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

Abstract

The present invention provides a technique for performing: (a) a step in which, on a substrate on which a first film and a second film covering the first film are formed, a portion of a portion of the first film covered by the second film is replaced with a barrier film, and the first film is divided into a first portion and a second portion by the barrier film; and (b) a step for removing the first portion from the end surface not covered by the second film to the barrier film, and remaining the second portion. According to the provided technology, when a film of a substrate is etched, a desired portion of the film can be removed with high precision.

Description

Technical Field

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

[0002] As one of the steps in the process of manufacturing a semiconductor device, a part of a film formed on a surface of a substrate may be etched (for example, see Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-160962 Summary of the invention

[0006] Problems to be solved by the invention

[0007] When etching a film on a substrate, it may be difficult to remove a desired portion of the film with high accuracy.

[0008] The present disclosure provides a technology that can remove a desired portion of a film with high precision when etching a film on a substrate.

[0009] Methods for solving problems

[0010] According to one embodiment of the present disclosure, a technology is provided to perform the following steps:

[0011] (a) on a substrate having a first film and a second film covering the first film, replacing a portion of the first film covered by the second film with a barrier film, thereby dividing the first film into a first portion and a second portion by the barrier film; and

[0012] (b) A step of removing the first portion from the end surface not covered by the second film to the barrier film, leaving the second portion.

[0013] Effects of the Invention

[0014] According to the present disclosure, when etching a film on a substrate, a desired portion of the film can be removed with high accuracy. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] [ Figure 1 ] is a schematic diagram of the structure of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present disclosure, and is a diagram showing a processing furnace 202 portion in a longitudinal cross-sectional view.

[0016] [ Figure 2 ] is a schematic diagram of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present disclosure, Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0017] [ Figure 3 ] is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitable for use in one embodiment of the present disclosure, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0018] [ Figure 4 ] is a diagram showing the processing order in one embodiment of the present disclosure.

[0019] [ Figure 5A ] is a cross-sectional view of a wafer 200 on which a first film portion 310, a second film portion 320, a third film portion 330 and a fourth film portion 340 are formed in one embodiment of the present disclosure.

[0020] [ Figure 5B ] is a stereoscopic view of a wafer 200 in one embodiment of the present disclosure.

[0021] [ Fig. 6A ] is a cross-sectional view of a wafer 200 processed in a substrate processing step in one embodiment of the present disclosure.

[0022] [ Figure 6B ] is from Fig. 6A FIG. 2 is a cross-sectional view of a state in which a hard mask 900 is provided on the second film portion 320 of the wafer 200 to form a groove portion 350 .

[0023] [ Figure 6C ] is from Figure 6B is a cross-sectional view of a state in which the hard mask 900 is removed.

[0024] [ Fig. 7A ] is a diagram illustrating a process of forming a blocking portion 314 on a first film portion 310 of a wafer 200 in one embodiment of the present disclosure; and is a cross-sectional view of a state in which a modified layer 324 is formed on a second end surface 322 of a second film portion 320.

[0025] [ Figure 7B ] is from Fig. 7A A cross-sectional view of a state in which a blocking portion 314 is formed between the first end surface 312 of the first film portion 310 .

[0026] [ Figure 7C ] is from Figure 7B FIG. 4 is a cross-sectional view of a state in which the modified layer 324 of the second end surface 322 of the second film portion 320 is removed.

[0027] [ Fig.7D ] is from Figure 7C A cross-sectional view of a state in which the groove portion 350 is restored by filling it with the second film portion 320.

[0028] [ Fig. 8A ] is a cross-sectional view of a state in which a hard mask 910 is formed on the second film portion 320 in one embodiment of the present disclosure.

[0029] [ Figure 8B ] is from Fig. 8A FIG. 4 is a cross-sectional view of a state in which the hard mask 910 is removed after the first portion 311A ​​of the first film portion 310 and the third film portion 330 are removed.

[0030] [ Figure 8C ] is from Figure 8B FIG. 4 is a cross-sectional view of a state in which a hard mask 920 is provided on the second film portion 320 and the barrier portion 314 is removed.

[0031] [ Fig.8D ] is from Figure 8C A cross-sectional view of a state in which the hard mask 920 is removed.

[0032] [ Fig. 9A ] is a cross-sectional view of a wafer 200 processed in a substrate processing step in another embodiment of the present disclosure.

[0033] [ Fig. 9B ] is from Fig. 9A FIG. 9 is a cross-sectional view of a state in which a hard mask 930 is provided on the second film portion 320 of the wafer 200 and a recessed portion 352 is formed in the second film portion 320 .

[0034] [ Fig. 9C ] is from Fig. 9B A cross-sectional view of a state in which the hard mask 920 is removed.

[0035] [ Fig.10 ] is a cross-sectional view illustrating a process of forming a blocking portion 314 on the first film portion 310 of the wafer 200 in a substrate processing process. DETAILED DESCRIPTION

[0036] <One embodiment of the present disclosure>

[0037] The following mainly refers to Figure 1 FIG. 9 illustrates an embodiment of the present disclosure. It should be noted that the drawings used in the following description are schematic, and the relationship between the dimensions of the elements shown in the drawings, the ratio of the elements, etc. may not be consistent with reality. In addition, the relationship between the dimensions of the elements, the ratio of the elements, etc. between multiple drawings may not be consistent. In addition, unless otherwise specified in the specification, each element is not limited to one, and multiple elements may exist.

[0038] (1) Configuration of substrate processing apparatus

[0039] like Figure 1 As shown, the processing furnace 202 constituting the substrate processing apparatus 10 includes a heater 207 as a temperature adjuster (heating unit). The heater 207 also functions as an activation mechanism (excitation unit) for activating (exciting) the gas by heat.

[0040] A reaction tube 203 is arranged concentrically with the heater 207 on the inner side of the heater 207. The reaction tube 203 is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. An O-ring 220a 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 part of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201.

[0041] In the processing chamber 201, nozzles 249a to 249c as first to third supply units are respectively provided so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are connected to the gas supply pipes 232a to 232c, respectively.

[0042] In the gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as switch valves are sequentially arranged from the upstream side of the gas flow. Gas supply pipes 232d and 232f are respectively connected to the downstream side of the gas supply pipe 232a than the valve 243a. Gas supply pipes 232e and 232g are respectively connected to the downstream side of the gas supply pipe 232b than the valve 243b. Gas supply pipe 232h is connected to the downstream side of the gas supply pipe 232c than the valve 243c. In the gas supply pipes 232d to 232h, MFCs 241d to 241h and valves 243d to 243h are respectively arranged from the upstream side of the gas flow.

[0043] Furthermore, the nozzle 249a is connected to a gas supply pipe 272. In the gas supply pipe 272, an MFC 271 as a flow controller (flow control unit) and a valve 273 as an on-off valve are sequentially provided from the upstream side of the gas flow. On the downstream side of the gas supply pipe 272 than the valve 273, the above-mentioned gas supply pipes 232a, 232d, and 232f are connected respectively.

[0044] like Figure 2As shown, the nozzles 249a to 249c are respectively arranged in the annular space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, and are arranged to stand upright from the lower part to the upper part of the inner wall of the reaction tube 203 toward the upper side of the arrangement direction of the wafer 200. The nozzles 249a and 249c are arranged to sandwich a straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened in a manner opposite to (opposite to) the exhaust port 231a when viewed from above, and can supply gas to the wafer 200.

[0045] from Figure 1 The gas supply pipe 232a shown in the figure supplies the modifier into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a. From the gas supply pipe 232b, the first raw material is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b. The first raw material is used as a first film-forming agent. From the gas supply pipe 232e, the second raw material is supplied into the processing chamber 201 via the MFC 241e, the valve 243e, and the nozzle 249b. The second raw material is used as a second film-forming agent. From the gas supply pipe 232c, the reactant is supplied into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c. The reactant is used as a film-forming agent. From the gas supply pipe 232d, the catalyst is supplied into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a. The catalyst is used as a film-forming agent. From the gas supply pipes 232f to 232h, inert gas is supplied into the processing chamber 201 via MFC 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, etc. In addition, from the gas supply pipe 272, a remover is supplied into the processing chamber 201 via MFC 271, valve 273, and nozzle 249a.

[0046] The modifier supply system is mainly composed of a gas supply pipe 232a, MFC241a, and valve 243a; the first raw material supply system is mainly composed of a gas supply pipe 232b, MFC241b, and valve 243b; the second raw material supply system is mainly composed of a gas supply pipe 232e, MFC241e, and valve 243e; the reactant supply system is mainly composed of a gas supply pipe 232c, MFC241c, and valve 243c; the catalyst supply system is mainly composed of a gas supply pipe 232d, MFC241d, and valve 243d; the inactive gas supply system is mainly composed of gas supply pipes 232f to 232h, MFC241f to 241h, and valves 243f to 243h. Each or all of the first raw material supply system, the second raw material supply system, the reactant supply system, and the catalyst supply system are also referred to as a film-forming agent supply system. In addition, the remover supply system is mainly composed of a gas supply pipe 272, MFC271, and valve 273.

[0047] Any one or all of the various supply systems described above may also be configured as an integrated supply system 248 formed by integrating valves 243a to 243h, 273 and MFCs 241a to 241h, 271, and the like.

[0048] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to the vacuum pump 246 via a pressure sensor 245 for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244. The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, so that the vacuum exhaust in the processing chamber 201 and the vacuum exhaust stop can be performed. Furthermore, by adjusting the valve opening based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be included in the exhaust system.

[0049] Below the manifold 209, a sealing cap 219 of a furnace cover body is provided, which can airtightly close the lower end opening of the manifold 209 by means of an O-ring 220b. Below the sealing cap 219, a rotating mechanism 267 for rotating the wafer box 217 is provided. The rotating shaft 255 of the rotating mechanism 267 is connected to the wafer box 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer box 217. The wafer box elevator 115 is configured as a transport device that transports the wafer 200 in and out of the processing chamber 201 by raising and lowering the sealing cap 219.

[0050] A baffle 219 s is provided below the manifold 209 , and when the sealing cap 219 is lowered to carry the wafer cassette 217 out of the processing chamber 201 , the lower end opening of the manifold 209 can be airtightly closed by the O-ring 220 c .

[0051] The wafer box 217 as a substrate support is configured to support multiple (e.g., 25 to 200) wafers 200 in a horizontal position and aligned with each other in a vertical direction in multiple stages, that is, arranged at intervals. At the bottom of the wafer box 217, a heat insulation plate 218 made of a heat-resistant material is supported in multiple stages.

[0052] A temperature sensor 263 is provided in the reaction tube 203. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 is adjusted to a desired temperature distribution.

[0053] like Figure 3 As shown, the controller 121 as a control unit is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, the storage device 121c, and the I / O interface 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel. In addition, an external storage device 123 may also be connected to the controller 121.

[0054] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the storage device 121c, a control program for controlling the action of the substrate processing device, a process recipe that records the steps and conditions of the substrate processing described later, etc., are recorded and stored in a readable form. The process recipe is composed in a manner that the controller 121 is used to enable the substrate processing device to execute the various steps of the substrate processing described later and to obtain a predetermined result, and functions as a program. In the following, at least any one of the process recipe, control program, etc. is also simply referred to as a program. In addition, the process recipe is also simply referred to as a recipe. RAM121b is configured as a storage area (working area) for temporarily storing programs, data, etc. read by CPU121a.

[0055] The I / O interface 121d is connected to the above-mentioned MFCs 241a to 241h, 271, valves 243a to 243h, 273, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, wafer box elevator 115, etc.

[0056] The CPU 121a is configured to read out a control program from the storage device 121c and execute it, and to read out a recipe from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241h and 271, the opening and closing operation of the valves 243a to 243h and 273, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the wafer box 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer box 217 by the wafer box elevator 115, and the like.

[0057] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into the computer. The external storage device 123 includes, for example, a disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a USB memory, a semiconductor memory such as an SSD, etc. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are also simply collectively referred to as recording media. It should be noted that providing the program to the computer can also be performed without using the external storage device 123, but using communication means such as the Internet and a dedicated line.

[0058] (2) Substrate processing steps

[0059] Next, the substrate processing step will be described.

[0060] First, the structure of the wafer 200 will be described.

[0061] It should be noted that Figure 5A In order to avoid making the figure complicated and difficult to read, the oblique lines showing the cross section of the second film portion 320 are omitted. Figure 5B In order to avoid the figure becoming complicated and difficult to read, the part of the first membrane portion 310 hidden in the second membrane portion 320 is represented by a solid line, rather than a single-point dashed line as a hidden line. In addition, in the following cross-sectional views, the oblique lines showing the cross section of the second membrane portion 320 are also omitted.

[0062] like Figure 5A and Figure 5B As shown, the wafer 200 schematically includes a rod-shaped first film portion 310 and a second film portion 320 covering the first film portion 310 on a base material 300. It should be noted that the "first film portion" and the "second film portion" are sometimes simply referred to as "first film" and "second film".

[0063] It should be noted that, for convenience, the vertical direction of the wafer 200 is filled in the processing furnace 202 (refer to Figure 1 ) is used to illustrate the state. In addition, for convenience, Figure 5A The left and right directions are set as the length direction of the first film portion 310, and the left and right directions are set as the length direction of the first film portion 310. Figure 5A The direction perpendicular to the paper surface is set as the front-back direction. The situation of viewing from the direction perpendicular to the upper surface of the base material 300 is set as a top view.

[0064] In the present embodiment, the first membrane portion 310 is formed by arranging a plurality of intervals in the front-to-back direction in a top view. In addition, in the present embodiment, the first membrane portion 310 is composed of a plurality of block-shaped (more specifically, rod-shaped) membranes arranged at intervals in a direction orthogonal to the longitudinal direction, that is, in the up-down direction orthogonal to the upper surface of the base material 300. If explained from another point of view, the first membrane portion 310 is formed to be at least partially buried in the second membrane portion 320, and is composed of block-shaped membranes arranged at intervals in the up-down direction and the front-to-back direction.

[0065] It should be noted that, for convenience, the portion formed by the first membrane portion 310 and the second membrane portion 320 is referred to as the main portion 302. The side surface of the main portion 302 in the left-right direction is the surface that exposes the side surfaces of the first membrane portion 310 and the second membrane portion 320. In detail, the side surface of the main portion 302 on the right side of the figure is the surface that exposes the first portion 311A ​​(see Fig.7D ) and the side surface of the end surface of the second film portion 320. The side surface on the left side of the main portion 302 in the figure is a second portion 311B (see Fig.7D ) and the side surface of the end surface of the second membrane portion 320.

[0066] In the present embodiment, the third film portion 330 is formed on the base material 300 of the wafer 200 in a manner adjacent to and covering one side in the length direction of the first film portion 310 of the main portion 302, in other words, the right side surface in the left-right direction. In addition, the fourth film portion 340 is formed on the base material 300 of the wafer 200 in a manner adjacent to and covering the other side in the length direction of the first film portion 310 of the main portion 302, in other words, the left side surface in the left-right direction. It should be noted that the "third film portion" and the "fourth film portion" are sometimes referred to as the "third film" and the "fourth film".

[0067] In addition, in the present embodiment, a surface film (not shown) is formed on the surface of the first film portion 310 that contacts the second film portion 320 .

[0068] It should be noted that, for convenience, the first film portion 310 is described as a silicon film (Si film) of a non-oxide film (non-oxygen-containing film), the surface film of the first film portion 310 is described as a SiO film of a gate insulating film, and the second film portion 320 is described as a silicon oxygen carbon film (SiOC film) of an oxide film (oxygen-containing film) and a carbonized film (carbon-containing film). In addition, the third film portion 330 and the fourth film portion 340 are both described as silicon oxide films (SiO films). The base material 300 is preferably not etched in the pre-process and post-process described later, or is formed of a material with a low etching rate relative to the etching object film. However, these are only representative examples and are not limited to these.

[0069] In an example of a substrate processing process according to an embodiment of the present disclosure, the following process is performed as one process of a semiconductor device manufacturing process:

[0070] (a) In the wafer 200 having the above structure, in which the first film portion 310 and the second film portion 320 covering the first film portion 310 are formed, a portion of the first film portion 310 covered by the second film portion 320 is replaced with the barrier portion 314 (see Fig.7D ), the first film portion 310 is divided into a first portion 311A ​​and a second portion 311B by the blocking portion 314 (refer to Fig.7D ) process; and

[0071] (b) a step of removing the first portion 311A ​​from the end surface not covered by the second film portion 320 to the stopper portion 314, leaving the second portion 311B;

[0072] Thus, the step of removing the first portion 311A ​​is performed while the second portion 311B, which is a part of the first film portion 310, remains.

[0073] Next, using the substrate processing apparatus 10, Figure 5B The following describes an example of a substrate processing step in which a first film portion 310 is formed on a base material 300 of a wafer 200 of the substrate shown in the figure, a barrier portion 314 is formed, and the first film portion 310 is divided into a first portion 311A ​​and a second portion 311B. In addition, a "barrier portion" is sometimes referred to as a "barrier film".

[0074] In addition, in the example of the substrate processing process of one embodiment of the present disclosure, a process is further included without using the substrate processing apparatus 10. Specifically, it includes forming a blocking portion 314 (see Fig.7D) before the substrate is formed, and the substrate processing apparatus 10 is not used in these "pre-processes" and "post-processes".

[0075] It should be noted that the substrate processing step example is also an example of a substrate processing method and a method for manufacturing a semiconductor device. In the following description, the operation of each unit constituting the substrate processing apparatus 10 is controlled by the controller 121 .

[0076] First, the pre-process in the substrate processing process example will be described in detail.

[0077] (Pre-process)

[0078] As a pre-process, relative to Fig. 6A The wafer 200 shown in FIG. Figure 6B As shown, a groove 350 is formed in the main portion 302 of the wafer 200 along the front-rear direction in a plan view.

[0079] Specifically, if Figure 6B As shown, a hard mask 900 is formed on the upper surface of the wafer 200 on the opposite side of the substrate 300, and a groove 350 penetrating the first film portion 310 and the second film portion 320 is formed by etching. More specifically, the groove 350 is formed to penetrate the second film portion 320 and a portion of the first film portion 310 covered by the second film portion 320. In addition, for convenience, the end face of the first film portion 310 exposed in the groove 350 is set as the first end face 312. Also for convenience, the end face of the second film portion 320 exposed in the groove 350 is set as the second end face 322.

[0080] Etching can use anisotropic etching performed by, for example, carbon fluoride (CF) plasma gas. In addition, in the case of anisotropic etching, it is desirable to use a plasma excited gas. As a CF gas, one or more of CF4, C4F6, C4F8, CH2F2 and CHF3 can be used. The etching treatment in this process can be performed using a known etching device that can perform an etching treatment on the wafer 200. The same is true for other etching treatments in subsequent processes. It should be noted that in the etching treatment in this process, it is preferred to use a plasma etching device that can perform anisotropic etching in the upper and lower directions such as penetrating the first film portion 310 and the second film portion 320.

[0081] Then, if Figure 6C As shown, after forming the groove 350, the hard mask 900 is removed. The hard mask removal process in this step can be performed using, for example, a known polishing device that can polish the hard mask on the wafer 200. The same applies to the removal process of other hard masks in subsequent steps.

[0082] Next, the process of forming the barrier portion 314 is specifically described. It should be noted that in the following description, as part of the barrier portion forming process, an example of further performing a removal step of removing the modified layer 324 described later and a second film forming step of filling the recovery groove portion 350 with the second film portion 320 is described, but the barrier portion forming process may be regarded as not including these steps.

[0083] (Block Forming Step)

[0084] Here, in the following examples, the case where the film-forming agent includes a raw material, a reactant and a catalyst is described. The molecular structures of the raw materials, reactants and catalysts are different. In addition, in the following examples, the case where the above-mentioned specific substance contained in the film-forming agent is a raw material is described. That is, the case where molecule X is a raw material molecule is described. It should be noted that the above-mentioned specific substance contained in the film-forming agent may also be a reactant. That is, molecule X may also be a reactant molecule. In addition, the above-mentioned specific substance contained in the film-forming agent may also be a catalyst. That is, molecule X may also be a catalyst molecule. That is, the above-mentioned specific substance contained in the film-forming agent may also contain at least any one of the raw materials, reactants and catalysts.

[0085] In addition, in the following example, Figure 4 As shown, in the first film forming step, a cycle including the step of supplying the first raw material to the wafer 200 and the step of supplying the reactant to the wafer 200 is performed a predetermined number of times, and a case where a catalyst is supplied to the wafer 200 in at least one of the step of supplying the first raw material and the step of supplying the reactant is described. It should be noted that Figure 4 In the embodiment, as a representative example, an example in which the catalyst is supplied in two steps, the step of supplying the first raw material and the step of supplying the reactant, is shown.

[0086] Right now, Figure 4 The processing sequence shown shows an example of performing the following steps in a non-plasma atmosphere:

[0087] A modifying step of supplying a modifying agent to the wafer 200 so that at least a part of the molecular structure of molecules constituting the modifying agent is deposited on a second end surface 322 of a second film portion 320 described later to form a modified layer 324;

[0088] By cycling a process including supplying a first raw material and a catalyst to the wafer 200 and a step including supplying a reactant and a catalyst to the wafer 200 a predetermined number of times (n times, where n is an integer greater than 1, and the same applies hereinafter), a first film forming step of forming a barrier portion 314 on the first end surface 312 of the first film portion 310 is performed.

[0089] If described from another point of view, the first film forming step is a step of replacing a part of the first film portion 310 with the barrier portion 314 , and dividing the first film portion 310 into the first portion 311A ​​and the second portion 311B by the barrier portion 314 .

[0090] In this specification, for convenience, the above-mentioned processing order may be shown as follows. The same reference numerals may also be used in the description of other embodiments and the like described later.

[0091] Modifier → (first raw material + catalyst → reactant + catalyst) × n

[0092] Note that, as in the following processing sequence, a catalyst may be supplied to the wafer 200 in at least one of the step of supplying the first raw material and the step of supplying the reactant.

[0093] Modifier → (first raw material + catalyst → reactant) × n

[0094] Modifier → (first raw material → reactant + catalyst) × n

[0095] Modifier → (first raw material + catalyst → reactant + catalyst) × n

[0096] It should be noted that the term "wafer" used in this specification may mean the wafer itself or a stack of a wafer and a predetermined layer or film formed on its surface. The term "wafer surface" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer, etc. formed on the wafer. In this specification, when it is stated as "forming a predetermined layer on the wafer", it may mean 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" has the same meaning as the term "wafer".

[0097] In addition, 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.

[0098] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, the inhibition layer may include a continuous layer, a discontinuous layer, or both as long as it can produce a film formation inhibitory effect.

[0099] (Wafer loading and wafer box loading)

[0100] First, Figure 6C The plurality of wafers 200 formed by the groove 350 shown are loaded in Figure 1After the wafer box 217 of the substrate processing apparatus 10 is removed, the lower end opening of the manifold 209 is opened by the shutter opening mechanism 115s. Figure 1 As shown, the wafer cassette 217 supporting the plurality of wafers 200 is lifted by the wafer cassette elevator 115 and carried into the processing chamber 201 (wafer cassette loading). In this state, the sealing cap 219 is in a state of closing the lower end of the manifold 209 .

[0101] (Pressure adjustment and temperature adjustment)

[0102] After the wafer box is loaded, the vacuum pump 246 performs vacuum exhaust (decompression exhaust) so that the space in the processing chamber 201 where the wafer 200 exists reaches the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on the measured pressure information. In addition, the heater 207 heats the wafer 200 in the processing chamber 201 so that it reaches the desired processing temperature. At this time, the power supply to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 so that the desired temperature distribution is achieved in the processing chamber 201. In addition, the rotation of the wafer 200 is started by the rotation mechanism 267. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0103] (Modification step)

[0104] Then, if Fig. 7A As shown, a modifying agent is supplied to the wafer 200 to form a modified layer 324 on the second end surface 322 of the second film portion 320 as the SiOC film exposed in the groove portion 350. That is, a modifying agent that reacts with the second end surface 322 of the groove portion 350 exposed in the wafer 200 is supplied to selectively form the modified layer 324 on the second end surface 322.

[0105] Specifically, open Figure 1 The valve 243a of the substrate processing device 10 shown in the figure allows the modifier to flow into the gas supply pipe 232a. The modifier is adjusted in flow rate by the MFC 241a, supplied to the processing chamber 201 through the nozzle 249a, and exhausted by the exhaust port 231a. At this time, the modifier is supplied to the wafer 200 from the side of the wafer 200 (modifier supply). At this time, the valves 243f to 243h can also be opened to supply inactive gas to the processing chamber 201 through the nozzles 249a to 249c respectively.

[0106] In this embodiment, Fig. 7AThe modified layer 324 shown is an inhibitory layer. Specifically, by supplying a modifier to the wafer 200 under the processing conditions described later, inhibitor molecules that are at least a part of the molecular structure of the molecules constituting the modifier are chemically adsorbed on the second end face 322 of the groove portion 350 where the wafer 200 is exposed, and the modified layer 324 as an inhibitory layer is formed on the second end face 322, so that the modified layer 324 is modified. That is, in this step, by supplying a modifier that reacts with the second end face 322 to the wafer 200, the inhibitor molecules contained in the modifier are adsorbed on the second end face 322 to form the modified layer 324, and the second end face 322 can be modified. It should be noted that inhibitor molecules are also called film-forming inhibitory molecules (adsorption inhibitory molecules, reaction inhibitory molecules). In addition, the modified layer 324 is also called a film-forming inhibitory layer (adsorption inhibitory layer, reaction inhibitory layer).

[0107] The modified layer 324 formed in this step contains at least a part of the molecular structure of the molecules constituting the modifier as a residue from the modifier. In the first film-forming step described later, the modified layer 324 prevents at least a part of the molecular structure of the molecules constituting the first raw material (film-forming agent) from being adsorbed to the first end face 312, thereby hindering (inhibiting) the film-forming reaction at the first end face 312.

[0108] As at least a part of the molecular structure of the molecule constituting the modifier, i.e., the inhibitor molecule, for example, trialkylsilyl such as trimethylsilyl (-SiMe3) and triethylsilyl (-SiEt3) can be exemplified. The trialkylsilyl group contains an alkyl group, i.e., a hydrocarbon group. In these cases, the Si of the trimethylsilyl group and the triethylsilyl group is adsorbed on the adsorption point of the second end face 322 of the wafer 200. When the second end face 322 is the surface of the SiOC film, the second end face 322 contains an OH terminal (OH group) as an adsorption point, and the Si of the trimethylsilyl group and the triethylsilyl group is bonded to the O of the OH terminal (OH group) of the second end face 322, and the second end face 322 is terminated by an alkyl group, i.e., a hydrocarbon group, such as a methyl group or an ethyl group. The second end face 322 is terminated with an alkyl group (alkylsilyl group), i.e., a hydrocarbon group, such as a methyl group (trimethylsilyl group) or an ethyl group (triethylsilyl group) to form an inhibition layer, which prevents at least a part of the molecular structure of the molecules constituting the first raw material (film-forming agent) from being adsorbed to the second end face 322 in the second film-forming step described later, thereby hindering (inhibiting) the film-forming reaction at the second end face 322.

[0109] It should be noted that in this step, at least a part of the molecular structure of the molecules constituting the modifier is adsorbed on a part of the first end face 312 of the first film portion 310 of the wafer 200 which is a Si film, but the adsorption amount is only a trace amount, and the adsorption amount on the second end face 322 of the wafer 200 is overwhelmingly large. This is because such selective (preferential) adsorption can be performed because the processing conditions in this step are set to the conditions where the modifier does not undergo gas phase decomposition in the processing chamber 201. In addition, this is because the entire area of ​​the second end face 322 is OH-terminated, while most of the first end face 312 is not OH-terminated. In this step, since the inside of the processing chamber 201 (refer to Figure 1 ) The modifier does not undergo gas phase decomposition, and therefore at least a portion of the molecular structure of the molecules constituting the modifier is not multi-stacked at the first end face 312 and the second end face 322, and at least a portion of the molecular structure of the molecules constituting the modifier is selectively adsorbed on the second end face 322 in the first end face 312 and the second end face 322, thereby the second end face 322 is selectively terminated by at least a portion of the molecular structure of the molecules constituting the modifier.

[0110] As treatment conditions when supplying the modifying agent in the modifying step, the following can be exemplified:

[0111] Treatment temperature: room temperature (25°C) to 500°C, preferably room temperature to 250°C

[0112] Processing pressure: 5-2000Pa, preferably 10-1000Pa

[0113] Treatment time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes

[0114] Modifier supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm

[0115] Inert gas supply flow rate (each gas supply pipe): 0~20slm

[0116] It should be noted that in this specification, a numerical range such as "5 to 2000 Pa" means that the range includes a lower limit and an upper limit. Therefore, for example, "5 to 2000 Pa" means "5 Pa or more and 2000 Pa or less". The same applies to other numerical ranges.

[0117] In addition, when the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied. This also applies to the following description.

[0118] In addition, the processing temperature in this specification means the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure means the pressure in the processing chamber 201. In addition, the processing time means the time during which the processing is continued. This also applies to the following description.

[0119] After selectively forming the modified layer 324 on the second end surface 322 of the second film portion 320 of the wafer 200, the Figure 1 The valve 243a shown stops the supply of the modifier into the processing chamber 201. The gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. In addition, the processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the modifier.

[0120] As the modifying agent, for example, a compound having a structure in which an amino group is directly bonded to silicon (Si) or a compound having a structure in which an amino group and an alkyl group are directly bonded to silicon (Si) can be used.

[0121] As the modifier, for example, (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3), (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dipropylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethyl ...butylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dipropylamino)trimethylsilane ((C3H7)2NSi(CH3)3 As the modifier, one or more of these can be used.

[0122] In addition, as a modifier, for example, bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2), bis(diethylamino)diethylsilane ([(C2H5)2N]2Si(C2H5)2), bis(dimethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2), bis(diethylamino)dimethylsilane ([(C2H5)2N]2Si(CH3)2), bis(dimethylamino)silane ([(CH3)2N]2SiH2), bis(diethylamino)silane ([(C2H5)2N]2SiH2), bis(dimethylaminodimethylsilyl)ethane ([(CH3)2N(CH3)2Si]2C2H6), bis(dipropylamino)silane ([(C3H7 )2N]2SiH2), bis(dibutylamino)silane ([(C4H9)2N]2SiH2), bis(dipropylamino)dimethylsilane ([(C3H7)2N]2Si(CH3)2), bis(dipropylamino)diethylsilane ([(C3H7)2N]2Si(C2H5)2), (dimethylsilyl)diamine ((CH3)2Si(NH2)2), (diethylsilyl)diamine ((C2H5)2Si(NH2)2), (dipropylsilyl)diamine ((C3H7)2Si(NH2)2), bis(dimethylaminodimethylsilyl)methane ([(CH3)2N(CH3)2Si]2CH2), and bis(dimethylamino)tetramethyldisilane ([(CH3)2N]2(CH3)4Si2). As the modifier, one or more of these can be used.

[0123] (First film forming step)

[0124] After the modification step, Figure 7B As shown, by supplying the first film-forming agent to the groove portion 350 of the wafer 200, the barrier portion 314 is formed on the first end surface 312 of the first film portion 310 as the Si film exposed in the groove portion 350 of the wafer 200. Specifically, by supplying the first raw material that reacts with the first end surface 312 to the groove portion 350 of the wafer 200, at least a part of the molecular structure of the molecules constituting the first raw material is selectively adsorbed on the first end surface 312. Thereafter, by reacting the adsorption layer formed by the adsorption with the reactant, at least a part of the barrier portion 314 is formed (i.e., deposited). More specifically, the barrier portion 314 is deposited from the first end surfaces 312 exposed on both sides of the groove portion 350, in other words, it is grown to fill the space between the first end surfaces 312.

[0125] One side of the stopper 314 of the first film portion 310 is set as the first portion 311A, and the other side is set as the second portion 311B. If described from another point of view, the stopper 314 is formed to fill between the first end faces 312 of the first film portion 310, thereby forming a structure in which a part of the first film portion 310 is replaced by the stopper 314. Therefore, the stopper 314 is a structure that divides the first film portion 310 into the first portion 311A ​​and the second portion 311B.

[0126] The barrier portion 314 and the second film portion 320 have different compositions. Specifically, in this embodiment, the barrier portion 314 is a silicon oxide film (SiO film). That is, as an example, the first film forming step selectively forms a SiO film using a halogen-containing Si raw material.

[0127] Specifically, the following raw material supply step and reactant supply step are performed in sequence. It should be noted that, in the following example, as described above, the first film-forming agent includes a first raw material, a reactant and a catalyst. In the raw material supply step and the reactant supply step, the output of the heater 207 is adjusted to maintain the temperature of the wafer 200 at a temperature lower than the temperature of the wafer 200 in the modification step. In particular, by maintaining a temperature substantially the same as the temperature of the wafer 200 in the modification step, the time required to change the temperature of the wafer 200 can be omitted, thereby shortening the processing time. In addition, by maintaining a lower temperature than the temperature of the wafer 200 in the modification step, it is possible to more effectively suppress the detachment of at least a portion of the modified layer 324.

[0128] [Raw material supply step]

[0129] In this process, for the wafer 200 after the modification step, that is, the wafer 200 after the modified layer 324 is selectively formed on the second end face 322 of the second film portion 320, a first raw material (first raw material gas) and a catalyst (catalyst gas) as a first film-forming agent are supplied to the groove portion 350 to form a first layer on the first end face 312 exposed in the groove portion 350.

[0130] It should be noted that the first layer formed in this step is a state before being oxidized in the reactant supply step described later.

[0131] In this step, open Figure 1The valves 243b and 243d of the substrate processing apparatus 10 shown in the figure allow the first raw material and the catalyst as the first film-forming agent to flow into the gas supply pipes 232b and 232d, respectively. The first raw material and the catalyst are respectively adjusted in flow rate by the MFCs 241b and 241d, supplied to the processing chamber 201 through the nozzles 249b and 249a, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the first raw material and the catalyst are supplied to the wafer 200 from the side of the wafer 200 (first raw material + catalyst supply). At this time, the valves 243f to 243h can also be opened to supply inactive gas to the processing chamber 201 through the nozzles 249a to 249c, respectively.

[0132] By supplying the first raw material and the catalyst to the wafer 200 under the processing conditions described later, it is possible to suppress the chemical adsorption of at least a portion of the molecular structure of the molecules constituting the first raw material to the second film portion 320, while selectively chemically adsorbing at least a portion of the molecular structure of the molecules constituting the first raw material to the first end surface 312. Thus, a first layer is formed on the first end surface 312 of the wafer 200. It should be noted that the first layer includes at least a portion of the molecular structure of the molecules constituting the first raw material as a residue of the first raw material. That is, the first layer includes at least a portion of the atoms constituting the first raw material.

[0133] In this step, by supplying a catalyst and a first raw material, the above reaction can be carried out in a non-plasma atmosphere or under low temperature conditions as described later. In this way, by carrying out the reaction in a non-plasma atmosphere or under low temperature conditions as described later, the formation of the first layer can be maintained while the molecules and atoms constituting the modified layer 324 formed on the second end surface 322 are not eliminated (detached) from the second end surface 322.

[0134] In addition, by performing the process in a non-plasma atmosphere or under low temperature conditions as described later, the first layer can be formed in a manner that the first raw material does not undergo thermal decomposition (gas phase decomposition), that is, does not self-decompose, in the processing chamber 201. As a result, it is possible to suppress at least a portion of the molecular structure of the molecules constituting the first raw material from being multiple-deposited on the first end surface 312 and the second end surface 322, and at least a portion of the molecular structure of the molecules constituting the first raw material can be selectively adsorbed on the first end surface 312.

[0135] It should be noted that, in this step, at least a portion of the molecular structure of the molecules constituting the first raw material is adsorbed on a portion of the second end surface 322 of the wafer 200, but the amount of adsorption is very small, while the amount of adsorption on the first end surface 312 of the wafer 200 is overwhelmingly large. Such selective adsorption is possible because the processing conditions of this step are set to low temperature conditions as described later, and the first raw material is not decomposed in the gas phase in the processing chamber 201. In addition, this is because, compared with the modified layer 324 formed on the second end surface 322, the modified layer 324 is not formed in most areas of the first end surface 312.

[0136] As the treatment conditions when the first raw material and the catalyst are supplied in the raw material supply step, the following can be exemplified:

[0137] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C

[0138] Processing pressure: 133~1333Pa

[0139] First raw material supply flow rate: 0.001~2slm

[0140] Catalyst supply flow rate: 0.001~2slm

[0141] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0142] Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0143] After the first layer is selectively formed on the wafer 200, the valves 243b and 243d are closed to stop the supply of the first raw material and the catalyst to the processing chamber 201. Then, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those in the purging in the modification step. In addition, the processing temperature during the purging in this step is preferably set to the same temperature as the processing temperature during the supply of the first raw material and the catalyst.

[0144] As the first raw material, for example, a gas containing Si and halogen can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br) and iodine (I) and the like. The gas containing Si and halogen preferably contains halogen in the form of a chemical bond between Si and halogen. As the gas containing Si and halogen, for example, a chlorosilane-based gas can be used. The gas containing Si and halogen can also further contain O, for example, containing O in the form of a siloxane bond (Si-O-Si bond). As the gas containing Si and halogen, for example, a chlorosilane-based gas can be used. These gases all preferably contain Cl in the form of a Si-Cl bond. As the first raw material, in addition to these, a gas containing amino groups such as an aminosilane-based gas can also be used.

[0145] As the first raw material, for example, tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), octachlorotrisilane (Si3Cl8) etc. can be used. In addition, as the first raw material, for example, hexachlorodisiloxane (Cl3Si-O-SiCl3) and octachlorotrisiloxane (Cl3Si-O-SiCl2-O-SiCl3) etc. can be used. As the first raw material, one or more of these can be used.

[0146] In addition, as the first raw material, for example, tetrakis(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]) can also be used. As the first raw material, one or more of these can be used.

[0147] As the catalyst, for example, an amine gas containing carbon (C), nitrogen (N) and hydrogen (H) can be used. As the amine gas, a cyclic amine gas or a chain amine gas can be used. As the catalyst, for example, pyridine (C5H5N), aminopyridine (C5H6N2), picoline (C6H7N), lutidine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), piperazine (C4H 10 N2) and piperidine (C5H 11 N), cyclic amines such as aniline (C6H7N). In addition, as catalysts, chain amines such as triethylamine ((C2H5)3N), diethylamine ((C2H5)2NH), monoethylamine ((C2H5)NH2), trimethylamine ((CH3)3N), dimethylamine ((CH3)2NH) and monomethylamine ((CH3)NH2) can be used. As catalysts, one or more of these can be used. This also applies to the reactant supply step described later.

[0148] [Reactant supply step]

[0149] After the raw material supply step is completed, a reactant (reaction gas) and a catalyst (catalyst gas) as a first film-forming agent are supplied to the wafer 200, that is, the wafer 200 after the first layer is selectively formed. Here, an example using an oxidant (oxidizing gas) as the reactant (reaction gas) is described.

[0150] Specifically, valves 243c and 243d are opened to allow the reactant and catalyst to flow into the gas supply pipes 232c and 232d, respectively. The reactant and catalyst are adjusted in flow rate by MFC241c and 241d, respectively, and supplied to the processing chamber 201 through nozzles 249c and 249a, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the reactant and catalyst are supplied to the wafer 200 from the side of the wafer 200 (reactant + catalyst supply). At this time, valves 243f to 243h can also be opened to supply inactive gas to the processing chamber 201 through nozzles 249a to 249c, respectively.

[0151] By supplying a reactant and a catalyst to the wafer 200 under the processing conditions described below, at least a portion of the first layer formed in the raw material supply step can be oxidized, thereby forming a second layer in which the first layer is oxidized.

[0152] In this step, by supplying a catalyst and a reactant, the above reaction can be performed in a non-plasma atmosphere or under low temperature conditions as described later. Thus, by performing the reaction in a non-plasma atmosphere or under low temperature conditions as described later, the oxidation of the barrier portion 314 can be maintained without eliminating (detaching) the molecules and atoms constituting the modified layer 324 formed on the second end surface 322 from the second end surface 322.

[0153] As the treatment conditions when supplying the reactant and the catalyst in the reactant supply step, the following can be exemplified:

[0154] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C

[0155] Processing pressure: 133~1333Pa

[0156] Reactant supply flow rate: 0.001~2slm

[0157] Catalyst supply flow rate: 0.001~2slm

[0158] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0159] Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0160] After the first layer is oxidized and changed (converted) into the second layer, the valves 243c and 243d are closed to stop the supply of the reactant and the catalyst into the processing chamber 201. Then, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those in the above-mentioned purging step. In addition, the processing temperature during purging in this step is preferably set to the same temperature as the processing temperature during the supply of the reactant and the catalyst.

[0161] As a reactant, i.e., an oxidant, for example, a gas containing oxygen (O) and hydrogen (H) can be used. As a gas containing O and H, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, and H2 gas + ozone (O3) gas can be used. That is, as a gas containing O and H, an O-containing gas + a H-containing gas can also be used. At this time, as a H-containing gas, a deuterium (D2) gas can also be used instead of the H2 gas. One or more of these can be used as a reactant.

[0162] It should be noted that the combined description of two gases such as "H2 gas + O2 gas" in this specification means a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed in a supply pipe (pre-mixed) and then supplied to the processing chamber 201; or the two gases can be supplied to the processing chamber 201 separately through different supply pipes and then mixed in the processing chamber 201 (post-mixed).

[0163] In addition, as a reactant, i.e., an oxidant, in addition to a gas containing O and H, an O-containing gas can be used. As an O-containing gas, for example, O2 gas, O3 gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, and carbon dioxide (CO2) gas can be used. As a reactant, i.e., an oxidant, in addition to these, the above-mentioned various aqueous solutions and various cleaning liquids can also be used. At this time, by exposing the wafer 200 to the cleaning liquid, the oxidized object on the surface of the wafer 200 can be oxidized. As a reactant, one or more of these can be used.

[0164] As the catalyst, for example, the same catalysts as the various catalysts exemplified in the above-mentioned raw material supplying step can be used.

[0165] [Scheduled number of implementations]

[0166] By performing the above-mentioned raw material supply step and reactant supply step alternately for a predetermined number of times (n times, n being an integer greater than 1), it is possible to Figure 7BAs shown, a film serving as a barrier 314 is selectively (preferentially) formed on the first end surface 312 of the first film portion 310 of the wafer 200. For example, when the first raw material, reactant, and catalyst are used, a SiO film serving as a barrier can be selectively grown on the first end surface 312. The above cycle is preferably repeated multiple times until the barrier 314 grown from the first end surfaces 312 exposed on both sides of the groove 350 fills the space between the first end surfaces 312. Thus, the barrier 314 is formed in a manner that fills the space between the first end surfaces 312.

[0167] (Remove step)

[0168] Next, after the film forming process, Figure 7C As shown, a removing agent is supplied to the wafer 200 to remove the modified layer 324 formed on the second end surface 322 of the second film portion 320 exposed in the groove portion 350. That is, a removing agent that reacts with the modified layer 324 as an inhibition layer formed on the second end surface 322 of the wafer 200 is supplied to selectively remove the modified layer 324.

[0169] Specifically, the valve 273 is opened to allow the remover to flow into the gas supply pipe 272. The remover is flow-regulated by the MFC 271, supplied to the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the remover is supplied to the wafer 200 from the side of the wafer 200 (remover supply).

[0170] By supplying a remover to the wafer 200 under predetermined processing conditions (eg, 500° C. or higher), the modified layer 324 formed on the second end surface 322 can be removed. In addition, as the remover, one or more of O3 plasma gas, O2 plasma gas, and annealing agent can be used.

[0171] (Second Film Formation Step)

[0172] After the removal step, Fig.7D As shown, a second film-forming agent is supplied to the wafer 200, and a film having a composition different from that of the barrier portion 314 and having the same composition as the second film portion 320 is formed in the groove portion 350 of the second film portion 320 of the wafer 200, thereby filling and restoring the groove portion 350. It should be noted that in this embodiment, an example of filling and restoring the groove portion 350 by a film having the same composition as the second film portion 320 (i.e., SiOC film) is described in this step, but the present disclosure is not limited to this. In the subsequent process described later, as long as it is a film having a composition that is not etched when the third film portion 330, the first portion 311A ​​of the first film portion 310, and the barrier portion 314 are removed, it can be used as a film for filling and restoring the groove portion 350. For example, a film containing O and C can be suitably used.

[0173] In this embodiment, in this step, a film having the same composition as the second film portion 320 is formed by the same process except that the raw material supplied is different from that in the first film forming step. That is, a second raw material (second raw material gas), a catalyst, and a reactant are used as a second film forming agent to form a film. Specifically, the second film forming step uses a Si raw material containing C and halogen as a second raw material different from the first raw material to form a SiOC film. The second raw material gas is supplied to the processing chamber 201 through the nozzle 249b by controlling the MFC241e and the valve 243e of the second raw material gas supply system.

[0174] As the second raw material, for example, a gas containing Si, C and halogen can be used. The gas containing Si, C and halogen preferably contains C in the form of Si-C bonding. As the gas containing Si, C and halogen, for example, an alkylene chlorosilane system gas containing an alkylene group can be used. The alkylene group includes methylene, vinyl, propenyl, butenyl, etc. In addition, as the gas containing Si, C and halogen, for example, an alkyl chlorosilane system gas containing an alkyl group can be used. The alkyl group includes methyl, ethyl, propyl, butyl, etc.

[0175] As the second raw material, for example, bis(trichlorosilyl)methane ((SiCl3)2CH2), 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4), 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2) and 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C2H4Cl4Si2) can be used. As the second raw material, one or more of these can be used.

[0176] An example of the processing sequence of the film formation process in this step can be expressed as follows:

[0177] (second raw material+catalyst→reactant+catalyst)×n.

[0178] In this step, a cycle including a raw material supplying step of supplying the second raw material and the catalyst to the wafer 200 and a reactant supplying step of supplying the reactant and the catalyst to the wafer 200 is repeated a plurality of times until the film formed by this cycle fills the groove portion 350 .

[0179] Here, in this step, when the groove portion 350 is filled and restored with the second film portion 320, in the case of gentle film formation such as when plasma is not used, it is preferred to perform the above-mentioned step of removing the modified layer 324 before the filling and restoration. However, in the case of using a film formation technique using plasma in this step, for example, using a plasma-excited gas such as O2 plasma as a reactant, using a gas with a high energy state such as O3, and performing this step by setting the temperature of the wafer 200 to, for example, 300°C or more (400°C or more as an example of a more significant effect), the above-mentioned removal step can be omitted because the modified layer 324 does not have the function of a film formation barrier layer.

[0180] (Post-Purge and Atmospheric Pressure Restoration)

[0181] After the second film forming step is completed, Figure 1 The nozzles 249a to 249c of the substrate processing apparatus 10 shown in the figure supply an inert gas as a purge gas into the processing chamber 201, and exhaust the gas from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the residual gas, reaction by-products, etc. in the processing chamber 201 are removed from the processing chamber 201. Then, the atmosphere in the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is restored to normal pressure.

[0182] (Cassette unloading and wafer release)

[0183] Then, the sealing cap 219 is lowered by the wafer box elevator 115 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer box 217 (wafer box unloading). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer box 217.

[0184] Here, the modification step and the first film forming step are preferably performed in the same processing chamber (in-situ). Thus, the modification step and the first film forming step can be performed without exposing the wafer 200 to the atmosphere, and selective growth can be appropriately performed. That is, by performing these processes in the same processing chamber, selective growth can be performed with high selectivity. In addition, in the case where the removal step can be omitted as described above, by performing the modification step, the first film forming step, and the second film forming step in the same processing chamber, the time required for moving the wafer 200 in and out can be omitted.

[0185] (Post-process)

[0186] In the later process, Figures 8A to 8D As shown, the third film portion 330 , the first portion 311A ​​of the first film portion 310 , and the blocking portion 314 are removed, and the second portion 311B remains.

[0187] Specifically, if Fig. 8A As shown, a hard mask 910 is formed on the upper surface of the wafer 200 in a manner that covers at least the fourth film portion 340, and the third film portion 330 is removed by etching. For example, the etching can be performed by anisotropic etching using a carbon fluoride (CF) plasma gas as in the previous step. It should be noted that anisotropic etching may not be used.

[0188] Then, if Figure 8B As shown in FIG. 1 , the first portion 311A ​​of the first film portion 310 is removed by etching to the stopper portion 314. More specifically, in a state where the fourth film portion 340 formed adjacent to the side surface where the second portion 311B of the first film portion 310 and the second film portion 320 are exposed remains, the first portion 311A ​​is removed by etching from the side surface where the first portion 311A ​​is exposed to the stopper portion 314. That is, the first portion 311A ​​is removed from the end surface not covered by the second film portion 320 to the stopper portion 314.

[0189] At this time, the blocking portion 314 prevents the etching of the second portion 311B of the first film portion 310. As an etchant (etching gas) for etching the first film portion 310 as a Si film, at least one of a fluorine (F) gas and a chlorine (Cl) gas can be used. For example, fluorine (F2) gas, chlorine (Cl2) gas, and chlorine trifluoride (ClF3) gas can be used. It should be noted that, here, it is preferred not to use a gas that has an etching effect on an oxide film such as a SiO film or a SiOC film (for example, hydrogen fluoride (HF) gas, etc.). In addition, here, when etching the second portion 311B, it is desirable to use an isotropic etching method.

[0190] Then, if Figure 8C As shown, a hard mask 920 is formed in a manner to cover at least the fourth film portion 340, and the blocking portion 314 of the first film portion 310 is removed by etching. The etching is performed in a manner that the second portion 311B of the first film portion 310 as a Si film and the second film portion 320 as a SiOC film remain, and the blocking portion 314 as a SiO film is selectively removed. For example, as an etching method, wet etching or dry etching using an etchant containing fluorine (F) can be used. As an etchant, for example, an aqueous solution or gas containing hydrogen fluoride (HF) can be used. In addition, as Fig.8D The hard mask 920 is removed as shown.

[0191] It should be noted that the above-mentioned etching treatments in the post-process may be performed using different etching apparatuses, or a plurality of these treatments may be performed using the same etching apparatus.

[0192] (3) Effects of this embodiment

[0193] According to the present embodiment, one or more of the following effects can be obtained.

[0194] The stopper 314 is formed on a part of the first film part 310 of the wafer 200, the first film part 310 is divided into the first part 311A ​​and the second part 311B, and the first part 311A ​​is removed to the stopper 314. Thus, the first part 311A, which is a part of the first film part 310, can be removed with high precision, leaving the second part 311B.

[0195] In addition, a groove portion 350 penetrating the first film portion 310 and the second film portion 320 is formed on the wafer 200, and a first raw material (first film-forming agent) is supplied into the groove portion 350, and at least a part of the molecular structure of the molecules constituting the raw material is selectively deposited on the first end surface 312 of the first film portion 310 exposed in the groove portion 350, thereby forming the barrier portion 314. Therefore, even if the first film portion 310 is a structure covered by the second film portion 320, the barrier portion 314 can be formed at a desired position of the first film portion 310.

[0196] Furthermore, the modified layer 324 that inhibits adsorption of the first raw material is selectively formed on the second end surface 322 of the second film portion 320 exposed in the groove portion 350. Thus, the formation of the barrier portion 314 on the second end surface 322 of the second film portion 320 can be suppressed or prevented.

[0197] In addition, after the modified layer 324 exposed in the groove 350 is removed, the second film portion 320 is formed in the groove 350 to restore the restoration. Thus, it is possible to avoid the modified layer 324 hindering the restoration of the restoration of the restoration of the second film portion 320.

[0198] In addition, after the first portion 311A ​​of the first film portion 310 is removed, the stopper portion 314 is removed to leave the second portion 311B. Thus, the second portion 311B of the first film portion 310 can be left with high accuracy.

[0199] In addition, in the wafer 200, the second film portion 320 covers the periphery of the first film portion 310. Furthermore, the other side end surface of the second portion 311B of the first film portion 310 is covered by the fourth film portion 340. Thus, when the first portion 311A ​​and the stopper portion 314 of the first film portion 310 are etched, the second film portion 320 can prevent the surrounding surface orthogonal to the length direction of the first film portion 310 from being etched, and the fourth film portion 340 can prevent the other side end surface of the second portion 311B from being etched.

[0200] In the wafer 200 , a plurality of first film portions 310 are formed at intervals in the second film portion 320 . Thus, by forming the groove portion 350 in the wafer 200 , the barrier portion 314 can be formed at the same position of the plurality of first film portions 310 .

[0201] Furthermore, by forming the stopper 314 at the same position of the first film portion 310 of the wafer 200, the first portions 311A ​​of the plurality of first film portions 310 can be removed uniformly. Similarly, the second portions 311B of the plurality of first film portions 310 can be uniformly left.

[0202] In addition, the first film portion 310 of the wafer 200 is a non-oxygen-containing film, and the second film portion 320 is an oxygen-containing film. Thus, the OH terminal density of the second end face 322 of the second film portion 320, which is an oxygen-containing film, can be made greater than the OH terminal density of the first end face 312 of the first film portion 310, which is a non-oxygen-containing film. Therefore, the modifier selectively reacts with the OH group of the second end face 322 of the second film portion 320 exposed in the groove portion 350 and is adsorbed, and the modified layer 324 is easily selectively formed.

[0203] The barrier portion 314 of the wafer 200 is an oxygen-containing film, so that when the first portion 311A ​​of the first film portion 310 is removed by etching, it can function as an etching barrier film against an etchant that etches the non-oxygen-containing film.

[0204] In addition, the first film portion 310 of the wafer 200 is composed of a Si film, the barrier portion 314 is composed of a SiO film, and the second film portion 320 is composed of a SiOC film. By using these combinations, the first film portion 310 as a Si film and the second film portion 320 as a SiOC film can remain by etching using HF, and only the barrier portion 314 as a SiO film can be selectively removed.

[0205] In addition, in the first film forming step and the second film forming step, by alternating the raw material supply step and the reactant supply step for a predetermined number of cycles and supplying a catalyst to the wafer 200 in at least one of the raw material supply step and the reactant supply step, selective growth can be performed with good control under the above-mentioned low temperature conditions.

[0206] <Other embodiments of the present disclosure>

[0207] The embodiments of the present disclosure have been specifically described above, but the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present disclosure.

[0208] (Other Embodiments 1)

[0209] In another embodiment 1 of the present disclosure, the same reference numerals are given to the same components as those in the above-mentioned embodiment, and overlapping descriptions are omitted or simplified.

[0210] In the previous step of the other embodiment 1, Fig. 9A The wafer 200 shown in FIG. Fig. 9B As shown, a recess 352 is formed in the second film portion 320 in a manner that a portion of the first film portion 310 is exposed. Specifically, a hard mask 930 is formed on the upper surface of the wafer 200, and the second film portion 320 is selectively removed by etching in a manner that the first film portion 310 remains, thereby forming the recess 352. As an etching method, dry etching, for example, by supplying an etching gas to the wafer 200 can be used. In addition, anisotropic etching by plasma gas can be particularly suitably used. In addition, as an etching gas, for example, a gas containing a halogen element, C and H (hydrogen) can be used. For example, one or more of a hydrofluorocarbon (CHF2) gas, a hydrochlorofluorocarbon (CHClF2) gas, and the like as a fluorocarbon system containing H can be used. In addition, a mixed gas of a CF-based gas such as carbon tetrafluoride (CF4) gas and a H-containing gas such as H2 gas can be used.

[0211] like Fig. 9C As shown, after forming the recess 352, the hard mask 930 is removed.

[0212] Then, if Fig.10 As shown, the second modifying agent is supplied to the wafer 200, and the portion of the first film portion 310 exposed in the recess 352 is modified by the second modifying agent. The portion of the first film portion 310 modified by the second modifying agent constitutes the blocking portion 314 (modification step). In this step, for example, a substrate processing apparatus having the same configuration as the substrate processing apparatus 10 and having a second modifying agent supply system for supplying the second modifying agent can be used instead of the modifying agent supply system.

[0213] One side of the barrier portion 314 of the first film portion 310 is set as the first portion 311A, and the other side is set as the second portion 311B. If described from another point of view, the first film portion 310 is partially modified and replaced by the barrier portion 314. Thus, the barrier portion 314 divides the first film portion 310 into the first portion 311A ​​and the second portion 311B.

[0214] The second modifier of this embodiment is an oxidant, and the barrier portion 314 is an oxide film as in the above embodiment. The oxidation rate of the first film portion 310 as a Si film by the oxidant is greater than the oxidation rate of the second film portion 320 as a SiOC film.

[0215] Thus, for example, by supplying O3 gas, O2 plasma gas, H2+O2 mixed plasma gas, etc. as a modifier (oxidant) into the recess 352, or supplying H2 gas and O2 gas as a modifier (oxidant) under conditions below atmospheric pressure, etc., the portion of the first film portion 310 exposed in the recess 352 is selectively oxidized to form a blocking portion 314.

[0216] Specifically, the following steps are the same as those in the above embodiment. Specifically, the steps after (the second film forming step) and (the post-step) are the same as those in the above embodiment.

[0217] In this embodiment, the same effects as those of the above-described embodiment can be obtained. In addition, in this embodiment, since the portion of the first film portion 310 exposed in the recessed portion 352 is modified to form the stopper portion 314, the process is simplified.

[0218] (Further other embodiments)

[0219] For example, the second film forming step is provided to fill and restore the groove 350 or the recess 352 in the wafer 200 with the second film portion 320. However, the second film forming step may not be provided. However, it is desirable to provide the second film forming step.

[0220] In addition, for example, the first film portion 310 of the wafer 200 may also be a non-oxygen-containing film other than a Si film, such as a silicon nitride film (SiN film), a metal-containing film, etc. The second film portion 320 of the wafer 200 may also be an oxygen-containing film other than a SiOC film, such as a SiO film, a silicon carbonitride film (SiOCN film), a metal oxide film, etc.

[0221] In addition, for example, the wafer 200 may include a plurality of regions made of different materials as the first film portion 310. In addition, the wafer 200 may include a plurality of regions made of different materials as the second film portion 320.

[0222] In addition to the above-mentioned combination of Si film and SiOC film, the first film portion 310 and the second film portion 320 of the wafer 200 can also be selected from semiconductor films such as silicon oxycarbon nitride film (SiOCN film), silicon carbon oxide film (SiOC film), silicon oxynitride film (SiON film), silicon carbon nitride film (SiCN film), silicon carbide film (SiC film), silicon borocarbon nitride film (SiBCN film), silicon boronitride film (SiBN film), silicon borocarbide film (SiBC film), silicon film (Si film), germanium film (Ge film), silicon germanium film (SiGe film), titanium nitride film (TiN film), tungsten film (W film), molybdenum film (Mo film), ruthenium film (Ru film), cobalt film (Co film), nickel film (Ni film), copper film (Cu film), amorphous carbon film (aC film) and single crystal Si (Si wafer) for use.

[0223] In addition, for example, as the blocking portion 314, in addition to the SiO film, for example, a semiconductor-containing film such as SiON film, SiOCN film, SiCN film, SiC film, SiN film, SiBCN film, SiBN film, SiBC film, Si film, Ge film, SiGe film, and a metal-containing film such as TiN film, W film, WN film, Mo film, Ru film, Co film, Ni film, Al film, AlN film, TiO film, WO film, WON film, MoO film, RuO film, CoO film, NiO film, AlO film, ZrO film, HfO film, and TaO film may be formed.

[0224] It should be noted that the barrier portion 314 and the second film portion 320 are selected from films having a composition that is relatively resistant to etching with respect to the etchant used when etching the first portion 311A ​​of the first film portion 310. In addition, the first film portion 310 and the second film portion 320 are selected from films having a composition that is relatively resistant to etching with respect to the etchant used when etching the barrier portion 314. In addition, the first film portion 310 and the second film portion 320 can be selected from a film combination having a composition that is relatively easy to form a modified layer (inhibiting layer) on the surface of the second film portion 320 compared to the surface of the first film portion 310. In the case of using these films, the same effect as the above-mentioned embodiment can be obtained.

[0225] The recipe used in each process is preferably prepared separately according to the process content, and recorded and stored in the storage device 121c in advance via the communication circuit and the external storage device 123. Furthermore, when starting each process, the CPU 121a preferably selects an appropriate recipe from the multiple recipes recorded and stored in the storage device 121c according to the process content.

[0226] In the above embodiment, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present disclosure is not limited to the above embodiment, and can be appropriately applied even when a film is formed using a single-piece substrate processing device that processes one or more substrates at a time. In addition, in the above embodiment, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present disclosure is not limited to the above embodiment, and can be appropriately applied when a film is formed using a substrate processing device having a cold-wall type processing furnace. When using these substrate processing devices, each process can be performed according to the same processing procedures and processing conditions as in the above embodiment, and the same effects as in the above embodiment and the modified example can be obtained.

[0227] The above-mentioned embodiments may be used in combination as appropriate. The processing procedure and processing conditions in this case may be the same as those in the above-mentioned embodiments, for example.

[0228] (Industrial Applicability)

[0229] According to the present disclosure, when etching a film on a substrate, a desired portion of the film can be removed with high accuracy.

[0230] Explanation of symbols

[0231] 200 Wafer

[0232] 310 First membrane section

[0233] 311A Part 1

[0234] 311B Part 2

[0235] 314 Blocking

Claims

1. A substrate processing method, comprising: (a) on a substrate having a first film and a second film covering the first film, replacing a portion of the first film covered by the second film with a barrier film, thereby dividing the first film into a first portion and a second portion by the barrier film; and (b) A step of removing the first portion from the end surface not covered by the second film to the barrier film, leaving the second portion.

2. The substrate processing method according to claim 1, wherein: (a) further possess: (c) forming a groove portion penetrating the second film and the portion of the first film covered by the second film; and (d) supplying a first raw material into the groove portion to deposit at least a portion of a molecular structure of molecules constituting the first raw material on an end surface of the first film exposed in the groove portion, thereby forming the barrier film.

3. The substrate processing method according to claim 2, wherein: (a) before supplying the first raw material into the groove, further comprising: (e) forming a modified layer that inhibits the deposition of the first raw material on the end surface of the second film exposed in the groove.

4. The substrate processing method according to claim 3, wherein: In (e), a modifying agent is adsorbed on the end surface of the second film exposed in the groove portion to form the modified layer.

5. The substrate processing method according to claim 4, wherein: In (e), the modifying agent is allowed to react with the OH group on the end surface of the second film exposed in the groove portion and adsorbed.

6. The substrate processing method according to claim 2, wherein: Before (b), further: (f) A step of supplying a second raw material into the groove portion to fill the groove portion with the second film.

7. The substrate processing method according to claim 6, wherein: (a) before supplying the first raw material into the groove portion, further comprising: (e) forming a modified layer that hinders the deposition of the first raw material on the end surface of the second film exposed in the groove portion; and before (f), further: (g) A step of removing the modified layer formed on the end surface of the second film exposed in the groove portion.

8. The substrate processing method according to claim 2, wherein: forming a third film on the substrate so as to cover the end surface of the first portion not covered by the second film and the end surface of the second film; and before (b), further: (h) A step of removing the third film.

9. The substrate processing method according to claim 8, wherein: In (b), an etchant is supplied to the end surface of the first portion exposed by removing the third film, and the first portion is removed down to the barrier film.

10. The substrate processing method according to claim 1, wherein: After (b), further: (i) A step of removing the barrier film.

11. The substrate processing method according to claim 2, wherein: The first film is at least partially formed in the second film and is composed of a plurality of blocks formed at intervals in a direction perpendicular to the longitudinal direction.

12. The substrate processing method according to claim 2, wherein: forming a fourth film on the substrate so as to cover an end surface of the second portion not covered by the second film and an end surface of the second film; In (b), the first portion is removed by etching from the end surface where the first portion is exposed to the stopper film.

13. The substrate processing method according to claim 2, wherein: The first film is a non-oxygen-containing film, and the second film is an oxygen-containing film.

14. The substrate processing method according to claim 2, wherein: The barrier film and the second film have different compositions from each other.

15. The substrate processing method according to claim 2, wherein: The first film is composed of a silicon film, the barrier film is composed of a silicon oxide film, and the second film is composed of a silicon oxygen carbon film.

16. The substrate processing method according to claim 1, wherein: (a) further possess: (j) forming a recessed portion in the second film so as to expose a portion of the first film; and (k) A step of supplying a second modifying agent into the recessed portion to modify a portion of the first film exposed in the recessed portion into the barrier film.

17. A method for manufacturing a semiconductor device, comprising: (a) on a substrate having a first film and a second film covering the first film, replacing a portion of the first film covered by the second film with a barrier film, thereby dividing the first film into a first portion and a second portion by the barrier film; and (b) A step of removing the first portion from the end surface not covered by the second film to the barrier film, leaving the second portion.

18. A substrate processing method comprising: (a) supplying a modifying agent to a substrate having a first film and a second film covering the first film, and having a groove penetrating the first film and the second film, thereby forming a modified layer that inhibits adsorption of the first raw material on an end surface of the second film exposed in the groove; and (b) supplying the first raw material into the groove portion, causing at least a portion of the molecular structure of the molecules constituting the first raw material to accumulate on the end surface of the first film exposed in the groove portion, thereby forming a barrier film that hinders etching of the first film, and dividing the first film into a first part and a second part by the barrier film.

19. A method for manufacturing a semiconductor device, comprising: (a) supplying a modifying agent to a substrate having a first film and a second film covering the first film, and having a groove penetrating the first film and the second film, thereby forming a modified layer that inhibits adsorption of the first raw material on an end surface of the second film exposed in the groove; and (b) supplying the first raw material into the groove portion, causing at least a portion of the molecular structure of the molecules constituting the first raw material to accumulate on the end surface of the first film exposed in the groove portion, thereby forming a barrier film that hinders etching of the first film, and dividing the first film into a first part and a second part by the barrier film.

20. A substrate processing device comprising: a first raw material supply system configured to supply a first raw material to the substrate; a modifying agent supply system configured to supply the modifying agent to the substrate; and The control unit is configured to control the first raw material supply system and the modifier supply system to perform the following processing: The process of supplying the modifying agent to the substrate having a first film and a second film covering the first film and having a groove portion penetrating the first film and the second film, thereby forming a modified layer that hinders the adsorption of the first raw material on the end face of the second film exposed in the groove portion; and supplying the first raw material to the substrate, causing at least a part of the molecular structure of the molecules constituting the first raw material to accumulate on the end face of the first film exposed in the groove portion, thereby forming a barrier film that hinders the etching of the first film, and dividing the first film into a first part and a second part by the barrier film.

21. A program that causes a substrate processing apparatus to execute the following process through a computer: (a) a process of supplying a modifying agent to a substrate having a first film and a second film covering the first film, and having a groove portion penetrating the first film and the second film, thereby forming a modified layer that inhibits adsorption of the first raw material on an end surface of the second film exposed in the groove portion; and (b) The first raw material is supplied into the groove portion, and at least a portion of the molecular structure of the molecules constituting the first raw material is deposited on the end surface of the first film exposed in the groove portion, thereby forming a barrier film that hinders the etching of the first film, and the first film is divided into a first part and a second part by the barrier film.

Images