a halogen atom) at the opening side of the recess is suppressed, and the amount (density) of nitriding may sometimes deviate within the recess.

[0129] (4) Variations (i) The processing order in this method can be changed as shown in the following variations. These variations can be combined arbitrarily. Unless otherwise specified, the processing steps and processing conditions in each step of each variation can be the same as the processing steps and processing conditions in each step of the above processing order.

[0130] (Variation Example 1) Step D may also begin after a specified time elapsed from the start of step C, and may include execution periods that overlap with the execution period of step C (see [link to step D]). Figure 7 ).

[0131] The same effect as described above can be achieved in this variation. In this variation, the time required for each cycle can be further shortened, increasing productivity. However, in this variation, in step C, nitriding is sometimes insufficient due to the reaction between NH3, which is the third processing agent, and Cl, which is the atom of the first halogen element. Therefore, from the viewpoint of uniformity of nitriding amount (density) within the recess, the above-described method is sometimes more preferable.

[0132] Alternatively, step B may begin after a predetermined time has elapsed since the start of step A, and may include execution periods that overlap with the execution period of step A (see [link to step A]). Figure 7 ).

[0133] The same effect as described above can be achieved in this variation. In this variation, the time required for each cycle can be further reduced, increasing productivity.

[0134] (Variation Example 2) The processing pressure in step D can also be greater than that in step C.

[0135] The same effect as described above can be achieved in this modified example. In this modified example, by further shortening the mean free path of the active species contained in the plasma-excited fourth treatment agent, it is possible to locally remove at least one of the first halogen element and the second halogen element remaining on the opening side of the recess.

[0136] (Variation Example 3) Alternatively, the magnitude of the RF power in step D can be smaller than the magnitude of the RF power in step C.

[0137] The same effect as described above can be achieved in this modified example. In this modified example, by further reducing the excitation power, shortening the lifetime of the active species contained in the fourth treatment agent, and / or reducing the concentration of the active species, it is possible to locally remove at least one of the first halogen element and the second halogen element remaining on the opening side of the recess.

[0138] (ii) The configuration of the processing apparatus in this embodiment can be modified as shown in the following variations. Unless otherwise specified, the configuration in each variation is the same as that in the embodiment described above. Figure 1 Elements that are substantially the same as those described in the figures are labeled with the same reference numerals and their descriptions are omitted.

[0139] (Variation Example 4) like Figure 8 As shown, the processing chamber may also include a buffer chamber, with the second nozzle configured to supply gas into the processing chamber via the buffer chamber, and the first nozzle configured to supply substance (gas) into the processing chamber without passing through the buffer chamber. Furthermore, a plasma excitation unit, comprising a first and second electrode and an electrode protection tube, may be provided inside the buffer chamber to excite the gas supplied to the buffer chamber via plasma.

[0140] Specifically, such as Figure 8 As shown, in the buffer chamber, two rod-shaped first electrodes and one rod-shaped second electrode, both made of conductors, are arranged along the loading direction (arrangement direction) of the wafer 200 from the lower to the upper part of the reaction tube 203. The first and second electrodes are arranged parallel to the second nozzle. The first and second electrodes are protected by electrode protection tubes. The two first electrodes located at both ends of the first and second electrodes are connected to a high-frequency power supply via a matching device, and the second electrode is grounded by connecting to a ground wire as a reference potential. The grounded second electrode is arranged in a manner that it is sandwiched between two adjacent first electrodes connected to the high-frequency power supply, thereby generating plasma by pairing one first electrode with the second electrode and the other first electrode with the second electrode.

[0141] The same effect as described above can be achieved in this variation.

[0142] <Other aspects of the invention> The present invention has been specifically described above. However, the present invention is not limited to the above-described manner, and various modifications can be made without departing from its spirit.

[0143] For example, as the first processing agent, a substance that does not contain the specified element but contains the second halogen element, i.e., a gas containing a halogen-containing substance, can be used. Examples of halogen-containing substances include F2, Cl2, Br2, I2, nitrogen fluoride (NF3), chlorine fluoride (ClF3), hydrogen fluoride (HF) gas, hydrogen chloride (HCl) gas, hydrogen bromide (HBr) gas, and hydrogen iodide (HI). The same effect as described above can be obtained in this method.

[0144] For example, as the first treatment agent, a substance containing Si and an amino group, i.e., a gas containing an aminosilane, can also be used. An amino group refers to a monovalent functional group from which hydrogen (H) has been removed from ammonia, primary amines, or secondary amines, and can be represented as -NH2, -NHR, or -NR2. It should be noted that R represents an alkyl group, and the two Rs in -NR2 can be the same or different. Examples of aminosilanes that can be used include tetra(dimethylamino)silane (Si[N(CH3)2]4), tris(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2), and (diisopropylamino)silane (SiH3[N(C3H7)2]). One or more of these can be used as the first treatment agent. The same effect as described above can be obtained in this method.

[0145] For example, the specified elements contained in the first and second treatment agents can be metallic elements such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W), and germanium (Ge). For example, when using the first and second treatment agents containing these metallic elements as specified elements and the third treatment agent as a nitriding agent, metallic nitride films such as titanium nitride (TiN film), zirconium nitride (ZrN film), hafnium nitride (HfN film), tantalum nitride (TaN film), niobium nitride (NbN film), aluminum nitride (AlN film), molybdenum nitride (MoN film), tungsten nitride (WN film), and germanium nitride (GeN film) can be formed. Furthermore, when using a substance containing N and C as the third treatment agent, metallic carbonitride films containing these metallic elements can be formed. The same effects as described above can be obtained in this method.

[0146] For example, oxygen (O2), ozone (O3), O2+H2, water vapor (H2O), hydrogen peroxide (H2O2), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), carbon dioxide (CO2), and other oxygen-containing substances can be used as the third processing agent, and an O-containing film, such as a silicon oxide film (SiO film), can be formed on the surface of the wafer 200 through the above processing sequence. It should be noted that in this specification, the description of "O2+H2" as two substances together refers to a mixture of H2 and O2. When supplying a mixed substance, the two substances can be mixed in a supply tube (pre-mixed) and then supplied to the processing chamber 201, or the two substances can be supplied to the processing chamber 201 separately from different supply tubes and mixed in the processing chamber 201 (post-mixed). One or more of these can be used as the third processing agent. At least some of the effects of the above methods can be obtained in this method.

[0147] For example, as a third treatment agent, substances consisting solely of nitrogen, such as N2, or mixtures such as N2 + H2, can be used. However, active species generated by plasma excitation of N2 (e.g.) The lifetime of these species is shorter than that of active species generated by plasma excitation of H2 (e.g., Therefore, considering the lifespan of the material and the need to locally remove the first halogen element from the opening side of the recess when using H2 as the fourth treatment agent, it is preferable not to use N2 as the third treatment agent. At least some of the effects of the methods described above can also be obtained in this approach.

[0148] For example, the step of supplying the aforementioned O-containing substance to the wafer 200 can be performed between step C and step D, whereby the nitriding agent is supplied to the wafer 200 as a third processing agent, thereby forming an O-containing film, such as a silicon oxynitride (SiON) film, on the surface of the wafer 200. At least some of the effects of the above-described method can also be obtained in this approach.

[0149] In step C, the wafer 200 can be supplied without plasma excitation of the third processing agent (i.e., in a non-plasma atmosphere). In this method, the processing temperature is preferably set to 600–750°C. Furthermore, in this method, a hydrogen nitride-based substance is preferably used as the third processing agent. At least some of the effects of the methods described above can also be obtained in this method.

[0150] For example, rare gases such as N2, Ar, He, Ne, and Xe can be used as the fourth treatment agent. At least some of the effects of the methods described above can also be obtained in this approach. It should be noted that the N2 gas generated through plasma excitation... Lifespan is shorter than Therefore, when using N2 as the fourth processing agent, the first halogen element on the opening side of the recess can be further locally removed in step D.

[0151] Alternatively, for example, inductively coupled plasma (ICP) can be used as a plasma generation method in addition to CCP. In this case, the same effect as the methods described above can be obtained.

[0152] The processes used for each treatment are preferably prepared separately according to the processing content, and recorded and stored in the storage device 121c via electrical communication lines and external storage device 123. Furthermore, when each processing begins, the CPU 121a preferably selects an appropriate process from the multiple processes recorded and stored in the storage device 121c according to the processing content. This allows for the reproducible formation of membranes of various types, compositions, qualities, and thicknesses using a single processing device. Additionally, it reduces the operator's workload, enabling rapid initiation of each processing step while minimizing operational errors.

[0153] The aforementioned process is not limited to the case of new manufacturing; for example, it can also be prepared by modifying an existing process already installed in the processing device. In the case of process modification, the modified process can also be installed in the processing device via an electrical communication line and a recording medium containing the process. Alternatively, the existing process already installed in the processing device can be directly modified by operating the input / output device 122 of the existing processing device.

[0154] In the various methods and modifications described above, examples of forming films using a batch processing apparatus that processes multiple substrates at a time have been explained. The present invention is not limited to the various methods and modifications described above; for example, it can also be suitably applied to the case of forming films using a monolithic processing apparatus that processes one or more substrates at a time. Furthermore, in the various methods and modifications described above, examples of forming films using a processing apparatus with a hot-wall type processing furnace have been explained. The present invention is not limited to the various methods and modifications described above; it can also be suitably applied to the case of forming films using a processing apparatus with a cold-wall type processing furnace.

[0155] When using these processing devices, each processing step and processing condition can be performed in the same manner and in the same conditions as those described in the various methods and variations, and the same effect as described in the various methods and variations can be obtained.

[0156] The various methods and variations described above can be used in appropriate combinations. The processing steps and conditions in this case can be set to be the same as those in the various methods and variations described above.

Claims

1. A substrate processing method, wherein, A film containing specified elements is formed within the recess by repeating the following process a specified number of times: (a) A process of supplying a first treatment agent to a substrate having a recess, thereby forming an adsorption barrier layer on the surface within the recess that prevents the adsorption of a second treatment agent. (b) After starting (a), a process of forming a first layer containing the specified element and the first halogen element on the surface of the recess by supplying the second processing agent containing the specified element and the first halogen element to the substrate; (c) A process of modifying the first layer into a second layer by supplying the substrate with a third processing agent that reacts with the first layer; and (d) A process of detaching at least a portion of the first halogen element from the surface of the second layer by supplying the substrate with a plasma-excited fourth treatment agent.

2. The substrate processing method as described in claim 1, wherein, The cycle is repeated at least twice.

3. The substrate processing method as described in claim 1 or 2, wherein, The first treatment agent contains a second halogen element. In (a), the adsorption barrier layer, which is atomically capped by the second halogen element, is formed on the surface within the recess.

4. The substrate processing method as described in claim 1 or 2, wherein, The first treatment agent comprises the specified element and the second halogen element. In (a), the adsorption barrier layer is formed on the surface within the recess, the adsorption barrier layer comprising the specified element and being capped by the atoms of the second halogen element in a state of atomic bonding with the specified element.

5. The substrate processing method as described in claim 4, wherein, The ratio of the number of atoms of the second halogen element in the adsorption barrier layer to the number of atoms of the specified element is greater than the ratio of the number of atoms of the first halogen element in the first layer to the number of atoms of the specified element.

6. The substrate processing method as described in claim 4 or 5, wherein, The first treatment agent comprises a compound having a molecular structure in which atoms of the second halogen element are bonded to all the bonding bonds of the atoms of the specified element.

7. The substrate processing method according to any one of claims 1 to 6, wherein, The second treatment agent comprises a compound having a molecular structure in which atoms containing the specified elements are bonded to each other.

8. The substrate processing method according to any one of claims 1 to 7, wherein, In (d), the first halogen element is detached from the surface of the second layer in such a way that the density of the first halogen element at the opening side of the recess is less than the density of the first halogen element at the bottom side of the recess.

9. The substrate processing method according to any one of claims 1 to 8, wherein, The third treatment agent contains nitrogen and hydrogen.

10. The substrate processing method according to any one of claims 1 to 9, wherein, The fourth treatment agent comprises at least one of H2 or D2.

11. The substrate processing method according to any one of claims 1 to 10, wherein, In (a), at least one of the structures of the first treatment agent and its molecules is adsorbed onto a first adsorption site present on the surface of a first region that is part of the recess. In (b), at least one of the partial structures of the second treatment agent and its molecules is adsorbed onto the first adsorption site on the surface of the second region, which is another part of the recess.

12. The substrate processing method according to any one of claims 1 to 11, wherein, In (d), by detaching at least a portion of the first halogen element from the surface of the second layer, a first adsorption site is formed on the surface within the recess, capable of adsorbing at least any one of the partial structures of the first treatment agent or its molecules.

13. The substrate processing method according to any one of claims 1 to 12, wherein, In (d), the density distribution of the first halogen element in the recess is adjusted by adjusting at least one of the magnitude of the high-frequency power applied for plasma excitation of the fourth processing agent, the pressure of the space for the substrate to be processed, or the supply time of the fourth processing agent.

14. The substrate processing method according to any one of claims 1 to 13, wherein, In (c), the third processing agent is supplied to the substrate in a plasma-excited state.

15. The substrate processing method as described in claim 14, wherein, The lifetime of the active species contained in the plasma-excited fourth treatment agent is shorter than that of the active species contained in the plasma-excited third treatment agent.

16. The substrate processing method according to any one of claims 1 to 15, wherein, (c) and (d) are executed at different times, and (d) is executed after (c).

17. The substrate processing method according to any one of claims 1 to 15, wherein, (d) begins after a specified time elapsed from (c) and includes an execution period that repeats the execution period of (c).

18. A method for manufacturing semiconductor devices, wherein, A film containing specified elements is formed within the recess by repeating the following process a specified number of times: (a) A process of supplying a first treatment agent to a substrate having a recess, thereby forming an adsorption barrier layer on the surface within the recess that prevents the adsorption of a second treatment agent. (b) After starting (a), a process of forming a first layer containing the specified element and the first halogen element on the surface of the recess by supplying the second processing agent containing the specified element and the first halogen element to the substrate; (c) A process of modifying the first layer into a second layer by supplying the substrate with a third processing agent that reacts with the first layer; and (d) A process of detaching at least a portion of the first halogen element from the surface of the second layer by supplying the substrate with a plasma-excited fourth treatment agent.

19. A program product which uses a computer to cause a substrate processing apparatus to perform the following steps: (a) The step of supplying a first treatment agent to a substrate having a recess, thereby forming an adsorption barrier layer on the surface within the recess that prevents the adsorption of a second treatment agent; (b) After starting (a), the step of forming a first layer containing the specified element and the first halogen element on the surface of the recess by supplying the second processing agent containing the specified element and the first halogen element to the substrate; (c) The step of modifying the first layer into a second layer by supplying the substrate with a third processing agent that reacts with the first layer; and (d) The step of supplying the substrate with a plasma-excited fourth treatment agent, thereby causing at least a portion of the first halogen element to detach from the surface of the second layer. The step of forming a film containing the specified element within the recess by repeating the above steps a specified number of times.

20. A substrate processing apparatus, comprising: A processing agent supply system that supplies a first processing agent, a second processing agent, a third processing agent, and a fourth processing agent to a substrate having a recess, respectively; The plasma excitation unit excites the fourth treatment agent using plasma; and The control unit is configured to control the processing agent supply system and the plasma excitation unit to perform a process in which a film containing a specified element is formed in the recess by performing a predetermined number of cycles including the following process: (a) A process in which the adsorption barrier layer is formed on the surface of the recess by supplying the first treatment agent to the substrate, thereby preventing the adsorption of the second treatment agent; (b) After starting (a), a first layer containing the specified element and the first halogen element is formed on the surface of the recess by supplying the second processing agent containing the specified element and the first halogen element to the substrate; (c) A process of modifying the first layer into a second layer by supplying the substrate with the third processing agent that reacts with the first layer; and (d) A process in which at least a portion of the first halogen element is detached from the surface of the second layer by supplying the substrate with the fourth treatment agent excited by plasma.

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