Substrate processing method, semiconductor device manufacturing method, recording medium, and substrate processing apparatus

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a recording medium, and a substrate processing apparatus. The present invention addresses the problem of precisely forming a film on a substrate. [Solution] A substrate having a structure in which the surfaces of a first material, a second material, and a third material are adjacent in this order, a step 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 with respect to the surface of the second material; and (b) a step for forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

Description

Technical Field

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

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

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2021-136349 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] The present invention provides a technique capable of precisely forming a film on a substrate.

[0008] Means for Solving the Problems

[0009] According to one aspect of the present invention, there is provided a technique having: (a) a step of 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 in a substrate 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, with respect to the surface of the second material; and (b) a step of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

[0010] Advantages of the Invention

[0011] According to the present invention, a film can be precisely formed on a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention, and is a diagram showing a cross section of the processing furnace 202 part in a longitudinal sectional view.

[0013] Figure 2 It is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention, and is a diagram showing a cross section of the processing furnace 202 part in a longitudinal sectional view. Figure 1 It is a diagram showing a cross section of the processing furnace 202 part taken along the line A-A of

[0014] Figure 3 It is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one aspect of the present invention, and is a diagram showing a control system of the controller 121 in a block diagram.

[0015] Figure 4 In (a) is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step A1 of forming the first adsorption barrier layer on the surface of the second material; Figure 4 In (b) shows starting from the state of Figure 4 In (a), it is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step A2 of forming the first dielectric film on the surface of the first material and forming the second dielectric film on the surface of the third material; Figure 4 In (c) shows starting from the state of Figure 4 In (b), it is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step C of modifying a part of the first material into the first replacement oxide film and modifying a part of the third material into the second replacement oxide film; Figure 4 In (d) shows starting from the state of Figure 4 In (c), it is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step B1 of forming the embedding film on the wafer 200; Figure 4 In (e) shows starting from the state of Figure 4 In (d), it is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step B2 of removing a part of the embedding film and forming the separation film on the wafer 200; Figure 4 In (f) shows starting from the state of Figure 4 In (e), it is a partial cross-sectional enlarged view of the surface portion of the wafer 200 in one embodiment of the present invention after performing step D of sequentially laminating the tunnel oxide film and the channel film on the wafer 200.

[0016] Explanation of reference numerals

[0017] 200 Wafer (substrate) Detailed description of the invention

[0018] <One embodiment of the present invention>

[0019] Hereinafter, mainly with reference to Figures 1 to 3 , Figure 4 in (a) to Figure 4 in (f), one embodiment of the present invention will be described. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships of the respective elements shown in the drawings, the ratios of the respective elements, etc. are not necessarily consistent with reality. In addition, among the multiple drawings, the dimensional relationships of the respective elements, the ratios of the respective elements, etc. are not necessarily consistent.

[0020] (1) Configuration of the substrate processing apparatus

[0021] As Figure 1 shown, 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 composed of 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.

[0022] A heater 207 for heating the wafer 200 in the processing chamber 201 is provided outside the reaction tube 203. The heater 207 also functions as an activation mechanism for activating the gas in the processing chamber 201 by heat. A temperature sensor 263 is provided inside the reaction tube 203.

[0023] Nozzles 249a to 249c are provided in the processing chamber 201. As Figure 2 shown, the nozzles 249a to 249c are arranged so as to stand upright in the arrangement direction of the wafer 200 along the inner wall of the reaction tube 203. On the side surfaces of the nozzles 249a to 249c, a plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0024] Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c. Mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c are provided on the gas supply pipes 232a to 232c. Gas supply pipes 232d and 232f are connected to the downstream side of the valve 243a in the gas supply pipe 232a. Gas supply pipes 232e and 232g are connected to the downstream side of the valve 243b in the gas supply pipe 232b. A gas supply pipe 232h is connected to the downstream side of the valve 243c in the gas supply pipe 232c. MFCs 241d to 241h and valves 241d to 241h are respectively provided on the gas supply pipes 232d to 232h.

[0025] A first raw material is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a.

[0026] A reactant (oxidant) is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b.

[0027] A modifier is supplied into the processing chamber 201 from the gas supply pipe 232c via the MFC 241c, the valve 243c, and the nozzle 249c.

[0028] A second raw material is supplied into the processing chamber 201 from the gas supply pipe 232d via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a.

[0029] Catalyst is supplied into the processing chamber 201 from the gas supply pipe 232e via the MFC 241e, the valve 243e, the gas supply pipe 232b, and the nozzle 249b.

[0030] Inert gas is supplied into the processing chamber 201 from the gas supply pipes 232f to 232h via the MFCs 241f to 241h, the valves 243f to 243h, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, etc.

[0031] The first raw material supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The reactant (oxidant) supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The modifier supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The second raw material supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The catalyst supply system is mainly composed of the gas supply pipe 232e, the MFC 241e, and the valve 243e. The inert gas supply system is mainly composed of the gas supply pipes 232f to 232h, the MFCs 241f to 241h, and the valves 243f to 243h. Any one or all of the above various supply systems may be configured as an integrated supply system 248 integrating the valves 243a to 243h, the MFCs 241a to 241h, etc. It should be noted that when different reactants are used in the subsequent respective processing steps (steps A, B, C), a reactant supply system for supplying the reactant to the nozzle 249b is provided for each different reactant.

[0032] An exhaust port 231a is provided below the reaction tube 203. A vacuum pump 246 is connected to the exhaust pipe 231 via a pressure sensor 245 and an APC (Auto Pressure Controller) valve 244. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0033] A seal cover 219 is provided below the manifold 209. A rotation mechanism 267 for rotating a susceptor 217 described later is provided on the seal cover 219. The seal cover 219 is lifted and lowered by a susceptor elevator 115. The susceptor elevator 115 functions as a transfer mechanism for transferring the wafer 200 in and out of the processing chamber 201.

[0034] Below the manifold 209, a shutter 219s is provided that can hermetically seal 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.

[0035] The susceptor 217, which is a substrate support, is configured to support multiple wafers 200, for example, 25 to 200 wafers, in a horizontal posture and in a state where their centers are aligned with each other in the vertical direction and in multiple layers. Heat insulating plates 218 are supported in multiple layers below the susceptor 217.

[0036] Furthermore, the substrate processing apparatus may also include an etching unit (etching device) that performs step B2 (separation film formation) described later. This unit includes, for example, an etching gas supply system that supplies an etching gas into the processing container housing 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 can be performed on the wafer 200 using this unit.

[0037] It should be noted that the substrate processing apparatus including the etching unit may also be configured as a processing system interconnected via a communication network.

[0038] As Figure 3 shown, the 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 perform data exchange 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. An external storage device 123 can be connected to the controller 121.

[0039] The storage device 121c is composed of a flash memory, an HDD, an SSD, etc. A control program that controls the operation of the processing device, a process recipe that describes the steps, conditions, etc. of the substrate processing described later, and the like are recorded and stored in the storage device 121c in a readable manner. The process recipe is combined in such a way that the processing device can execute each step of the substrate processing described later through the controller 121 and obtain a specified result, and functions as a program. Hereinafter, the process recipe, the control program, etc. will be collectively and simply referred to as a program. In addition, the process recipe will also be simply referred to as a recipe. When the term "program" is used in this specification, it may sometimes include only the recipe, sometimes only the control program, or sometimes both.

[0040] The I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, susceptor lifter 115, gate opening / closing mechanism 115s, etc. The I / O port 121d can also be connected to an etching unit.

[0041] The CPU 121a is configured to be able to read a control program from the storage device 121c and execute it, and read a process from the storage device 121c according to the input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be able to control, according to the content of the read process: the flow rate adjustment operations of various substances based on the MFCs 241a to 241h, the opening / closing operations of the valves 243a to 243h, the opening / closing operations of the APC valve 244, and the pressure adjustment operations using the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operations of the heater 207 based on the temperature sensor 263, the rotation of the susceptor 217 based on the rotation mechanism 267 and the rotation speed adjustment operations, the lifting operations of the susceptor 217 based on the susceptor lifter 115, the opening / closing operations of the gate 219s based on the gate opening / closing mechanism 115s, etc. The CPU 121a can also be configured to be able to control an etching unit.

[0042] The controller 121 can be configured by installing the above program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, USB memories, semiconductor memories such as SSDs, etc. The storage device 121c and the external storage device 123 are configured as record media readable by a computer. Hereinafter, they are collectively and simply referred to as record media. When the term "record medium" is used in this specification, it sometimes includes only the storage device 121c alone, sometimes includes only the external storage device 123 alone, or sometimes includes both. Programs can also be provided to a computer using communication means such as the Internet.

[0043] (2) Substrate processing process

[0044] Mainly use Figure 4 in (a) to Figure 4 in (f) to illustrate an example of the processing sequence for forming a film on the surface of a wafer 200 as a substrate in one process of a semiconductor device manufacturing process (manufacturing method) using the above substrate processing apparatus, etc. Some of the processes (steps A1, A2, C, B1) in the following series of processing sequences are implemented by the above substrate processing apparatus. At this time, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0045] In the processing sequence of this embodiment, the following are performed:

[0046] (a) In a wafer 200 having a structure in which surfaces of a first material, a second material, and a third material are adjacent to each other in this order, step A of 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 with respect to the surface of the second material; and

[0047] (b) Step B of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

[0048] It should be noted that in the following examples, as in Figure 4 (a), Figure 4 in (b) shown below, the case where the following steps are performed in step A will be described:

[0049] (a-1) Step A1 of selectively forming a first adsorption barrier layer that hinders 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; and

[0050] (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 by supplying the first raw material to the wafer 200.

[0051] In addition, in the following examples, as in Figure 4 (c) shown below, the case where the following steps are further performed after step A will be described:

[0052] Step C of modifying a part of the first material in contact with the interface between the first material and the first dielectric film into a first substitution oxide film via the first dielectric film and modifying a part of the third material in contact with the interface between the third material and the second dielectric film into a second substitution oxide film by supplying an oxidant to the wafer 200.

[0053] It should be noted that in the following examples, the case where step C is performed before step B will be described.

[0054] In addition, in the following examples, as in Figure 4 (d), Figure 4 in (e) shown below, the case where the following steps are performed in step B will be described:

[0055] (b-1) Step B1 of forming an embedding film that embeds 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; and

[0056] Step B2 of leaving the portion formed in the recess in the embedding film as the separation film and removing the other portions.

[0057] In addition, in the following examples, as Figure 4 shown in (f) below, the case where, after performing Step B, 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, is described.

[0058] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" in this specification may refer to the surface of the wafer itself or to the surface of a specified layer or the like formed on the wafer. When it is described in this specification that "a specified layer is formed on the surface of the wafer", it may refer to the case where the specified layer is directly formed on the surface of the wafer itself or to the case where the specified layer is formed on a layer or the like formed on the wafer. The case where the term "substrate" is used in this specification is synonymous with the case where the term "wafer" is used.

[0059] The terms "agent" and "substance" used in this specification include at least any one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, each of the modifiers, 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.

[0060] Hereinafter, the processing sequence in this embodiment will be specifically described.

[0061] If a plurality of wafers 200 are loaded into the boat 217 (wafer filling), the shutter 219s is moved to open the lower end opening of the manifold 209 (shutter opening). 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 loading).

[0062] As Figure 4As shown in (a) etc. in [description], the wafer 200 to be processed has 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 on its surface (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. Sometimes, three-dimensional structures such as grooves and holes are provided on the surface of the wafer 200, and the above-mentioned adjacent structure is sometimes provided on three-dimensional parts such as the side wall surfaces of the grooves and holes. In addition, the above-mentioned adjacent structure is sometimes also provided on the flat part of 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 any one of an oxide or a non-oxide in which the oxygen content ratio (that is, the ratio of oxygen in the composition of the material or the oxygen content concentration) is smaller than that of the second material. For example, the first material and the third material can be nitrides such as silicon nitride (SiN) respectively, and the second material can be an oxide such as silicon oxide (SiO). In addition, the first material and the third material can also be materials in which at least a part of the surface of a non-oxide such as SiN is naturally oxidized. Even in this case, the oxygen content ratio of the naturally oxidized surface is smaller than that of the second material.

[0063] After the wafer boat loading is completed, vacuum exhaust (pressure reduction exhaust) is performed by the vacuum pump 246 so that the inside of the processing chamber 201 becomes a desired pressure (vacuum degree). In addition, heating is performed using the heater 207 so that the wafer 200 inside the processing chamber 201 becomes a desired processing temperature. In addition, rotation of the wafer 200 by the rotation mechanism 267 is started. Exhaust inside the processing chamber 201, heating of the wafer 200, and rotation are all continued at least until the processing of the wafer 200 is completed.

[0064] (Step A)

[0065] Next, the following steps A1 and A2 are performed on the wafer 200 prepared in the processing chamber 201.

[0066] [Step A1: Formation of the first adsorption barrier layer]

[0067] In this step, the valve 243c is opened, and a modifier (inhibitor) is supplied to the wafer 200. At this time, the valves 243f to 243h can also be opened to supply an inert gas into the processing chamber 201.

[0068] By performing step A1 under the processing conditions described later, as Figure 4As shown in (a) of [], a first adsorption inhibiting 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 inhibiting layer contains at least a part of the molecular structure of the molecules constituting the modifier. In the present invention, the expression "selectively form the first adsorption inhibiting layer on the surface of the second material" does not mean "form the first adsorption inhibiting layer only on the surface of the second material", but "preferably form the first adsorption inhibiting 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 expression does not completely exclude the formation of the first adsorption inhibiting layer on the surface of the first material and the formation of the first adsorption inhibiting layer on the surface of the third material. This expression of "selectively" is used with substantially the same meaning in the following respective steps.

[0069] After selectively forming the first adsorption inhibiting layer on the surface of the second material, the valve 243c is closed, and the supply of the modifier to the wafer 200 is stopped. Then, the inside of the processing chamber 201 is evacuated, and gaseous substances and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201. In addition, the valves 243f to 243h are opened, and an inert gas is supplied into the processing chamber 201 to purge the inside of the processing chamber 201 (purge).

[0070] 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.

[0071] 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]) can be used.

[0072] As the modifier, one or more of these silicon (Si)-containing substances can be used.

[0073] As the processing conditions when supplying the Si-containing substance as the modifier in step A1, the following can be exemplified:

[0074] Processing temperature: room temperature (25 °C) to 500 °C, preferably room temperature to 250 °C

[0075] Processing pressure: 5 - 1000 Pa

[0076] Processing time: 1 second - 120 minutes, preferably 30 seconds - 60 minutes

[0077] Modifier supply flow rate: 0.001 - 3 slm, preferably 0.001 - 0.5 slm

[0078] Inert gas supply flow rate (for each gas supply pipe): 0 - 20 slm.

[0079] It should be noted that the expression of the numerical range such as "25 - 500 °C" in this specification means that the lower limit value and the upper limit value are included in this range. Therefore, for example, "25 - 500 °C" means "25 °C or higher and 500 °C or lower". The same applies to other numerical ranges. In addition, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the time during which this processing is continued. In addition, when the supply flow rate includes 0 slm, 0 slm means that this substance is not supplied. The same applies to the following descriptions.

[0080] In addition, as the modifier, fluorine (F2), nitrogen fluoride (NF3), chlorine fluoride (ClF3), hydrogen fluoride (HF), etc. can be used. As the modifier, one or more of these fluorine (F)-containing substances can be used.

[0081] As the processing conditions when supplying an F-containing substance as the modifier in step A1, examples can be cited as follows:

[0082] Processing temperature: room temperature (25 °C) - 300 °C, preferably room temperature - 200 °C

[0083] Processing pressure: 1 - 2000 Pa, preferably 1 - 1000 Pa

[0084] Processing time: 1 second - 60 minutes

[0085] Modifier supply flow rate: 0.001 - 2 slm, preferably 0.001 - 0.5 slm

[0086] Inert gas supply flow rate (for each gas supply pipe): 0 - 20 slm.

[0087] It should be noted that in step A1, the step A1(Si) of supplying a Si-containing substance as the modifier to the wafer 200 and the step A1(F) of supplying an F-containing substance as the modifier can be carried out in sequence.

[0088] [Step A2: Formation of the first dielectric film and the second dielectric film]

[0089] In this step, after forming the first adsorption barrier layer on the surface of the second material, the wafer 200 is subjected to the following steps (first raw material supply, reactant supply). As the reactant, an oxidizing agent can be used.

[0090] 〔First raw material supply〕

[0091] 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 can also be opened to supply an inert gas into the processing chamber 201.

[0092] 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.

[0093] After forming the adsorption layer of the first raw material, the valve 243a is closed to stop supplying the first raw material to the wafer 200. Then, through the above steps, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201, and the inside of the processing chamber 201 is purged (purged) with an inert gas.

[0094] 〔Reactant supply〕

[0095] In this step, the valve 243b is opened to supply the reactant to the wafer 200. At this time, the valves 243f to 243h can also be opened to supply an inert gas into the processing chamber 201.

[0096] By performing this step (reactant supply) under the processing conditions described later, 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 reactant, 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.

[0097] After modifying the adsorption layer of the first raw material, the valve 243b is closed to stop supplying the reactant to the wafer 200. Then, through the above steps, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201, and the inside of the processing chamber 201 is purged with an inert gas.

[0098] 〔Execute a specified number of times〕

[0099] Then, the cycle including the first raw material supply and the reactant supply is performed a specified number of times (n A times. n A is an integer of 1 or 2 or more). Thus, as Figure 4As shown in (b) thereof, it is possible to 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. When a metal-containing substance is used as the first raw material and an oxidant is used as the reactant, for example, as the first dielectric film and the second dielectric film, it is possible to form metal oxide films such as an aluminum oxide film (AlO film), a titanium oxide film (TiO film), a hafnium oxide film (HfO film), a zirconium oxide film (ZrO film), etc., that is, it is possible to form a dielectric film which is a metal oxide film containing oxygen (O) and has a higher electron trap density than the SiN film. As the dielectric film, a high-k dielectric film can be particularly applied. It should be noted that by forming the first dielectric film and the second dielectric film, a recess is formed on the surface of the wafer 200 with the first dielectric film and the second dielectric film as sidewalls and the surface of the second material as the bottom.

[0100] In addition, for the expression of "selectively forming 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", as described above, it does not completely exclude the formation of the first dielectric film and the second dielectric film on the surface of the second material. Therefore, for example, since a part of the first adsorption barrier layer detaches during step A2, a discontinuous oxide layer may sometimes be formed on a part of the surface of the second material. In addition, for example, as Figure 4 shown in (b) thereof, in step A2, the first dielectric film can be formed in such a manner that it protrudes (i.e., exposes, covers, crosses) more toward the surface of the second material than the boundary between the surface of the second material and the surface of the first material. This is to enable the first dielectric film to grow in a manner that protrudes above the second material with the first dielectric film itself as a base during the process of repeatedly performing the cycle of forming the first dielectric film. In addition, for example, in step A2, the second dielectric film can be formed in the same manner as the first dielectric film, that is, it protrudes (i.e., exposes, covers, crosses) more toward the surface of the second material than the boundary between the surface of the second material and the surface of the third material.

[0101] As the first raw material, for example, aluminum trichloride (AlCl3), trimethylaluminum (Al(CH3)3), titanium tetrachloride (TiCl4), hafnium tetrafluoride (HfF4), hafnium tetramethylethylenediamine (Hf[N(CH3)(CH2CH3)]4), zirconium tetrafluoride (ZrF4), zirconium tetramethylethylenediamine (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 halogenated metals) can be used.

[0102] As a 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 (O)-containing substances can be used. It should be noted that here, in order to suppress the rapid detachment of the first adsorption blocking layer due to the reactant, a reactant with a weaker oxidizing power is preferably used. For example, a reactant with an oxidizing ability weaker than the oxidizing agent used in step C described later can be used. However, in the case where a modifier that is relatively difficult to detach with respect to the oxidizing agent is used, etc., in the case where a reactant with a strong oxidizing power can be used, an oxidizing agent with a relatively strong oxidizing power exemplified in step C described later can also be used.

[0103] As the processing conditions when supplying the first raw material in step A2, the following can be exemplified:

[0104] Processing temperature: room temperature (25 °C) to 500 °C, preferably 350 to 400 °C

[0105] Processing pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa

[0106] Processing time: 1 to 180 seconds, preferably 10 to 120 seconds

[0107] First raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm

[0108] Inert gas supply flow rate (for each gas supply pipe): 0 to 20 slm.

[0109] As the processing conditions when supplying the reactant in step A2, the following can be exemplified:

[0110] Processing pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa

[0111] Reactant supply flow rate: 0.01 to 20 slm, preferably 0.01 to 10 slm.

[0112] Other processing conditions can be set the same as those when supplying the first raw material.

[0113] It should be noted that a nitriding agent can also be used as the reactant. As the reactant, for example, ammonia (NH3), diazene (N2H2), hydrazine (N2H4), hydrazoic acid such as N3H8 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.

[0114] (Step C: Formation of the first replacement oxide film and the second replacement oxide film)

[0115] Next, step C is performed on the wafer 200 after the first dielectric film and the second dielectric film are formed on the surface.

[0116] In this step, the valve 243b is opened, and a reactant containing oxygen (i.e., an oxidant) is supplied to the wafer 200. At this time, the valves 243f to 243h may also be opened to supply an inert gas into the processing chamber 201.

[0117] 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 can be modified (oxidized) to the first replacement oxide film via 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 can be modified (oxidized) to the second replacement oxide film via the second dielectric film. The first replacement oxide film and the second replacement oxide film are configured as, for example, SiO films and SiON films. It should be noted that in step C, the characteristics of the first dielectric film and the second dielectric film as oxide films can be further improved without impairing these characteristics. For example, the first dielectric film and the second dielectric film can be re-oxidized (additional oxidation), impurities can be removed from these films, and these films can be densified.

[0118] It should be noted that step C is performed after step A and before step B, that is, in a state where there is no other film formed in contact with the upper surface and side surfaces of the first dielectric film and the second dielectric film. Therefore, in step C, the first dielectric film formed on the first replacement oxide film can be moved by the expansion generated by modifying a part of the first material to the first replacement oxide film. In addition, the second dielectric film formed on the second replacement oxide film can be moved by the expansion generated by modifying a part of the third material to the second replacement oxide film. That is, in step C, by expanding a part of the first material and the second material in a state where there is no other film that hinders the movement of the first dielectric film and the second dielectric film, the movement (lifting) of these films can be achieved while suppressing film stress such as compressive stress applied to the first dielectric film and the second dielectric film, and these films can be moved in a stress-free state.

[0119] 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 barrier layer is formed between the portion formed to protrude toward the surface side of the second material and the surface of the second material, and the two are separated by the first adsorption barrier 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 will not be hindered due to the bonding (healing) of the portion where the first dielectric film and / or the second dielectric film is formed in a protruding manner to the surface of the second material, and an increase in film stress can be suppressed.

[0120] After the above modification is completed, valve 243b is closed, and the supply of the oxidant into processing chamber 201 is stopped. Then, through the above steps, gaseous substances and the like remaining in processing chamber 201 are exhausted from processing chamber 201, and processing chamber 201 is purged with an inert gas.

[0121] As the oxidant, for example, oxygen-containing substances such as ozone (O3), oxygen (O2) + hydrogen (H2), O2 + deuterium (D2), O3 + H2, O3 + D2, hydrogen peroxide (H2O2), O2 excited to a plasma state, and O3 can be used. One or more of them can be used as the oxidant. Here, the combined description of two substances such as "O2 + H2" refers to a mixture of O2 and H2. When supplying the mixture, the two substances can be mixed (pre-mixed) in the supply pipe and then supplied into processing chamber 201, or the two substances can be supplied into processing chamber 201 separately from different supply pipes and mixed in processing chamber 201 (post-mixed). It should be noted that when the first replacement oxide film and the second replacement oxide film can be formed via the first dielectric film and the second dielectric film by adjusting the processing conditions and the like, an oxidant with relatively weak oxidation ability exemplified in the above step A can also be used.

[0122] As the processing conditions when supplying the oxidant in step C, the following can be exemplified:

[0123] Processing temperature: 350 to 1000 °C, preferably 400 to 650 °C

[0124] Processing pressure: 1 to 105000 Pa, preferably 10 to 10000 Pa

[0125] Processing time: 1 to 10000 seconds, preferably 5 to 3600 seconds

[0126] Oxidant supply flow rate: 0.01 to 10 slm, preferably 0.1 to 5 slm

[0127] Inert gas supply flow rate (for each gas supply pipe): 0 to 20 slm.

[0128] (Step B)

[0129] Next, the following steps B1 and B2 are performed on the wafer 200 after the formation of the first replacement oxide film and the second replacement oxide film.

[0130] [Step B1: Embedding film formation]

[0131] In this step, the following steps (second raw material supply, reactant supply) are performed on the wafer 200. As the reactant, an oxidant can be used, for example. In at least one of the second raw material supply and the reactant supply steps, a catalyst can be supplied to the wafer 200. Hereinafter, the case where the catalyst is supplied in both the second raw material supply and the reactant supply steps will be described.

[0132] [Second raw material supply]

[0133] In this step, valves 243d and 243e are opened to supply the second raw material and the catalyst to the wafer 200. At this time, valves 243f to 243h can also be opened to supply an inert gas into the processing chamber 201.

[0134] By performing this step (second raw material supply) under the processing conditions described later, 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.

[0135] After the adsorption layer of the second raw material is formed, valves 243d and 243e are closed to stop the supply of the second raw material and the catalyst to the wafer 200. Then, through the above steps, gaseous substances and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201, and the inside of the processing chamber 201 is purged (purged) with an inert gas.

[0136] [Reactant supply]

[0137] In this step, valves 243b and 243e are opened to supply the reactant and the catalyst to the wafer 200. At this time, valves 243f to 243h can also be opened to supply an inert gas into the processing chamber 201.

[0138] By performing this step (reactant supply) under the processing conditions described below, it is possible to modify the adsorption layer of the second raw material formed in the recess with 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, respectively. When using an oxidant as the reactant, it is possible to oxidize the adsorption layer of the second raw material and form an oxide layer containing the constituent elements of the second raw material on the inner surfaces of 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, respectively.

[0139] After modifying the adsorption layer of the second raw material, valves 243b and 243e are closed to stop the supply of the reactant and the catalyst to the wafer 200. Then, through the above steps, gaseous substances and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201, and the processing chamber 201 is purged with an inert gas.

[0140] 〔Implementation for a specified number of times〕

[0141] Then, the cycle including the supply of the second raw material and the supply of the reactant is performed a specified number of times (n B times. n B is an integer of 1 or more). Thus, as shown in (d) of Figure 4 , it is possible to form an embedded film 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, respectively. This cycle is performed until the recesses are embedded with the embedded film. When using a Si-containing substance as the second raw material and an oxidant as the reactant, an oxide film such as a silicon oxide film (SiO film) can be formed as the embedded film.

[0142] As the second raw material, for example, the above alkylaminosilane and aminosilane can be used. In addition, as the second raw material, chlorosilanes such as dichlorosilane (SiH2Cl2), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), and octachlorotrisilane (Si3Cl8) can be used. One or more of these Si-containing substances can be used as the second raw material.

[0143] As the reactant (oxidant), one or more of the above O-containing substances can be used.

[0144] As the catalyst, for example, pyridine (C5H5N), methylpyridine (C6H7N), dimethylpyridine (C7H9N), triethylamine ((C2H5)3N), etc. can be used. One or more of these amines can be used as the catalyst.

[0145] As the processing conditions when supplying the second raw material and the catalyst in step B1, the following can be exemplified:

[0146] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C

[0147] Treatment pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa

[0148] Treatment time: 1 to 180 seconds, preferably 10 to 120 seconds

[0149] Flow rate of the second raw material supply: 0.001 to 2 slm, preferably 0.01 to 1 slm

[0150] Flow rate of the catalyst supply: 0.001 to 2 slm, preferably 0.01 to 1 slm.

[0151] As the treatment conditions when supplying the reactant and the catalyst in step B1, the following can be exemplified:

[0152] Treatment pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa

[0153] Flow rate of the reactant supply: 0.001 to 2 slm, preferably 0.01 to 1 slm

[0154] Flow rate of the catalyst supply: 0.001 to 2 slm, preferably 0.01 to 1 slm.

[0155] Other treatment conditions can be made the same as those for the supply of the second raw material and the catalyst.

[0156] After the formation of the embedding film on the surface of the wafer 200 is completed, the inside of the processing chamber 201 is purged to remove the gas, reaction by-products, etc. remaining in the processing chamber 201 (post-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 atmospheric pressure (atmospheric pressure restoration). Then, the processed wafer 200 is unloaded (boat unloading) outside the reaction tube 203, and taken out (wafer take-out) from the boat 217. It should be noted that after the boat unloading, the lower end opening of the manifold 209 is sealed with the gate 219s (gate closing).

[0157] [Step B2: Separation membrane formation]

[0158] Next, step B2 is performed on the wafer 200 after the wafer is taken out, that is, the wafer 200 on which the embedding film has been formed on the surface.

[0159] In step B2, among the embedding films formed on the surface of the wafer 200, the portion formed in the recess is left as the 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 embedding 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 device with known processing steps 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. It should be noted that the partial removal of the embedding film is not limited to the case of being performed by anisotropic etching. In the case where the above-described adjacent structure is provided in the flat portion on the surface of the wafer 200, for example, the partial removal of the embedding film can also be performed by CMP (chemical mechanical polishing).

[0160] By performing step B2, as shown in (e) of Figure 4 , the surface of the wafer 200 becomes a state in which the first dielectric film, the separation film, and the second dielectric film are adjacent and exposed in this order. The first dielectric film and the second dielectric film are physically and electrically separated (isolated) with the separation film interposed therebetween. In the case where the partial removal of the embedding film is performed by anisotropic etching or CMP as described above, the exposed surfaces of the first dielectric film, the separation film, and the second dielectric film can be made into smooth surfaces (flat surfaces, curved surfaces) that are adjacent to each other without a step difference overall.

[0161] (Step D: Formation of tunnel oxide film and channel film)

[0162] Next, step D is performed on the wafer 200 after the first replacement oxide film and the second replacement oxide film are formed.

[0163] In this step, a tunnel oxide film and a channel film are sequentially stacked on the surfaces of the separation 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 that are known as part of the manufacturing process of memory cells in flash memories. It should be noted that step D can be performed in the above-described processing chamber 201 in which steps A1, A2, C, and B1 are performed, and can also be performed in the processing chamber of other substrate processing devices.

[0164] As described above, the laminated structure shown in (f) of Figure 4 is obtained through steps A to D.

[0165] The stacked structure can be suitably used as part of a component of a memory cell such as a flash memory. That is, the first dielectric film and the second dielectric film formed by the above method have a higher electron trap density than the SiN film by being configured as a metal oxide film, and are precisely formed with high dimensional accuracy in a proper shape, so they can be respectively suitably used as charge trapping layers of a memory cell. In addition, since the separation film is composed of an oxide film such as SiO film, it can be suitably used as a separation layer for insulating adjacent charge trapping layers in a memory cell of a flash memory. Further, since the first replacement oxide film and the second replacement oxide film are composed of oxide films (SiO film, SiON film), they can be respectively suitably used as barrier layers for suppressing carrier leakage from the charge trapping layer.

[0166] (3) Effects of this method

[0167] According to this method, one or more of the following effects can be obtained.

[0168] (a) According to this method, a film can be precisely formed on a substrate. That is, in the above step A, in a substrate having the above structure with the surfaces of the first to third materials adjacent to each other, a dielectric film (the first dielectric film, the second dielectric film) can be selectively formed on the surface of a substrate made of a specific material (the first material, the third material). These formed dielectric films can be suitably used, for example, as charge trapping layers in a memory cell of a flash memory. In addition, in the above step B, a separation film can be formed between these dielectric films. The formed separation film can be suitably used, for example, as a separator (diaphragm) for separating adjacent charge trapping layers in a memory cell of a flash memory.

[0169] (b) By making the first material to the third material the above materials, the above effects can be obtained more reliably. For example, by making the first material to the third material the above materials, 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 by using the OH termination (hydroxyl termination) selectively formed on the surface of the second material which is an oxide. In addition, by making the first material to the third material the above materials, the structure in which they are adjacent in this order can be suitably used as part of a component of a memory cell of a flash memory, for example.

[0170] (c) By making the separation film an oxide film such as SiO film, the above effects can be obtained more reliably. In addition, by making the separation film an oxide film such as SiO film, the film can be suitably used, for example, as a separation layer for insulating adjacent charge trapping layers in a memory cell of a flash memory.

[0171] (d) By making the first dielectric film and the second dielectric film each an oxide film such as a metal oxide film, the first dielectric film and the second dielectric film can each be suitably used as, for example, a charge trapping layer of a memory cell.

[0172] In addition, by making the first dielectric film and the second dielectric film each an oxide film such as a metal oxide film, when forming the first replacement oxide film and the second replacement oxide film in step C, even if a part of the first material and a part of the third material are oxidized (modified) via the first dielectric film and the second dielectric film, the characteristics of these films as oxide films can be maintained as they are. In contrast, for example, when the first dielectric film and the second dielectric film are nitride films, if a part of the first material and a part of the third material are oxidized via the first dielectric film and the second dielectric film, at least a part of the nitrogen in the film escapes, and it sometimes becomes difficult to maintain the characteristics of these films as nitride films.

[0173] In addition, by making the first dielectric film and the second dielectric film each have an electron trap density larger than that of a silicon nitride film, these films can be suitably used as, for example, a charge trapping layer of a memory cell.

[0174] (e) In step A, by performing the above-described steps A1 and A2, the first dielectric film and the second dielectric film can be selectively and efficiently formed with respect to the surface of the second material, respectively.

[0175] (f) In step A, by forming the first dielectric film in a manner that protrudes more toward the surface of the second material than the boundary between the surface of the second material and the surface of the first material, and by forming the second dielectric film in a manner that protrudes more toward the surface of the second material than the boundary between the surface of the second material and the surface of the third material, these films can be made into a suitable shape and size when used as a charge trapping layer of a memory cell. For example, by forming the films in such a shape, it is easy to ensure a sufficient area as a charge trapping layer of a memory cell.

[0176] (g) After step A, by performing step C of supplying an oxidant to the wafer 200, the first replacement oxide film and the second replacement oxide film, which are oxide films having high insulation, can be formed adjacent to the first dielectric film and the second dielectric film. In addition, by performing modification (oxidation) via 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, making these films more suitable films, for example, as a charge trapping layer of a memory cell.

[0177] (h) In step C, by utilizing the expansion generated when a part of the first material is modified into the first replacement oxide film, the first dielectric film can be moved (lifted). Additionally, by utilizing the expansion generated when a part of the third material is modified into the second replacement oxide film, the second dielectric film can be moved (lifted). That is, in step C, these films can be lifted without individually compressing the first dielectric film and the second dielectric film. Thereby, a reduction in the quality of each of the first dielectric film and the second dielectric film can be avoided. It should be noted that by implementing step C before performing step B, that is, by performing step C before the formation of the separation film, the effects described herein can be obtained more reliably.

[0178] (i) When performing steps B1 and B2 in step B, by using the recesses with the first dielectric film and the second dielectric film as sidewalls as a frame to form the separation film, the separation film can be formed with good controllability and high dimensional accuracy. Additionally, through the process of 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 that fills the recess without gaps or voids. Thereby, the separation film can be suitably used as, for example, a separation layer for insulating adjacent charge trapping layers.

[0179] Furthermore, in step B1, by performing the cycle including the supply of the second raw material and the supply of the reactant a specified number of times, the embedding film can be formed with good step coverage controllability. Thereby, the quality of the separation film can be improved, and this film can be suitably used as, for example, the separation film of the charge trapping layer.

[0180] (j) By aligning the surfaces of the first material, the second material, and the third material on the same plane, the laminated structure obtained through steps A and B can be suitably used as, for example, a part of the constituent elements of a memory cell of a flash memory.

[0181] (k) When using the first dielectric film and the second dielectric film formed by the method of the present invention as the films of the charge trapping layer constituting the memory cell, for example, the performance of the flash memory device can be improved.

[0182] (l) The above effects can also be obtained similarly when arbitrarily selecting and using specified substances from the above various modifiers, various raw materials, various reactants (oxidants), and various inert gases.

[0183] <Other aspects of the present invention>

[0184] The above has specifically described the aspects of the present invention. However, the present invention is not limited to the above aspects, and various modifications can be made without departing from its gist.

[0185] For example, after performing step A, step B can also be carried out without performing step C. In this case, in step B, a separation film can also be formed by supplying a second raw material and an oxidant to the wafer 200, and a part of the first material in contact with the interface between the first material and the first dielectric film can be modified to a first replacement oxide film via the first dielectric film. In addition, a part of the third material in contact with the interface between the third material and the first dielectric film can be modified to a second replacement oxide film via the second dielectric film. In step B1, by using an oxidant with strong oxidizing power (O3, O2 + H2, O2 + D2, O3 + H2, O3 + D2, H2O2, O2 or O3 excited to a plasma state, etc.) exemplified in step C, as described herein, the formation of the separation film, the modification of a part of the first material to the first replacement oxide film, and the modification of a part of the third material to the second replacement oxide film can be carried out simultaneously in parallel, and the productivity of the device can be improved.

[0186] In addition, for example, in step B, for the wafer 200 after the first dielectric film and the second dielectric film are formed on the surface, the following can also be carried out:

[0187] (b-1) Step B1' of selectively forming a second adsorption barrier layer (second inhibitor layer) on the surfaces of the first dielectric film and the second dielectric film to hinder the adsorption of the second raw material with respect to the surface of the second material; and

[0188] (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.

[0189] The processing steps and conditions in step B1' can be set to be the same as the processing steps and conditions in the above step A1 (formation of the first adsorption barrier layer), for example. The processing steps and conditions in step B2' can be set to be the same as the processing steps and conditions in the above step B1 (formation of the embedding film), for example.

[0190] In this case, the same effects as the above method can also be obtained. In addition, in such a case, a separation film can be selectively and efficiently formed on the surface of the second material with respect to the surfaces of the first dielectric film and the second dielectric film. In addition, after the separation film is formed, step B2 for removing the unnecessary embedding film can be omitted, and the productivity of the device can be improved.

[0191] It should be noted that in step B, when performing steps B1' and B2', step B2' is preferably carried out until the concave portion is embedded by the separation film. By embedding the concave portion without gaps using the separation film, this film can be suitably used as a separation layer for insulating adjacent charge trapping layers in the memory cells of the flash memory.

[0192] Preferably, the processes used in each process are prepared individually corresponding to the processing content, and are recorded and pre-stored in the storage device 121c via the electrical communication line and the external storage device 123. And preferably, when starting each process, the CPU 121a appropriately selects a suitable process from the multiple processes recorded and stored in the storage device 121c corresponding to the processing content. Thereby, films of various film types, composition ratios, film qualities, and film thicknesses can be reproducibly formed by the processing device. In addition, while reducing the burden on the operator and avoiding operation errors, each process can be quickly started.

[0193] The above-mentioned processes are not limited to the case of newly made ones. For example, they can also be prepared by changing the existing processes already installed in the processing device. When changing the process, the changed process can also be installed in the processing device via the electrical communication line and the recording medium recording the process. In addition, the input / output device 122 provided in the existing processing device can also be operated to directly change the existing process already installed in the processing device.

[0194] In the above manner, an example of film formation processing using a batch processing device that processes multiple substrates at a time has been described. The present invention is not limited to the above manner. For example, it can also be appropriately applied when performing film formation processing using a single-substrate processing device that processes one or several substrates at a time. In addition, in the above manner, an example of performing film formation processing using a processing device having a hot-wall type processing furnace has been described. The present invention is not limited to the above manner, and it can also be appropriately applied when performing film formation processing using a processing device having a cold-wall type processing furnace.

[0195] In addition, in the above manner, an example of a series of processing sequences continuously performing steps A1, A2, C, and B1 in the same processing chamber (in-situ) of the same processing device has been described. The present invention is not limited to the above manner. Regarding any one of steps A1, A2, C, and B1 and any other step, they can be carried out in different processing chambers (ex-situ) of different processing devices, or can be carried out in different processing chambers of the same processing device respectively.

[0196] In the case of using the above processing device, each process can also be performed under the same processing steps and processing conditions as those in the above-described method and modification example, and the same effects as those in the above-described method and modification example can be obtained.

[0197] The above-described method and modification example can be used in appropriate combination. The processing steps and processing conditions at this time can be the same as those of the above-described method and modification example, for example.

Claims

1. Substrate processing method, comprising: (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 step of 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; and (b) A step of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

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 at least any one of an oxide having an oxygen content ratio smaller than that of 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 nitrides, respectively, 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 silicon nitrides, respectively, 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 metal oxide films, respectively.

8. The substrate processing method according to claim 1, wherein, (a) Comprising: (a-1) A step of selectively forming a first adsorption barrier layer that hinders 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, respectively; and (a-2) A step 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.

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

10. The substrate processing method according to claim 1, comprising: (c) After (a), a step of modifying a part of the first material in contact with the interface between the first material and the first dielectric film into a first replacement oxide film by supplying an oxidant to the substrate through the first dielectric film.

11. The substrate processing method according to claim 10, wherein, In (c), the first dielectric film is moved by the expansion generated by modifying a part of the first material into the first replacement oxide film.

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

13. The substrate processing method according to claim 1, wherein, In (b), the separation film is formed and 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 replacement oxide film through the first dielectric film by supplying a second raw material and an oxidant to the substrate.

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

15. The substrate processing method according to claim 1, wherein, (b) Comprising: (b-1) A step of selectively forming a second adsorption barrier layer that hinders the 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; and (b-2) A step of forming 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 by supplying the second raw material to the substrate.

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

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

18. A method of manufacturing a semiconductor device, comprising: (a) A step of selectively forming an oxygen-containing first dielectric film on the surface of the first material and an oxygen-containing second dielectric film on the surface of the third material in a substrate 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, with respect to the surface of the second material; and (b) A step of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

19. A computer-readable recording medium that records a program for causing a substrate processing apparatus to execute the following steps by a computer: (a) A step of selectively forming an oxygen-containing first dielectric film on the surface of the first material and an oxygen-containing second dielectric film on the surface of the third material in a substrate 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, with respect to the surface of the second material; and (b) A step of forming a separation film in a recess having the first dielectric film and the second dielectric film as side walls.

20. A substrate processing apparatus, which is a substrate processing apparatus for the substrate processing method according to claim 1, the substrate processing apparatus comprising: A first raw material supply system configured to supply a first raw material to the substrate; and A control unit configured to control the first raw material supply system in such a manner as to execute the following process: 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 by supplying the first raw material to the substrate.

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