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

Abstract

To precisely form a film on a substrate.SOLUTION: A substrate processing method includes the steps of: (a) in a substrate having a structure in which respective surfaces of a first material, a second material, and a third material are adjacent to each other in order, selectively forming each of a first dielectric film containing oxygen on a surface of the first material and a second dielectric film containing oxygen on a surface of the third material with respect to a surface of the second material; and (b) forming a separation film in a recess having the first dielectric film and the second dielectric film as a sidewall.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technique capable of precisely forming a film on a substrate.

Means for Solving the Problems

[0005] According to one aspect of the present disclosure, (a) In a substrate having a structure in which the surfaces of a first material, a second material, and a third material are adjacent to each other in this order, a first dielectric film containing oxygen is selectively formed on the surface of the first material, and a second dielectric film containing oxygen is selectively formed on the surface of the third material, respectively, with respect to the surface of the second material; and (b) forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls; A technique having the above is provided.

Effects of the Invention

[0006] According to the present disclosure, it becomes possible to precisely form a film on a substrate.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0008] <One Aspect of the Present Disclosure> Hereinafter, one aspect of the present disclosure will be mainly described with reference to FIGS. 1 to 3 and FIGS. 4(a) to 4(f). Note that the drawings used in the following description are all schematic, and the dimensional relationships of each element, the ratios of each element, etc. shown in the drawings do not necessarily match the actual ones. Also, the dimensional relationships of each element, the ratios of each element, etc. do not necessarily match among a plurality of drawings.

[0009] (1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, the processing furnace 202 of the substrate processing apparatus includes a reaction tube 203. A manifold 209 is disposed below the reaction tube 203. The processing container is mainly constituted by the reaction tube 203 and the manifold 209. A processing chamber 201 is formed inside the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate.

[0010] Outside the reaction tube 203, a heater 207 for heating the wafer 200 in the processing chamber 201 is provided. The heater 207 also functions as an activation mechanism for activating the gas in the processing chamber 201 with heat. A temperature sensor 263 is installed inside the reaction tube 203.

[0011] Nozzles 249a to 249c are provided inside the processing chamber 201. As shown in FIG. 2, the nozzles 249a to 249c are provided along the inner wall of the reaction tube 203 so as to rise upward in the arrangement direction of the wafers 200. A plurality of gas supply holes 250a to 250c are provided on the side surfaces of the nozzles 249a to 249c over the lower part to the upper part of the reaction tube 203.

[0012] Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c. Mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c are provided in gas supply pipes 232a to 232c. Gas supply pipes 232d and 232f are connected to the downstream side of valve 243a of gas supply pipe 232a. Gas supply pipes 232e and 232g are connected to the downstream side of valve 243b of gas supply pipe 232b. Gas supply pipe 232h is connected to the downstream side of valve 243c of gas supply pipe 232c. MFCs 241d to 241h and valves 241d to 241h are provided in gas supply pipes 232d to 232h.

[0013] From gas supply pipe 232a, the first raw material is supplied into the processing chamber 201 via MFC 241a, valve 243a, and nozzle 249a.

[0014] From gas supply pipe 232b, the reactant (oxidizing agent) is supplied into the processing chamber 201 via MFC 241b, valve 243b, and nozzle 249b.

[0015] From gas supply pipe 232c, the modifier is supplied into the processing chamber 201 via MFC 241c, valve 243c, and nozzle 249c.

[0016] From gas supply pipe 232d, the second raw material is supplied into the processing chamber 201 via MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a.

[0017] From gas supply pipe 232e, the catalyst is supplied into the processing chamber 201 via MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0018] From gas supply pipes 232f to 232h, the inert gas is supplied into the processing chamber 201 via MFCs 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0019] Primarily, the gas supply pipe 232a, MFC 241a, and valve 243a constitute the first raw material supply system. Primarily, the gas supply pipe 232b, MFC 241b, and valve 243b constitute the reactant (oxidant) supply system. Primarily, the gas supply pipe 232c, MFC 241c, and valve 243c constitute the reformer supply system. Primarily, the gas supply pipe 232d, MFC 241d, and valve 243d constitute the second raw material supply system. Primarily, the gas supply pipe 232e, MFC 241e, and valve 243e constitute the catalyst supply system. Primarily, the gas supply pipes 232f to 232h, MFCs 241f to 241h, and valves 243f to 243h constitute the inert gas supply system. Among the various supply systems described above, any one or all of the supply systems may be configured as an integrated supply system 248 in which the valves 243a to 243h, MFCs 241a to 241h, etc. are integrated. When different reactants are used in each of the processing steps (steps A, B, C) described later, a reactant supply system for supplying the reactant to the nozzle 249b is provided individually for each different reactant.

[0020] Below the reaction tube 203, an exhaust port 231a is provided. To the exhaust pipe 231, a vacuum pump 246 is connected via a pressure sensor 245 and an APC (Auto Pressure Controller) valve 244. Primarily, the exhaust pipe 231, APC valve 244, and pressure sensor 245 constitute the exhaust system. The vacuum pump 246 may be included in the exhaust system.

[0021] Below the manifold 209, a seal cap 219 is provided. On the seal cap 219, a rotation mechanism 267 for rotating a boat 217 described later is installed. The seal cap 219 is lifted and lowered by a boat elevator 115. The boat elevator 115 functions as a transfer mechanism for transferring the wafer 200 in and out of the processing chamber 201.

[0022] Below the manifold 209, a shutter 219s is provided that can airtight close the lower end opening of the manifold 209. The opening and closing operation of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0023] As a substrate support, a boat 217 is configured to support a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture, aligned with each other in the vertical direction in a state where their centers are aligned, and support them in multiple stages. Below the boat 217, heat insulating plates 218 are supported in multiple stages.

[0024] Furthermore, the substrate processing apparatus may include an etching unit (etching apparatus) that executes step B2 (separation film formation) described later. This unit includes, for example, an etching gas supply system that supplies etching gas into a processing container that houses the wafer 200, a plasma generation unit that plasma-excites the etching gas in the processing container by an electrode (antenna) supplied with high-frequency power, a bias adjustment unit that adjusts the potential (bias) of the wafer 200, and the like. In step B2, anisotropic plasma etching on the wafer 200 can be executed using this unit.

[0025] Note that the substrate processing apparatus including the etching unit may be configured as a processing system connected to each other via a communication network.

[0026] As shown in FIG. 3, a controller 121, which is a control unit, is configured as a computer including a CPU 121a, a RAM 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as a touch panel or the like is connected to the controller 121. It is possible to connect an external storage device 123 to the controller 121.

[0027] The storage device 121c is composed of a flash memory, an HDD, an SSD, etc. In the storage device 121c, a control program for controlling the operation of the processing device, a process recipe describing procedures and conditions for substrate processing to be described later, etc. are recorded and stored in a readable manner. The process recipe is a combination of each procedure in the substrate processing to be described later, which is executed by the controller 121 on the processing device so as to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. Also, the process recipe is simply referred to as a recipe. When the term "program" is used in this specification, it may include only the recipe alone, only the control program alone, or both of them.

[0028] The I / O port 121d is connected to the MFCs 241a to 241h, the valves 243a to 243h, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the temperature sensor 263, the heater 207, the rotation mechanism 267, the boat elevator 115, the shutter opening / closing mechanism 115s, etc. The I / O port 121d may be further connected to an etching unit.

[0029] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to be able to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a is configured to control various operations such as the flow rate adjustment operation of various substances by the MFCs 241a to 241h, the opening and closing operations of the valves 243a to 243h, the opening and closing operation of the APC valve 244, the pressure adjustment operation by 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 boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the content of the read recipe. The CPU 121a may further be configured to be able to control an etching unit.

[0030] The controller 121 can be configured by installing the above-described program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory or an SSD, and the like. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term "recording medium" is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using communication means such as the Internet.

[0031] (2) Substrate processing step Using the above-described substrate processing apparatus and the like, as one step of the manufacturing process (manufacturing method) of a semiconductor device, an example of a processing sequence for forming a film on the surface of a wafer 200 as a substrate will be mainly described with reference to FIGS. 4(a) to 4(f). Among the series of processing sequences shown below, some steps (steps A1, A2, C, B1) are performed by the above-described substrate processing apparatus. At this time, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0032] In the processing sequence in this aspect, (a) In the wafer 200 having a structure in which the surfaces of the first material, the second material, and the third material are adjacent to each other in this order, a first dielectric film containing oxygen is selectively formed on the surface of the first material, and a second dielectric film containing oxygen is selectively formed on the surface of the third material, each with respect to the surface of the second material in step A; (b) Step B of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls is performed.

[0033] In the following example, in step A, as shown in FIGS. 4(a) and 4(b), (a-1) Step A1 of selectively forming a first adsorption inhibition layer that inhibits the adsorption of the first raw material on the surface of the second material with respect to the surfaces of the first material and the third material respectively; (a-2) Step A2 of forming a first dielectric film on the surface of the first material and a second dielectric film on the surface of the third material respectively by supplying the first raw material to the wafer 200; will be described.

[0034] Also, in the following example, after performing step A, as shown in FIG. 4(c), By supplying an oxidizing agent to the wafer 200, a part of the first material in contact with the interface between the first material and the first dielectric film is modified into a first substitution oxide film through the first dielectric film, and a part of the third material in contact with the interface between the third material and the second dielectric film is modified into a second substitution oxide film through the second dielectric film. The case of further performing step C will be described. In the following example, the case where step C is performed before performing step B will be described.

[0035] Also, in the following example, in step B, as shown in FIGS. 4(d) and 4(e), (b-1) Step B1 of forming an embedded film that fills the inside of the recess and covers at least a part of the upper surfaces of the first dielectric film and the second dielectric film; (b-2) Step B2 of leaving the portion formed in the recess in the embedded film as a separation film and removing the other portions; will be described.

[0036] Also, in the following example, after performing step B, as shown in FIG. 4(f), The case of further performing step D of sequentially laminating a tunnel oxide film and a channel film on the surface of the wafer 200, that is, on the surfaces of the separation film, the first dielectric film, and the second dielectric film formed on the wafer 200 will be described.

[0037] As used herein, the term "wafer" may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. As used herein, the phrase "surface of the wafer" may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is described herein that "a predetermined layer is formed on the surface of 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 or the like formed on the wafer. When the term "substrate" is used herein, it has the same meaning as when the term "wafer" is used.

[0038] As used herein, the terms "agent" and "substance" include at least one of gaseous substances and liquid substances. The liquid substance includes mist-like substances. That is, each of the modifier, the first to third raw materials, and the reactants (oxidizing agent, nitriding agent) described later may include a gaseous substance, may include a liquid substance such as a mist-like substance, or may include both of them.

[0039] Hereinafter, the processing sequence in this embodiment will be specifically described.

[0040] When a plurality of wafers 200 are loaded (wafer charge) into the boat 217, the shutter 219s is moved to open the lower end opening of the manifold 209 (shutter open). Thereafter, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load).

[0041] As shown in Fig. 4(a) and the like, the wafer 200 to be processed has, on its surface, a structure in which the surfaces of the first material, the second material, and the third material are adjacent to each other in this order (hereinafter also referred to as an adjacent structure). The surfaces of the first material, the second material, and the third material are formed on the same plane. There may be a three-dimensional structure such as a trench or a hole provided on the surface of the wafer 200, and the above-described adjacent structure may be provided on a three-dimensional portion such as the side wall surface of the trench or the hole. Further, the above-described adjacent structure may be provided on a flat portion on the surface of the wafer 200. The second material can be an oxide, and each of the first material and the third material can be at least one of an oxide or a non-oxide having a smaller oxygen content ratio (i.e., the ratio of oxygen in the material composition or the oxygen content concentration) than the second material. For example, each of the first material and the third material can be a nitride such as silicon nitride (SiN), and the second material can be an oxide such as silicon oxide (SiO). Further, each of the first material and the third material may be a material in which at least a part of the surface of a non-oxide such as SiN is naturally oxidized. Even in this case, the naturally oxidized surface has a smaller oxygen content ratio than the second material.

[0042] After the boat load is completed, vacuum evacuation (pressure reduction evacuation) is performed by the vacuum pump 246 so that the inside of the processing chamber 201 reaches a desired pressure (degree of vacuum). Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature. Further, the rotation of the wafer 200 by the rotation mechanism 267 is started. Exhaustion of the inside of the processing chamber 201, heating of the wafer 200, and rotation are all continuously performed until at least the processing of the wafer 200 is completed.

[0043] (Step A) Subsequently, the following steps A1 and A2 are performed on the wafer 200 prepared in the processing chamber 201.

[0044] [Step A1: Formation of the first adsorption inhibition layer] In this step, valve 243c is opened to supply a modifier (inhibitor) to wafer 200. At this time, valves 243f - 243h may be opened to supply an inert gas into processing chamber 201.

[0045] By performing step A1 under the processing conditions described later, as shown in Fig. 4(a), a first adsorption inhibition layer (first inhibitor layer) that inhibits the adsorption of the first raw material can be selectively formed on the surface of the second material with respect to the surfaces of the first material and the third material. The first adsorption inhibition layer contains at least a part of the molecular structure of the molecules constituting the modifier. In the present disclosure, the phrase "selectively form a first adsorption inhibition layer on the surface of the second material" does not mean "form the first adsorption inhibition layer only on the surface of the second material", but means "preferentially form the first adsorption inhibition layer on the surface of the second material among the surfaces of the first material, the second material, and the third material". That is, this phrase does not completely exclude the formation of the first adsorption inhibition layer on the surface of the first material or the formation of the first adsorption inhibition layer on the surface of the third material. This phrase "selectively" is used with substantially the same meaning in each of the following steps.

[0046] After selectively forming the first adsorption inhibition layer on the surface of the second material, valve 243c is closed to stop the supply of the modifier to wafer 200. Then, the inside of processing chamber 201 is evacuated to remove gaseous substances and the like remaining in processing chamber 201 from inside processing chamber 201. Also, valves 243f - 243h are opened to supply an inert gas into processing chamber 201 to purge (purge) the inside of processing chamber 201.

[0047] As the modifier, for example, alkylaminosilanes such as (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) can be used.

[0048] In addition, as the modifier, for example, aminosilanes such as 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), (diisopropylamino)silane (SiH3[N(C3H7)2]), etc. can be used.

[0049] As the modifier, one or more of these silicon (Si)-containing substances can be used.

[0050] When supplying the Si-containing substance as the modifier in Step A1, the processing conditions are as follows: Processing temperature: room temperature (25°C) to 500°C, preferably room temperature to 250°C Processing pressure: 5 to 1000 Pa Processing time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Modifier supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm are exemplified.

[0051] Note that the notation of a numerical range such as "25 to 500°C" in this specification means that the lower limit value and the upper limit value are included in that range. Therefore, for example, "25 to 500°C" means "25°C or higher and 500°C or lower". The same applies to other numerical ranges. Also, the processing temperature in this specification means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure means the pressure inside the processing chamber 201. Also, the processing time means the time for which the processing is continued. Also, when 0 slm is included in the supply flow rate, 0 slm means the case where the substance is not supplied. These are the same in the following description.

[0052] In addition, as the modifier, fluorine (F2), nitrogen trifluoride (NF3), chlorine trifluoride (ClF3), hydrogen fluoride (HF), etc. can be used. As the modifier, one or more of these fluorine (F)-containing substances can be used.

[0053] As the processing conditions for supplying the F-containing substance as the modifier in Step A1, Processing temperature: room temperature (25°C) to 300°C, preferably room temperature to 200°C Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa Processing time: 1 second to 60 minutes Modifier supply flow rate: 0.001 to 2 slm, preferably 0.001 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm are exemplified.

[0054] Note that in Step A1, Step A1(Si) of supplying the Si-containing substance as the modifier to the wafer 200 and Step A1(F) of supplying the F-containing substance as the modifier can be performed in this order.

[0055] [Step A2: Formation of the first dielectric film and the second dielectric film] In this step, after forming the first adsorption inhibition layer on the surface of the second material, the following steps (first raw material supply, reactant supply) are performed on the wafer 200. As the reactant, an oxidizing agent can be used.

[0056] [First raw material supply] In this step, the valve 243a is opened to supply the first raw material to the wafer 200. At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201.

[0057] By performing this step (first raw material supply) under the processing conditions described later, an adsorption layer of the first raw material can be selectively formed on the surfaces of the first material and the third material with respect to the surface of the second material. The adsorption layer of the first raw material contains at least a part of the molecular structure of the molecules constituting the first raw material.

[0058] After forming the adsorption layer of the first raw material, close valve 243a to stop the supply of the first raw material to wafer 200. Then, by the above-described procedure, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201, and processing chamber 201 is purged with an inert gas (purging).

[0059] 〔Reagent Supply〕 In this step, open valve 243b to supply a reagent to wafer 200. At this time, valves 243f to 243h may be opened to supply an inert gas into processing chamber 201.

[0060] By performing this step (reagent supply) under the processing conditions described below, the adsorption layer of the first raw material selectively formed on the surfaces of the first material and the third material can be modified. When an oxidizing agent is used as the reagent, the adsorption layer of the first raw material can be oxidized to form an oxide layer containing the constituent elements of the first raw material on the surfaces of the first material and the third material, respectively.

[0061] After modifying the adsorption layer of the first raw material, close valve 243b to stop the supply of the reagent to wafer 200. Then, by the above-described procedure, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201, and processing chamber 201 is purged with an inert gas.

[0062] 〔Perform a Predetermined Number of Times〕 Then, a cycle including the first raw material supply and the reagent supply is performed a predetermined number of times (n A times. n A(where \(n\) is an integer of 1 or 2 or more). As a result, as shown in FIG. 4(b), a first dielectric film can be selectively formed on the surface of the first material and a second dielectric film can be selectively formed on the surface of the third material with respect to the surface of the second material. When a metal-containing substance is used as the first raw material and an oxidizing agent is used as the reactant, as the first dielectric film and the second dielectric film, for example, metal oxide films such as aluminum oxide film (AlO film), titanium oxide film (TiO film), hafnium oxide film (HfO film), zirconium oxide film (ZrO film), etc., that is, dielectric films containing oxygen (O) having a higher electron trap density than the SiN film can be formed. As the dielectric film, a high-k dielectric film (High-k film) can be particularly applied. By forming the first dielectric film and the second dielectric film, a recess will be formed on the surface of the wafer 200 with the first dielectric film and the second dielectric film as side walls and the surface of the second material as the bottom.

[0063] Note that the statement "selectively form a first dielectric film on the surface of the first material and a second dielectric film on the surface of the third material with respect to the surface of the second material" does not completely exclude the formation of the first dielectric film and the second dielectric film on the surface of the second material as described above. Therefore, for example, due to a part of the first adsorption inhibition layer desorbing during the process of step A2, a discontinuous oxide layer may be formed on a part of the surface of the second material. Also, for example, as shown in FIG. 4(b), in step A2, the first dielectric film can be formed so as to protrude (i.e., overhang, cover, cross the border) to the side of the surface of the second material rather than the boundary between the surface of the second material and the surface of the first material. This is because during the process of repeating the cycle of forming the first dielectric film, the first dielectric film itself can grow so as to protrude above the second material with the first dielectric film as the base. Also, for example, in step A2, the second dielectric film can be formed so as to protrude (i.e., overhang, cover, cross the border) to the side of the surface of the second material rather than the boundary between the surface of the second material and the surface of the third material, similar to the first dielectric film.

[0064] As the first raw material, for example, aluminum trichloride (AlCl3), trimethylaluminum (Al(CH3)3), titanium tetrachloride (TiCl4), hafnium tetrafluoride (HfF4), tetrakis(ethylmethylamino)hafnium (Hf[N(CH3)(CH2CH3)]4), zirconium tetrafluoride (ZrF4), tetrakis(ethylmethylamino)zirconium (Zr[N(CH3)Cp]4), etc. can be used. As the first raw material, one or more of these substances, that is, substances containing metal elements such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), etc. (organometals or metal halides) can be used.

[0065] As the reactant (oxidizing agent), for example, oxygen (O2), ozone (O3), water vapor (H2O), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon dioxide (CO2), carbon monoxide (CO), etc. can be used. As the reactant, one or more of these oxygen-containing substances can be used. Here, in order to suppress the rapid desorption of the first adsorption inhibition layer by the reactant, it is preferable to use a reactant with relatively weak oxidizing power. For example, a reactant with weaker oxidizing power than the oxidizing agent used in step C described later can be used. However, when using a modifier that is difficult to desorb with respect to the oxidizing agent, and when it is possible to use a reactant with strong oxidizing power, a relatively strong oxidizing agent exemplified in step C described later can also be used.

[0066] As the processing conditions when supplying the first raw material in step A2, Processing temperature: room temperature (25°C) to 500°C, preferably 350 to 400°C Processing pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa Processing time: 1 to 180 seconds, preferably 10 to 120 seconds First raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm are exemplified.

[0067] As the processing conditions for supplying the reactant in Step A2, Processing pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa Reactant supply flow rate: 0.01 to 20 slm, preferably 0.01 to 10 slm are exemplified. Other processing conditions can be the same as those in the case of supplying the first raw material.

[0068] Note that a nitriding agent can also be used as the reactant. As the reactant, for example, hydrogen nitrides such as ammonia (NH3), diazene (N2H2), hydrazine (N2H4), N3H8, etc. can be used. As the reactant, one or more of these nitrogen (N)-containing substances can be used. When a Si-containing substance is used as the first raw material and a nitriding agent is used as the reactant, a SiN film can be formed as the first dielectric film and the second dielectric film.

[0069] (Step C: Formation of the first substitutional oxide film and the second substitutional oxide film) Subsequently, Step C is performed on the wafer 200 after the first dielectric film and the second dielectric film are formed on the surface.

[0070] In this step, the valve 243b is opened, and a reactant containing oxygen (i.e., an oxidizing agent) is supplied to the wafer 200. At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201.

[0071] By performing Step C under the processing conditions described below, a part of the first material in contact with the interface between the first material and the first dielectric film is modified (oxidized) into the first substitution oxide film through the first dielectric film, and a part of the third material in contact with the interface between the third material and the second dielectric film is modified (oxidized) into the second substitution oxide film through the second dielectric film. The first substitution oxide film and the second substitution oxide film will be formed as, for example, SiO films or SiON films. Note that in Step C, it is possible to further enhance the characteristics of the first dielectric film and the second dielectric film without impairing the characteristics as oxide films that they have. For example, it is possible to re-oxidize (post-oxidize) the first dielectric film and the second dielectric film, desorb impurities from these films, and densify these films.

[0072] Note that Step C is performed after Step A and before Step B, that is, in a state where there are no other films or the like formed so as to be in contact with the upper surfaces and side surfaces of the first dielectric film and the second dielectric film. Therefore, in Step C, due to the expansion caused by the modification of a part of the first material into the first substitution oxide film, the first dielectric film formed on the first substitution oxide film can be moved. Also, due to the expansion caused by the modification of a part of the third material into the second substitution oxide film, the second dielectric film formed on the second substitution oxide film can be moved. That is, in Step C, by expanding a part of the first material and the second material in a state where there are no other films or the like that inhibit the movement of the first dielectric film and the second dielectric film, it is possible to move (lift) these films in a stress-free state while suppressing the application of film stress such as compressive stress to the first dielectric film and the second dielectric film.

[0073] In addition, in the aforementioned step A2, when at least one of the first dielectric film and the second dielectric film is formed to protrude toward the surface side of the second material, a first adsorption inhibition layer is formed between the portion protruding toward the surface side of the second material and the surface of the second material, and the two are separated by the first adsorption inhibition layer. Therefore, in step C, even when a part of the first material and the second material expands, the movement of the first dielectric film and / or the second dielectric film is not inhibited by the bonding (adhesion) between the portion formed to protrude of the first dielectric film and / or the second dielectric film and the surface of the second material, and an increase in film stress can be suppressed.

[0074] After completing the above modification, close valve 243b and stop the supply of the oxidant into processing chamber 201. Then, according to the above procedure, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201, and processing chamber 201 is purged with an inert gas.

[0075] As the oxidant, for example, ozone (O3), oxygen (O2) + hydrogen (H2), O2 + deuterium (D2), O3 + H2, O3 + D2, hydrogen peroxide (H2O2), oxygen-containing substances such as O2 or O3 excited to a plasma state can be used. As the oxidant, one or more of these can be used. Here, the combined description of two substances such as "O2 + H2" means a mixture of O2 and H2. When supplying a mixture, the two substances may be mixed (premixed) in the supply pipe and then supplied into processing chamber 201, or the two substances may be separately supplied into processing chamber 201 from different supply pipes and mixed (postmixed) in processing chamber 201. In addition, when it is possible to form the first substitution oxide film and the second substitution oxide film through the first dielectric film and the second dielectric film by adjusting processing conditions and the like, an oxidant with relatively weak oxidizing power exemplified in step A described above can also be used.

[0076] As processing conditions when supplying the oxidant in step C, Processing temperature: 350 to 1000 °C, preferably 400 to 650 °C Processing pressure: 1 to 105,000 Pa, preferably 10 to 10,000 Pa Processing time: 1 to 10,000 seconds, preferably 5 to 3,600 seconds Oxidant supply flow rate: 0.01 to 10 slm, preferably 0.1 to 5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0077] (Step B) Subsequently, after the first substitution oxide film and the second substitution oxide film are formed, the following steps B1 and B2 are performed on the wafer 200.

[0078] [Step B1: Embedded film formation] In this step, the following steps (second raw material supply, reactant supply) are performed on the wafer 200. As the reactant, for example, an oxidant can be used. In at least one of the steps of the second raw material supply and the reactant supply, a catalyst can be supplied to the wafer 200. Hereinafter, the case where the catalyst is supplied in both steps of the second raw material supply and the reactant supply will be described.

[0079] [Second raw material supply] In this step, the valves 243d and 243e are opened, and the second raw material and the catalyst are supplied to the wafer 200. At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201.

[0080] By performing this step (second raw material supply) under the processing conditions described below, an adsorption layer of the second raw material can be formed in the recesses with the first dielectric film and the second dielectric film as side walls, and on at least a part of the upper surfaces of the first dielectric film and the second dielectric film. The adsorption layer of the second raw material contains at least a part of the molecular structure of the molecules constituting the second raw material.

[0081] After forming the adsorption layer of the second raw material, close valves 243d and 243e to stop the supply of the second raw material and the catalyst to wafer 200. Then, by the above-described procedure, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201, and processing chamber 201 is purged with an inert gas (purging).

[0082] 〔Reactant Supply〕 In this step, open valves 243b and 243e to supply the reactant and the catalyst to wafer 200. At this time, valves 243f to 243h may be opened to supply an inert gas into processing chamber 201.

[0083] By performing this step (reactant supply) under the processing conditions described later, the adsorption layer of the second raw material formed in the recess having the first dielectric film and the second dielectric film as side walls, and the adsorption layer of the second raw material formed on at least a part of the upper surfaces of the first dielectric film and the second dielectric film can be respectively modified. When an oxidant is used as the reactant, the adsorption layer of the second raw material is oxidized, and an oxide layer containing the constituent elements of the second raw material can be formed in the recess having the first dielectric film and the second dielectric film as side walls, and on at least a part of the upper surfaces of the first dielectric film and the second dielectric film respectively.

[0084] After modifying the adsorption layer of the second raw material, close valves 243b and 243e to stop the supply of the reactant and the catalyst to wafer 200. Then, by the above-described procedure, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201, and processing chamber 201 is purged with an inert gas.

[0085] 〔Perform a Predetermined Number of Times〕 Then, a cycle including the second raw material supply and the reactant supply is performed a predetermined number of times (n B times. n Bis performed one or more times (wherein the number of times is an integer of 1 or more). As a result, as shown in FIG. 4(d), an embedded film can be formed in the recess having the first dielectric film and the second dielectric film as side walls, and on at least a part of the upper surface of each of the first dielectric film and the second dielectric film. This cycle is executed until the recess is filled with the embedded film. When a Si-containing substance is used as the second raw material and an oxidizing agent is used as the reactant, an oxide film, for example, a silicon oxide film (SiO film), can be formed as the embedded film.

[0086] As the second raw material, for example, the above-mentioned alkylaminosilane or aminosilane can be used. Further, as the second raw material, chlorosilanes such as dichlorosilane (SiH2Cl2), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), octachlorotrisilane (Si3Cl8), etc. can be used. As the second raw material, one or more of these Si-containing substances can be used.

[0087] As the reactant (oxidizing agent), one or more of the above-mentioned O-containing substances can be used.

[0088] As the catalyst, for example, pyridine (C5H5N), picoline (C6H7N), lutidine (C7H9N), triethylamine ((C2H5)3N), etc. can be used. As the catalyst, one or more of these amines can be used.

[0089] As the processing conditions when supplying the second raw material and the catalyst in step B1, Processing temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C Processing pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa Processing time: 1 to 180 seconds, preferably 10 to 120 seconds Second raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Catalyst supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm are exemplified.

[0090] When supplying the reactant and the catalyst in Step B1, the processing conditions are as follows: Processing pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa Reactant supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Catalyst supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm These are exemplified. Other processing conditions can be the same as those during the supply of the second raw material and the catalyst.

[0091] After the formation of the embedded film on the surface of the wafer 200 is completed, the inside of the processing chamber 201 is purged, and gases, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (after purge). Then, the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is restored to normal pressure (atmospheric pressure restoration). Then, the processed wafer 200 is carried out of the reaction tube 203 (boat unloading) and taken out from the boat 217 (wafer discharge). Note that after the boat unloading, the lower end opening of the manifold 209 is sealed by the shutter 219s (shutter close).

[0092] [Step B2: Separation film formation] Subsequently, Step B2 is performed on the wafer 200 after the wafer discharge, that is, the wafer 200 after the embedded film is formed on the surface.

[0093] In step B2, among the embedded films formed on the surface of the wafer 200, the portion formed in the concave portion is left as a separation film, and the other portions are removed so that at least a part of the first dielectric film and the second dielectric film are exposed. The partial removal of the embedded film can be performed, for example, by anisotropic etching using a plasma-excited etching gas, such as a carbon fluoride (CF)-based gas. The anisotropic etching can be performed, for example, using the above-described etching unit as a plasma etching apparatus according to known processing procedures and processing conditions. As the CF-based gas, for example, one or more of CF4 gas, C4F6 gas, C4F8 gas, CH2F2 gas, and CHF3 gas can be used. Note that the partial removal of the embedded film is not limited to the case of being performed by anisotropic etching. When the above-described adjacent structure is provided on a flat portion on the surface of the wafer 200, the partial removal of the embedded film can also be performed, for example, by CMP (chemical mechanical polishing).

[0094] By performing step B2, as shown in FIG. 4(e), the surface of the wafer 200 is in a state where the first dielectric film, the separation film, and the second dielectric film are exposed adjacent to each other in this order. The first dielectric film and the second dielectric film are physically and electrically separated (isolated) with the separation film interposed therebetween. When the partial removal of the embedded film is performed by anisotropic etching or CMP as described above, the entire exposed surfaces of the first dielectric film, the separation film, and the second dielectric film can be made into smooth surfaces (flat surfaces or curved surfaces) that are adjacent to each other without a step.

[0095] (Step D: Tunnel Oxide Film and Channel Film Formation) Subsequently, step D is performed on the wafer 200 after the first substitution oxide film and the second substitution oxide film are formed.

[0096] In this step, a tunnel oxide film and a channel film are sequentially laminated on the surfaces of the isolation film, the first dielectric film, and the second dielectric film formed on the wafer 200. The formation of the tunnel oxide film and the channel film can be performed by known methods, each of which is known as a part of the manufacturing process of memory cells in a flash memory. Note that step D may be performed in the above-described processing chamber 201 in which steps A1, A2, C, and B1 are performed, or may be performed in a processing chamber of another substrate processing apparatus.

[0097] Through the above steps A to D, the laminated structure shown in FIG. 4(f) is manufactured.

[0098] This laminated structure can be suitably used, for example, as a part of the components of a memory cell of a flash memory. That is, the first dielectric film and the second dielectric film formed by the above-described method are configured as metal oxide films and have a higher electron trap density than the SiN film, and are precisely formed with high dimensional accuracy so as to have an appropriate shape. Therefore, they can be suitably used as the charge trap layers of the memory cell, respectively. In addition, since the isolation film is composed of an oxide film such as a SiO film, it can be suitably used as an isolation layer for insulating between adjacent charge trap layers in the memory cell of the flash memory. In addition, since the first substitution oxide film and the second substitution oxide film are composed of an oxide film (SiO film or SiON film), they can be suitably used as blocking layers for suppressing carrier leakage from the charge trap layer, respectively.

[0099] (3) Effects according to this aspect According to this aspect, one or more of the following effects can be obtained.

[0100] (a) According to this aspect, it becomes possible to precisely form a film on a substrate. That is, in the above-mentioned step A, in a substrate having the above-mentioned structure in which the surfaces of the first to third materials are adjacent to each other, a dielectric film (first dielectric film, second dielectric film) can be selectively formed on the surface of the base layer composed of a specific material (first material, third material). These formed dielectric films can be suitably used, for example, as a charge trap layer or the like in a memory cell of a flash memory. Also, in the above-mentioned step B, it becomes possible to form a separation film between these dielectric films. The formed separation film can be suitably used, for example, as a separator or the like that separates adjacent charge trap layers in a memory cell of a flash memory.

[0101] (b) Since the first material to the third material are the above-mentioned materials, the above-mentioned effects can be obtained more reliably. For example, since the first material to the third material are the above-mentioned materials, by utilizing the OH-terminated (hydroxyl-terminated) groups selectively formed on the surface of the second material which is an oxide, the first dielectric film and the second dielectric film can be selectively formed on the surfaces of the first material and the third material, respectively. Also, since the first material to the third material are the above-mentioned materials, the structure in which they are adjacent in this order can be suitably used, for example, as a part of the components of a memory cell of a flash memory.

[0102] (c) Since the separation film is an oxide film such as a SiO film, the above-mentioned effects can be obtained more reliably. Also, since the separation film is an oxide film such as a SiO film, this film can be suitably used, for example, as a separation layer that insulates between adjacent charge trap layers in a memory cell of a flash memory.

[0103] (d) Since each of the first dielectric film and the second dielectric film is an oxide film such as a metal oxide film, each of the first dielectric film and the second dielectric film can be suitably used, for example, as a charge trap layer of a memory cell.

[0104] In addition, since each of the first dielectric film and the second dielectric film is an oxide film such as a metal oxide film, when forming the first substituted oxide film and the second substituted oxide film in step C, even if oxidation (modification) is performed on a part of the first material and a part of the third material through the first dielectric film and the second dielectric film, the characteristics of these films as oxide films can be maintained as they are. On the other hand, for example, when the first dielectric film and the second dielectric film are nitride films, if oxidation is performed on a part of the first material and a part of the third material through the first dielectric film and the second dielectric film, at least a part of the nitrogen in the film will desorb, and it may become difficult to maintain the characteristics of these films as nitride films.

[0105] In addition, since each of the first dielectric film and the second dielectric film has an electron trap density larger than that of a silicon nitride film, these films can be suitably used, for example, as a charge trap layer of a memory cell.

[0106] (e) In step A, by performing the above-described steps A1 and A2, each of the first dielectric film and the second dielectric film can be efficiently and selectively formed on the surface of the second material.

[0107] (f) In step A, by forming the first dielectric film so as to protrude to the side of the surface of the second material rather than the boundary between the surface of the second material and the surface of the first material, and by forming the second dielectric film so as to protrude to the side of the surface of the second material rather than the boundary between the surface of the second material and the surface of the third material, it becomes possible to make these films have a suitable shape and size when used as a charge trap layer of a memory cell. For example, by making the film have such a shape, it becomes easy to secure a sufficient area as a charge trap layer of a memory cell.

[0108] (g) After step A, by performing step C of supplying an oxidizing agent to the wafer 200, it becomes possible to form the first substitution oxide film and the second substitution oxide film as oxide films having high insulation properties so as to be adjacent to the first dielectric film and the second dielectric film. Further, by performing modification (oxidation) through the first dielectric film and the second dielectric film, the film quality of the first dielectric film and the second dielectric film can be improved, and these films can be made into more suitable films, for example, as a charge trap layer of a memory cell.

[0109] (h) In step C, due to the expansion caused by the modification of a part of the first material into the first substitution oxide film, the first dielectric film can be moved (lifted), and due to the expansion caused by the modification of a part of the third material into the second substitution oxide film, the second dielectric film can be moved (lifted). That is, in step C, each of the first dielectric film and the second dielectric film can be lifted without compressing them. By these, it becomes possible to avoid the quality degradation of each of the first dielectric film and the second dielectric film. Note that by performing step C before performing step B, that is, before forming the separation film, the effects described here can be obtained more reliably.

[0110] (i) When performing steps B1 and B2 in step B, by forming a separation film using the recess having the first dielectric film and the second dielectric film as side walls as a frame, it becomes possible to form the separation film with good controllability and high dimensional accuracy. Further, by covering at least a part of the upper surfaces of the first dielectric film and the second dielectric film with an embedding film in step B1 and removing the unnecessary part of the embedding film in step B2, the separation film can be made into a film without voids or the like that fills the inside of the recess without gaps. By these, the separation film can be suitably used, for example, as a separation layer that insulates between adjacent charge trap layers.

[0111] Also, in step B1, by performing a cycle including the second raw material supply and the reactant supply a predetermined number of times, it becomes possible to form the embedded film with good step coverage and good controllability. As a result, the quality of the separation membrane can be improved, and this membrane can be suitably used, for example, as the separation membrane of the charge trap layer.

[0112] (j) Since the surfaces of the first material, the second material, and the third material are aligned on the same plane, the laminated structure obtained through steps A and B can be suitably used, for example, as a part of the components of the memory cell of a flash memory.

[0113] (k) If the first dielectric film and the second dielectric film formed by the method of the present disclosure are used, for example, as the films constituting the charge trap layer of the memory cell, it becomes possible to improve the performance of the flash memory device.

[0114] (l) The above-described effects can be similarly obtained even when a predetermined substance is arbitrarily selected and used from the above-described various modifiers, various raw materials, various reactants (oxidants), and various inert gases.

[0115] <Other aspects of the present disclosure> The aspects of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above-described aspects, and various modifications can be made without departing from the gist thereof.

[0116] For example, after performing step A, step B may be performed without performing step C. In this case, in step B, by supplying a second raw material and an oxidizing agent to the wafer 200, a separation film is formed, and through the first dielectric film, a part of the first material in contact with the interface between the first material and the first dielectric film is modified into a first substitution oxide film, and through the second dielectric film, a part of the third material in contact with the interface between the third material and the first dielectric film may be modified into a second substitution oxide film. In step B1, by using an oxidizing agent having a strong oxidizing power exemplified in step C (O3, O2 + H2, O2 + D2, O3 + H2, O3 + D2, H2O2, O2 or O3 excited to a plasma state, etc.), as described herein, the formation of the separation film, the modification of a part of the first material into the first substitution oxide film, and the modification of a part of the third material into the second substitution oxide film can proceed simultaneously in parallel, and it becomes possible to improve the productivity of the device.

[0117] Also, for example, in step B, after forming the first dielectric film and the second dielectric film on the surface of the wafer 200, (b-1) Step B1' of selectively forming a second adsorption inhibition layer (second inhibitor layer) that inhibits the adsorption of the second raw material on the surfaces of the first dielectric film and the second dielectric film on the surface of the second material; (b-2) Step B2' of selectively forming a separation film on the surface of the second material with respect to the surfaces of the first dielectric film and the second dielectric film by supplying the second raw material to the wafer 200; may be performed.

[0118] The processing procedures and processing conditions in step B1' can be the same as, for example, the processing procedures and processing conditions in step A1 (first adsorption inhibition layer formation) described above. The processing procedures and processing conditions in step B2' can be the same as, for example, the processing procedures and processing conditions in step B1 (embedded film formation) described above.

[0119] Even in this case, the same effects as those in the above-described embodiments can be obtained. Also, in such a case, it becomes possible to efficiently form the separation film selectively on the surface of the second material with respect to the surfaces of the first dielectric film and the second dielectric film. Further, after the formation of the separation film, the implementation of step B2 for removing the unnecessary embedding film can be omitted, and it becomes possible to improve the productivity of the device.

[0120] In addition, in step B, when performing steps B1' and B2', it is preferable to perform step B2' until the inside of the recess is filled with the separation film without any gaps. By filling the inside of the recess with the separation film without any gaps, this film can be suitably used as a separation layer for insulating between adjacent charge trap layers in the memory cell of the flash memory.

[0121] The recipe used for each process is preferably prepared individually according to the process content, recorded and stored in the storage device 121c via a telecommunication line or an external storage device 123. Then, when starting each process, it is preferable for the CPU 121a to appropriately select an appropriate recipe according to the process content from among the plurality of recipes recorded and stored in the storage device 121c. As a result, it becomes possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility in the processing device. Also, the burden on the operator can be reduced, operation mistakes can be avoided, and each process can be started quickly.

[0122] The above-described recipe is not limited to the case of newly creating it. For example, it may be prepared by changing an existing recipe already installed in the processing device. When changing the recipe, the changed recipe may be installed in the processing device via a telecommunication line or a recording medium on which the recipe is recorded. Also, the input / output device 122 provided in the existing processing device may be operated to directly change the existing recipe already installed in the processing device.

[0123] In the above-described aspect, an example of performing a film-forming process using a batch-type processing apparatus that processes a plurality of substrates at once has been described. The present disclosure is not limited to the above-described aspect, and for example, it can also be suitably applied when performing a film-forming process using a single-wafer type processing apparatus that processes one or several substrates at once. Further, in the above-described aspect, an example of performing a film-forming process using a processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-described aspect, and it can also be suitably applied when performing a film-forming process using a processing apparatus having a cold-wall type processing furnace.

[0124] Also, in the above-described aspect, an example of continuously performing (in-situ) a series of processing sequences leading to steps A1, A2, C, B1 in the same processing chamber of the same processing apparatus has been described. The present disclosure is not limited to the above-described aspect. Any one of steps A1, A2, C, B1 and any other one of the steps may be performed (ex-situ) in different processing chambers of different processing apparatuses, or may be performed in different processing chambers of the same processing apparatus, respectively.

[0125] Even when using these processing apparatuses, each process can be performed under the same processing procedures and processing conditions as in the above-described aspect and modified examples, and the same effects as in the above-described aspect and modified examples can be obtained.

[0126] The above-described aspect and modified examples can be used in appropriate combinations. At this time, the processing procedures and processing conditions can be, for example, the same as the processing procedures and processing conditions of the above-described aspect and modified examples.

Description of Reference Numerals

[0127] 200 Wafer (substrate)

Claims

1. (a) In a substrate having a structure in which the surfaces of a first material, a second material, and a third material are adjacent to each other in this order, a first dielectric film containing oxygen is formed on the surface of the first material, and a second dielectric film containing oxygen is formed on the surface of the third material, each selectively with respect to the surface of the second material; (b) forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls; A substrate processing method comprising:

2. The substrate processing method according to claim 1, wherein the second material is an oxide, and the first material and the third material are each at least one of an oxide having a lower oxygen content ratio than the second material or a non-oxide.

3. The substrate processing method according to claim 1, wherein the first material and the third material are each a nitride, and the second material is an oxide.

4. The substrate processing method according to claim 1, wherein the first material and the third material are each silicon nitride, and the second material is silicon oxide.

5. The substrate processing method according to any one of claims 2 to 4, wherein the separation film is an oxide film.

6. The substrate processing method according to any one of claims 2 to 4, wherein the separation film is a silicon oxide film.

7. The substrate processing method according to claim 1, wherein the first dielectric film and the second dielectric film are each a metal oxide film.

8. (a) includes: (a-1) selectively forming a first adsorption inhibition layer that inhibits the adsorption of a first raw material on the surface of the second material, with respect to the surfaces of the first material and the third material; (a-2) forming the first dielectric film on the surface of the first material and the second dielectric film on the surface of the third material, respectively, by supplying the first raw material to the substrate. The substrate processing method according to claim 1.

9. In (a), the first dielectric film is formed so as to protrude to a side of the surface of the second material rather than a boundary between the surface of the second material and the surface of the first material, according to the substrate processing method of claim 1.

10. (c) After (a), a step of reforming a part of the first material in contact with an interface between the first material and the first dielectric film into a first substitution oxide film by supplying an oxidizing agent to the substrate through the first dielectric film, according to the substrate processing method of claim 1.

11. The substrate processing method according to claim 10, wherein in (c), the first dielectric film is moved by expansion caused by modification of a part of the first material into the first substitution oxide film.

12. The substrate processing method according to claim 10, wherein (c) is performed before (b).

13. The substrate processing method according to claim 1, wherein in (b), a second raw material and an oxidizing agent are supplied to the substrate to form the separation film, and a part of the first material in contact with the interface between the first material and the first dielectric film through the first dielectric film is modified into a first substitution oxide film.

14. (b) is (b-1) a step of forming an embedding film that fills the inside of the recess and covers at least a part of the upper surfaces of the first dielectric film and the second dielectric film; (b-2) a step of leaving a portion formed in the recess in the embedding film as the separation film and removing other portions. The substrate processing method according to claim 1, comprising:

15. (b) is (b-1) a step of selectively forming a second adsorption inhibition layer that inhibits adsorption of a second raw material on the surfaces of the first dielectric film and the second dielectric film with respect to the surface of the second material; (b-2) a step of selectively forming the separation film on the surface of the second material with respect to the surfaces of the first dielectric film and the second dielectric film by supplying the second raw material to the substrate. The substrate processing method according to claim 10, comprising:

16. In the substrate processing method according to claim 1, the surfaces of the first material, the second material, and the third material are formed on the same plane.

17. In the substrate processing method according to claim 1, the first dielectric film and the second dielectric film are respectively films constituting a charge trap layer of a memory cell.

18. (a) In a substrate having a structure in which the surfaces of a first material, a second material, and a third material are adjacent to each other in this order, a first dielectric film containing oxygen is selectively formed on the surface of the first material, and a second dielectric film containing oxygen is selectively formed on the surface of the third material with respect to the surface of the second material; (b) a step of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls. A method for manufacturing a semiconductor device, comprising:

19. In a substrate having a structure in which the surfaces of a first material, a second material, and a third material are adjacent to each other in that order, a procedure for selectively forming a first dielectric film containing oxygen on the surface of the first material and a second dielectric film containing oxygen on the surface of the third material, respectively, with respect to the surface of the second material; A procedure for forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls; A program that causes a computer to execute the procedures on a substrate processing apparatus.

20. A substrate processing apparatus used in the substrate processing method according to Claim 1, A first raw material supply system configured to supply a first raw material to the substrate; A control unit configured to be able to control the first raw material supply system so as to execute a process of forming the first dielectric film on the surface of the first material and the second dielectric film on the surface of the third material, respectively, by supplying the first raw material to the substrate; A substrate processing apparatus comprising the above.

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