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

Abstract

A film is formed on a substrate by performing a predetermined number of times a cycle including: (a) supplying a first raw material and an additive to the substrate, generating a second raw material that is chemically more stable than the first raw material, and exposing and adsorbing the first raw material and the second raw material to the surface of the substrate to form a first layer; and (b) supplying a reaction body to the substrate to change the first layer into a second layer.

Description

Technical Field

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

[0002] As one of the steps in the manufacturing process of a semiconductor device, there is a case where a process of forming a film on a substrate is performed (for example, refer to Japanese Patent Application Publication No. 2013-077805 and Japanese Patent Application Publication No. 2018-137356). Summary of the invention

[0003] Problems to be solved by the invention

[0004] As semiconductor devices become smaller, there is a strong demand for improvement in the step coverage of a film formed on a substrate.

[0005] The present invention provides a technology capable of improving the step coverage of a film formed on a substrate.

[0006] Methods for solving problems

[0007] According to one embodiment of the present invention, a technology is provided for forming a film on a substrate by performing a cycle comprising the following steps a predetermined number of times: (a) supplying a first raw material and an additive to the substrate to generate a second raw material that is chemically more stable than the first raw material, exposing the first raw material and the second raw material to and adsorbing them on the surface of the substrate to form a first layer; and (b) supplying a reactant to the substrate to change the first layer into a second layer.

[0008] Effects of the Invention

[0009] According to the present invention, the step coverage of a film formed on a substrate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 This is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus that is preferably used in one embodiment of the present invention, and shows a processing furnace 202 portion in a vertical cross-sectional view.

[0011] Figure 2 1 is a schematic diagram of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present invention. Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0012] Figure 3 This is a schematic configuration diagram of a controller 121 of a substrate processing apparatus that is preferably used in one embodiment of the present invention, and shows a control system of the controller 121 in the form of a block diagram. DETAILED DESCRIPTION

[0013] <One aspect of the present invention>

[0014] The following mainly refers to Figure 1 to Figure 3 One mode of the present invention is described. In addition, the drawings used in the following description are schematic drawings, and the dimensional relationship of each element in the drawings, the ratio of each element, etc. are not necessarily consistent with the actual. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings are not necessarily consistent.

[0015] (1) Configuration of substrate processing apparatus

[0016] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and supported by a holding plate and installed vertically. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas using heat.

[0017] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is disposed concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is configured to engage with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The reaction tube 203 and the manifold 209 constitute a processing container (reaction container). The processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0018] In the processing chamber 201, nozzles 249a to 249c as the first to third supply parts are respectively arranged to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as the first to third nozzles. The nozzles 249a to 249c are respectively made of heat-resistant materials such as quartz or SiC. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are respectively different nozzles, and the nozzles 249a and 249c are respectively arranged adjacent to the nozzle 249b.

[0019] In the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as switch valves are sequentially provided from the upstream side of the gas flow. A gas supply pipe 232d is connected to the gas supply pipe 232a on the downstream side of the valve 243a. A gas supply pipe 232e is connected to the gas supply pipe 232b on the downstream side of the valve 243b. A gas supply pipe 232f is connected to the gas supply pipe 232c on the downstream side of the valve 243c. In the gas supply pipes 232d to 232f, MFCs 241d to 241f and valves 243d to 243f are respectively provided in sequence from the upstream side of the gas flow. The gas supply pipes 232a to 232f are made of metal materials such as SUS, for example.

[0020] like Figure 2 As shown, the nozzles 249a to 249c are respectively arranged in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, and are respectively arranged to stand up from the lower part of the inner wall of the reaction tube 203 along the upper part, toward the arrangement direction of the wafer 200. That is, in the side of the wafer arrangement area where the wafers 200 are arranged, in the area horizontally surrounding the wafer arrangement area, the nozzles 249a to 249c are respectively arranged along the wafer arrangement area. In a plan view, the nozzle 249b is arranged to face the center of the wafer 200 carried into the processing chamber 201 between the exhaust port 231a described later, and is on a straight line. The nozzles 249a and 249c are arranged along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200) and sandwich the straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides. The straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200. That is, the nozzle 249c may be provided on the opposite side of the nozzle 249a while sandwiching the straight line L. The nozzles 249a and 249c are arranged to be line symmetrical with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are opened in a manner opposite to (opposite to) the exhaust port 231a when viewed from above, and gas can be supplied to the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0021] The first raw material is supplied into the processing chamber 201 from the gas supply pipe 232 a via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0022] The additive is supplied into the processing chamber 201 from the gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the nozzle 249 b .

[0023] The reactant is supplied into the processing chamber 201 from the gas supply pipe 232 c via the MFC 241 c , the valve 243 c , and the nozzle 249 c .

[0024] Inert gas is supplied from gas supply pipes 232d to 232f into the processing chamber 201 via MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0025] The first raw material supply system is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The additive supply system is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The reactant supply system is mainly composed of the gas supply pipe 232c, MFC241c, and valve 243c. The inert gas supply system is mainly composed of the gas supply pipes 232d to 232f, MFC241d to 241f, and valves 243d to 243f.

[0026] Among the various supply systems described above, any one or all of the supply systems may also be configured as an integrated supply system 248 in which valves 243a to 243f, MFCs 241a to 241f, etc. are integrated. The integrated supply system 248 is configured such that the gas supply pipes 232a to 232f are connected respectively, and the supply action of various substances (various gases) in the gas supply pipes 232a to 232f, i.e., the opening and closing action of the valves 243a to 243f or the flow rate adjustment action of the MFCs 241a to 241f, etc., is controlled by the controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and the gas supply pipes 232a to 232f, etc. can be loaded and unloaded as an integrated unit, and the integrated supply system 248 can be maintained, replaced, and added as an integrated unit.

[0027] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2As shown, the exhaust port 231a is provided at a position opposite to the nozzles 249a to 249c (gas supply holes 250a to 250c) while sandwiching the wafer 200 when viewed from above. The exhaust port 231a is provided from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulating unit). The APC valve 244 is configured to open and close the valve when the vacuum pump 246 is in operation, so that the vacuum exhaust in the processing chamber 201 can be performed and the vacuum exhaust can be stopped. Furthermore, when the vacuum pump 246 is in operation, the valve opening is adjusted according to the pressure information detected by the pressure sensor 245 to adjust the pressure in the processing chamber 201. 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.

[0028] Below the manifold 209, there is provided a sealing cover 219 as a furnace port cover body that can airtightly close the lower end opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS, for example, and is formed in a disc shape. On the upper surface of the sealing cover 219, there is provided an O-ring 220b as a sealing component that abuts against the lower end of the manifold 209. Below the sealing cover 219, there is provided a rotating mechanism 267 for rotating the wafer boat 217 described later. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer boat lifter 115 as a lifting mechanism provided outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 in and out (transports) the wafer 200 in and out of the processing chamber 201 by raising and lowering the sealing cover 219 .

[0029] Below the manifold 209, a shutter 219s is provided as a furnace cover body that can hermetically close the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that abuts against the lower end of the manifold 209. The opening and closing action (lifting action or rotating action, etc.) of the shutter 219s is controlled by the shutter opening and closing mechanism 115s.

[0030] The wafer boat 217 as a substrate support is configured to support a plurality of, for example, 25 to 200 wafers 200 in a horizontal position and aligned with each other's centers, in a vertical direction in multiple stages, that is, arranged at intervals. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the bottom of the wafer boat 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple stages.

[0031] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263 so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0032] like Figure 3 As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 such as a touch panel is connected to the controller 121. In addition, the controller 121 can be connected to an external storage device 123.

[0033] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SDD (Solid State Drive), etc. A control program for controlling the actions of the substrate processing device is readable and stored in the storage device 121c, and a process recipe (recipe) that records the sequence or conditions of the substrate processing described later is recorded. The process recipe is composed of a combination of methods that can obtain a predetermined result by causing the substrate processing device to execute each sequence of the substrate processing described later through the controller 121, and functions as a program. Hereinafter, the process recipe or control program is referred to as a program. In addition, the process recipe is sometimes referred to as a process. In this specification, the use of the term program refers to a case where only a single recipe is included, a case where only a single control program is included, or a case where both are included. RAM121b is composed of a memory area (working area) that temporarily stores programs or data read out by CPU121a.

[0034] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter switch mechanism 115s, etc.

[0035] The CPU 121a is configured to read the control program from the storage device 121c and execute it, and to read the recipe from the storage device 121c according to the input of the operation command from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241f, the opening and closing operation of the valves 243a to 243f, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 by the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 by the temperature sensor 263, the rotation and rotation speed adjustment operation of the wafer boat 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer boat 217 by the wafer boat lifter 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc. according to the contents of the read recipe.

[0036] The controller 121 can be configured by installing the above-mentioned program recorded and stored by the external storage device 123 into the computer. The external storage device 123 includes, for example, a magnetic disk such as HDD, an optical disk such as CD, a magneto-optical disk such as MO, a USB memory, a semiconductor memory such as SSD, etc. The storage device 121c or the external storage device 123 is configured as a recording medium that can be read by a computer. Hereinafter, as a general term for these, it is referred to as a recording medium. In this specification, the use of the term recording medium refers to a case where only a single storage device 121c is included, a case where only a single external storage device 123 is included, or a case where both are included. In addition, the provision of the program to the computer can also be carried out without using the external storage device 123, but using a communication unit such as a network or a dedicated line.

[0037] (2) Substrate processing steps

[0038] As one step of the manufacturing process (manufacturing method) of a semiconductor device using the substrate processing apparatus, an example of a processing sequence for processing a substrate, that is, forming a film on a wafer 200 as a substrate, is described. In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121.

[0039] In the substrate processing sequence of this embodiment, a film is formed on the wafer 200 by performing a cycle including the following steps a predetermined number of times (n times, where n is an integer greater than or equal to 1 or 2):

[0040] (a) Step A of supplying a first raw material and an additive to the wafer 200 to generate a second raw material that is chemically more stable than the first raw material, and exposing and adsorbing the first raw material and the second raw material on the surface of the wafer 200 to form a first layer;

[0041] (b) Step B of supplying a reactant to the wafer 200 to change the first layer into the second layer.

[0042] In this specification, for convenience, the above-mentioned substrate processing sequence is expressed as follows. In addition, the same notation is also used in the description of the following modified examples, etc.

[0043] (first raw material + additive → reactant) × n

[0044] The term "wafer" used in this specification refers to the wafer itself, or to a laminate of predetermined layers or films formed on the wafer and its surface. The term "wafer surface" used in this specification refers to the surface of the wafer itself, or to the surface of a predetermined layer, etc. formed on the wafer. "Forming a predetermined layer on a wafer" as described in this specification refers to directly forming a predetermined layer on the surface of the wafer itself, or to forming a predetermined layer on a layer, etc. formed on a wafer. The use of terms such as "substrate" in this specification is synonymous with the use of the term "wafer".

[0045] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, the additive, oxidizing agent, and nitriding agent may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0046] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, either the first layer or the second layer may include a continuous layer, a discontinuous layer, or both.

[0047] (Wafer charging and wafer boat loading)

[0048] When a plurality of wafers 200 are loaded (wafer filling) in the wafer boat 217, the shutter 219s is moved by the shutter opening and closing mechanism 115s to open the lower end opening of the manifold 209 (shutter opening). Figure 1 As shown, the wafer boat 217 supporting a plurality of wafers 200 is lifted by the wafer boat lifter 115 and carried into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared in the processing chamber 201.

[0049] In addition, the wafers 200 loaded into the wafer boat 217 have a three-dimensional surface, that is, a non-planar surface, for example, a surface having a concave portion or a step formed by a groove, a hole, or both.

[0050] (Pressure adjustment and temperature adjustment)

[0051] After the loading of the wafer boat is completed, the vacuum pump 246 performs vacuum exhaust (decompression exhaust) in such a manner that the space in the processing chamber 201, i.e., the space where the wafer 200 exists, becomes the required pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, the heater 207 heats the wafer 200 in the processing chamber 201 so that it becomes the required processing temperature. At this time, the degree of power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 becomes the required temperature distribution. In addition, the rotation of the wafer 200 is started by the rotation mechanism 267. Any one of the exhaust in the processing chamber 201, the heating and rotation of the wafer 200 is continuously performed at least until the processing of the wafer 200 is completed.

[0052] (Step A)

[0053] Thereafter, the first raw material and the additive are supplied to the wafer 200 .

[0054] Specifically, valves 243a and 243b are opened to allow the first raw material and additive to flow through gas supply pipes 232a and 232b, respectively. The first raw material and additive are flow-regulated by MFCs 241a and 241b, respectively, and supplied to the processing chamber 201 through nozzles 249a and 249b, mixed in the processing chamber 201, and exhausted through exhaust port 231a. At this time, the first raw material and additive are supplied to the wafer 200 from the side of the wafer 200 (first raw material + additive supply). At this time, valves 243d to 243f may also be opened to supply inert gas to the processing chamber 201 through each of nozzles 249a to 249c.

[0055] The treatment conditions when the first raw material and the additive are supplied in step A may be exemplified as follows:

[0056] Processing temperature: 350-800°C, preferably 350-650°C

[0057] Processing pressure: 1~1333Pa, preferably 1~931Pa

[0058] First raw material supply flow rate: 0.01 to 5 slm, preferably 0.1 to 2 slm

[0059] Additive supply flow rate: 0.01-10slm, preferably 0.1-5slm

[0060] Inert gas supply flow rate (per gas supply pipe): 0~10slm

[0061] Supply time of each substance: 1 to 120 seconds, preferably 1 to 60 seconds

[0062] In addition, the expression of a numerical range such as "350-800°C" in this specification means that the range includes a lower limit and an upper limit. Therefore, for example, "350-800°C" means "above 350°C and below 800°C". The same applies to other numerical ranges. In addition, the processing temperature in this specification means the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure means the pressure in the processing chamber 201. In addition, the processing time means the time during which the processing lasts. In addition, when the supply flow rate includes 0slm, 0slm means that the substance (gas) is not supplied. These are also the same in the following descriptions.

[0063] By supplying the first raw material and the additive to the wafer 200 under the above-mentioned processing conditions, a second raw material that is chemically more stable than the first raw material is generated, and the first raw material and the second raw material are exposed on the surface of the wafer 200. The first raw material and the second raw material exposed on the surface of the wafer 200 are adsorbed on the surface of the wafer 200 to form a first layer on the surface of the wafer 200.

[0064] The second raw material generated in this step is chemically more stable than the first raw material, so it is not easy to decompose compared to the first raw material, and it can be said that it is a compound that is not easy to undergo a gas phase reaction (also called a CVD reaction). Therefore, if the first raw material and the second raw material are exposed to the surface of the wafer 200, under the same processing conditions, compared with the case where only the first raw material is exposed to the surface of the wafer 200, the proportion of raw materials (first raw material, second raw material) in a state where no decomposition (undecomposed) and no gas phase reaction occurs that contribute to the formation of the first layer becomes higher. Since the raw materials (first raw material, second raw material) in a state where no decomposition and no gas phase reaction occur are easily supplied to various places in the concave portion of the wafer 200, a first layer with a small difference in thickness between the bottom and the top of the concave portion can be formed. Such a first layer is formed in step A, so by performing a cycle including step A and step B a predetermined number of times, the step coverage of the film formed on the surface of the wafer 200 can be improved. Hereinafter, “improving the step coverage of the film formed on the surface of the wafer 200 ” will also be simply referred to as “improving the step coverage”.

[0065] In this step, it is preferred that a portion of the first raw material react with the additive to change a first bond contained in a portion of the first raw material into a second bond having a higher bond energy than the first bond, thereby changing a portion of the first raw material into a second raw material. In this way, a second raw material that is chemically more stable than the first raw material can be generated from the first raw material, and the effect of improving the step coverage can be fully obtained.

[0066] Furthermore, when generating the second raw material, it is preferred that the bond with the lowest bond energy contained in the second raw material has a higher bond energy than the bond with the lowest bond energy contained in the first raw material. Thus, the chemical stability of the second raw material can be made higher than that of the first raw material, and the effect of improving the step coverage can be fully obtained.

[0067] In addition, in this step, it is preferred to decompose a part of the first raw material to generate an intermediate, and react the intermediate with an additive to generate a second raw material that is more chemically stable than the first raw material, or than the intermediate and the first raw material, respectively. At this time, by changing the first bond contained in a part of the first raw material to a second bond with a higher bond energy than it, a part of the first raw material can also be changed into the second raw material. In addition, the bond with the lowest bond energy contained in the generated second raw material can also have a higher bond energy than the bond with the lowest bond energy contained in the first raw material. In this way, in step A, a second raw material that is more chemically stable than the first raw material, or than the intermediate and the first raw material generated by decomposing the first raw material, respectively, can be generated, thereby fully obtaining the effect of improving the step coverage.

[0068] In addition, in this step, it is preferred that the activation energy required for the generated second raw material to react with the second layer described later is greater than the activation energy required for the first raw material to react with the second layer, so that the activation energy required for the first raw material to react with the second layer is higher than the activation energy required for the intermediate generated by decomposing the first raw material to react with the second layer. As a result, the reactivity of the second raw material with the second layer becomes lower than the reactivity of the first raw material with the second layer, and the reactivity of the first raw material with the second layer can be lower than the reactivity of the second layer with the intermediate generated by decomposing the first raw material. In addition, as a result, the adsorption of the generated second raw material to the second layer can be made lower than the adsorption of the first raw material to the second layer, and the adsorption of the first raw material to the second layer can be made lower than the adsorption of the intermediate generated by decomposing the first raw material to the second layer. Therefore, compared with the case of using only the first raw material, the decomposed first raw material can be suppressed from being adsorbed multiple times on the upper part of the recessed portion of the wafer 200, and as a result, the effect of improving the step coverage can be fully obtained. Furthermore, the raw materials (first raw material and second raw material) can be easily supplied to various locations on the wafer 200 , for example, can easily reach the bottom of the recess of the wafer 200 , and from this point of view, the effect of improving the step coverage can be fully obtained.

[0069] In this step, the first raw material and the second raw material generated from a part of the first raw material are exposed and adsorbed on the surface of the wafer 200 to form the first layer. At this time, in this step, it is preferred that the total exposure amount of the first raw material to the surface of the wafer 200 and the exposure amount of the second raw material to the surface of the wafer 200 be set to be greater than the exposure amount of the decomposed first raw material to the surface of the wafer 200, and it is more preferred that the total exposure amount of the first raw material to the surface of the wafer 200 and the exposure amount of the second raw material to the surface of the wafer 200 be set to be greater than the exposure amount of the decomposed first raw material to the surface of the wafer 200. By setting the exposure amount of the first raw material and the second raw material to the surface of the wafer 200 in this way, the effect of improving the step coverage can be significantly obtained. In addition, in this specification, when only the terms "first raw material", "second raw material" and the like are used as terms to represent a substance, it means that the substance is in an undecomposed state. On the other hand, when the terms "decomposed first raw material" and the like are used as terms to represent a substance, it means that the substance is in a decomposed state. Therefore, the "first raw material to be decomposed" includes an intermediate produced by decomposing the first raw material.

[0070] In this step, the sum of the adsorption amount of the first raw material on the surface of the wafer 200 and the adsorption amount of the second raw material on the surface of the wafer 200 is preferably set to be greater than the adsorption amount of the decomposed first raw material on the surface of the wafer 200, and more preferably the sum of the adsorption amount of the first raw material on the surface of the wafer 200 and the adsorption amount of the second raw material on the surface of the wafer 200 is set to be greater than the adsorption amount of the decomposed first raw material on the surface of the wafer 200. By setting the adsorption amount of the first raw material and the second raw material on the wafer 200 in this way, the effect of improving the step coverage can be significantly obtained.

[0071] In this step, the ratio of the sum of the amount of adsorption of the first raw material on the surface of the wafer 200 and the amount of adsorption of the second raw material on the surface of the wafer 200 to the sum of the amount of adsorption of the first raw material on the surface of the wafer 200, the amount of adsorption of the second raw material on the surface of the wafer 200, and the amount of adsorption of the first raw material on the surface of the wafer 200 by the decomposition is preferably set to 50% or more, more preferably 60% or more, and further preferably 70% or more. In addition, the ratio of the sum of the amount of adsorption of the first raw material on the surface of the wafer 200 and the amount of adsorption of the second raw material on the surface of the wafer 200 to the sum of the amount of adsorption of the first raw material on the surface of the wafer 200, the amount of adsorption of the second raw material on the surface of the wafer 200, and the amount of adsorption of the first raw material on the surface of the wafer 200 by the decomposition is 95% or less, more preferably 90% or less, and further preferably 80% or less.

[0072] In this step, when the ratio of the sum of the adsorption amount of the first raw material on the surface of the wafer 200 and the adsorption amount of the second raw material on the surface of the wafer 200 to the sum of the adsorption amount of the first raw material on the surface of the wafer 200, the adsorption amount of the second raw material on the surface of the wafer 200, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200 is less than 50%, the decomposition amount of the first raw material is excessive, and there is a situation where the step coverage rate deteriorates. By setting the ratio to more than 50%, the decomposition of the first raw material can be suppressed, the decomposition amount of the first raw material can be reduced, and the step coverage rate can be improved. By setting the ratio to more than 60%, the decomposition of the first raw material can be further suppressed, the decomposition amount of the first raw material can be further reduced, and the step coverage rate can be further improved. By setting the ratio to more than 70%, the decomposition of the first raw material can be further suppressed, the decomposition amount of the first raw material can be further reduced, and the step coverage rate can be further improved. Therefore, in step A, preferably, the ratio of the total amount of the first raw material adsorbed on the surface of the wafer 200 and the second raw material adsorbed on the surface of the wafer 200 to the total amount of the first raw material adsorbed on the surface of the wafer 200, the second raw material adsorbed on the surface of the wafer 200, and the decomposed first raw material adsorbed on the surface of the wafer 200 is set to be greater than 50%, more preferably the ratio is set to be greater than 60%, and even more preferably the ratio is set to be greater than 70%.

[0073] In addition, in this step, when the ratio of the sum of the adsorption amount of the first raw material on the surface of the wafer 200 and the adsorption amount of the second raw material on the surface of the wafer 200 to the sum of the adsorption amount of the first raw material on the surface of the wafer 200, the adsorption amount of the second raw material on the surface of the wafer 200, and the decomposed adsorption amount of the first raw material on the surface of the wafer 200 is higher than 95%, the film formation rate decreases and productivity may deteriorate. By setting this ratio to less than 95%, the decrease in the film formation rate can be suppressed and productivity can be improved. By setting this ratio to less than 90%, the decrease in the film formation rate can be further suppressed and productivity can be further improved. By setting this ratio to less than 80%, the decrease in the film formation rate can be further suppressed and productivity can be further improved. Therefore, in step A, preferably, the ratio of the adsorption amount of the first raw material on the surface of the wafer 200 to the total of the adsorption amount of the first raw material on the surface of the wafer 200, the adsorption amount of the second raw material on the surface of the wafer 200, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200 is set to less than 95%, more preferably the ratio is set to less than 90%, and further preferably the ratio is set to less than 80%.

[0074] In addition, in this step, the exposure amount (adsorption amount) of the second raw material to the surface of the wafer 200 can also be set to be greater than the total of the exposure amount (adsorption amount) of the first raw material to the surface of the wafer 200 and the exposure amount (adsorption amount) of the decomposed first raw material to the surface of the wafer 200, and the exposure amount (adsorption amount) of the second raw material to the surface of the wafer 200 can also be greater than the total of the exposure amount (adsorption amount) of the first raw material to the surface of the wafer 200 and the exposure amount (adsorption amount) of the decomposed first raw material to the surface of the wafer 200. Furthermore, in this step, the exposure amount (adsorption amount) of the first raw material to the surface of the wafer 200 may be set to be greater than the sum of the exposure amount (adsorption amount) of the second raw material to the surface of the wafer 200 and the exposure amount (adsorption amount) of the decomposed first raw material to the surface of the wafer 200, or the exposure amount of the first raw material to the surface of the wafer 200 may be set to be greater than the sum of the exposure amount of the second raw material to the surface of the wafer 200 and the exposure amount of the decomposed first raw material to the surface of the wafer 200. By setting the exposure amounts of the first raw material and the second raw material to the surface of the wafer 200 in this way, the effect of improving the step coverage can be significantly obtained as described above.

[0075] After the first layer is formed on the surface of the wafer 200, the valves 243a and 243b are closed to stop the supply of the first raw material and the additive into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove the gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243d to 243f are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging (purging) the processing chamber 201.

[0076] The following are examples of treatment conditions when purging is performed in step A:

[0077] Processing pressure: 1~30Pa

[0078] Processing time: 1 to 120 seconds, preferably 1 to 60 seconds

[0079] Inert gas supply flow rate (each gas supply pipe): 0.5~20slm.

[0080] In addition, the treatment temperature when purging is performed in this step is preferably set to the same temperature as the treatment temperature when the first raw material and the additive are supplied.

[0081] -First Raw Material-

[0082] As the first raw material, for example, a compound containing a main element (main component) constituting a film formed on the wafer 200 and a halogen can be used. As a compound containing a main element constituting a film and a halogen, for example, a halosilanes containing silicon (Si) and a halogen can be used. Here, a halosilanes refers to silanes having a halogen element as a substituent. As halogen elements contained in halosilanes, for example, chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. can be cited, preferably Cl, Br, I, and more preferably Cl. That is, among the halosilanes, chlorosilanes are more preferably used. As the first raw material, a halosilanes containing one Si in one molecule can be used, and a halosilanes containing two or more (preferably two) Si in one molecule can also be used. As the first raw material, a halosilanes containing at least one of a Si-Si bond and a Si-hydrogen (H) bond in one molecule is preferably used.

[0083] As the first raw material, for example, chlorosilane gas having Si-H bond, such as monochlorosilane (SiH3Cl) gas, dichlorosilane (SiH2Cl2) gas, trichlorosilane (SiHCl3) gas, or chlorosilane gas having Si-Si bond, such as hexachlorodisilane (Si2Cl6) gas, can be used. In addition, as the first raw material, for example, bromosilane gas having Si-H bond, such as monobromosilane (SiH3Br) gas, dibromosilane (SiH2Br2) gas, tribromosilane (SiHBr3) gas, or iodosilane gas having Si-H bond, such as monoiodosilane (SiH3I) gas, diiodosilane (SiH2I2) gas, triiodosilane (SiHI3) gas, can be used. As the first raw material, one or more of these can be used.

[0084] As the first raw material, for example, an alkyl halosilane containing Si, a halogen and an alkyl group can be used. As the alkyl halosilane gas, for example, an alkyl chlorosilane gas having a Si-Si bond, such as 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2) gas, can be used. In addition, as the first raw material, for example, an alkyl chlorosilane gas having a Si-H bond, such as dimethylchlorosilane ((CH3)2SiHCl) can be used. As the first raw material, one or more of these can be used.

[0085] As the first raw material, for example, a compound containing a main element constituting a film formed on the wafer 200 and an amino group can be used. As the compound containing a main element constituting a film and an amino group, for example, aminosilane containing Si and an amino group can be used. Aminosilane refers to a silane having an amino group as a substituent. The amino group contained in the aminosilane may be any of an unsubstituted amino group and a substituted amino group. As a substituted amino group, for example, a substituted amino group substituted by an alkyl group having 1 to 4 carbon atoms and a substituted amino group substituted by SiH3 can be used. The two substituents possessed by the substituted amino group may be the same or different.

[0086] As aminosilane, in addition to the Si-N bond between Si and nitrogen (N) constituting the amino group, it is preferred that the aminosilane further contains at least one of a Si-H bond between Si and H and a Si-O bond between Si and oxygen (O). In addition, the aminosilane preferably contains at least one of a Si-N bond, a Si-H bond and a Si-O bond, and a Si-C bond between Si and carbon (C).

[0087] As aminosilane, for example, aminosilane gases having three Si-H bonds in the molecule, such as diisopropylaminosilane (SiH3[N(C3H7)]2) gas and di-sec-butylaminosilane (SiH3[H(C4H9)]2) gas, can be used. In addition, as aminosilane, for example, aminosilane gases having two Si-H bonds in the molecule, such as bis(diethylamino)silane (SiH2[N(C3H7)2]2) gas and bis(dipropylamino)silane (SiH2[N(C3H7)2]2) gas, can be used. In addition, as aminosilane, for example, aminosilane gases having one Si-H bond in the molecule, such as tris(dimethylamino)silane (SiH[N(CH3)2]3) gas, can be used. As the first raw material, one or more of these can be used.

[0088] As the first raw material, for example, a compound containing a main element constituting a film formed on the wafer 200 and an alkoxy group can be used. As a compound containing a main element constituting a film and an alkoxy group, for example, an alkoxysilane containing Si and an alkoxy group can be used. Alkoxysilane refers to a silane having an alkoxy group as a substituent. Alkoxysilane has chemically stable and thermally stable properties, and by using this compound, the step coverage can be further improved. As an alkoxy group, for example, an alkoxy group having 1 to 4 carbon atoms can be used. Alkoxysilane is more preferably an alkoxyaminosilane containing an amino group as a substituent. That is, the alkoxysilane preferably contains an alkoxyaminosilane containing a Si-N bond between Si and N constituting an alkoxy group in addition to a Si-O bond between Si and O constituting an alkoxy group.

[0089] Alkoxyaminosilane is, for example, a compound that can take into account both adsorption to the wafer 200 and chemical and thermal stability. By using this compound, the step coverage can be further improved. The number of alkoxy groups in one molecule is preferably greater than the number of amino groups, and more preferably greater than the number of amino groups. The number of chemical bonds between Si and alkoxy groups (i.e., the number of Si-O bonds) is preferably greater than the number of chemical bonds between Si and amino groups (i.e., the number of Si-N bonds), and more preferably greater than the number of chemical bonds between Si and amino groups.

[0090] As the alkoxyaminosilane, for example, an alkoxyaminosilane gas having three Si-O bonds in the molecule, such as (dimethylamino)trimethoxysilane (Si(OCH3)3[N(CH3)2]) gas, can be used. As the alkoxyaminosilane, for example, an alkoxyaminosilane gas having two Si-O bonds in the molecule, such as bis(dimethylamino)dimethoxysilane (Si(OCH3)2[N(CH3)2]2) gas, can be used. As the alkoxyaminosilane, for example, an alkoxyaminosilane gas having one Si-O bond in the molecule, such as tris(dimethylamino)methoxysilane (Si(OCH3)N(CH3)2]3) gas, can be used. As the first raw material, one or more of these can be used.

[0091] As the first raw material, for example, silylamine can be used. As the silylamine, for example, a silylamine-based gas having three Si-N bonds in the molecule, such as trimethylsilylamine (N(SiH 3 ) 3 ) gas, can be used.

[0092] -additive-

[0093] As the additive, for example, a halogen monomer, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon, a halogenated carbon, hydrogen (H 2 ), hydrogen nitride, or an alcohol can be used.

[0094] As halogen monomers, for example, fluorine (F2), chlorine (Cl2), and bromine (Br2) can be used. As hydrogen halides, for example, hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), and hydrogen iodide (HI) can be used. As hydrocarbons, for example, methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H 10) and other saturated hydrocarbons, and unsaturated hydrocarbons such as ethylene (C2H4), propylene (C3H6), and butene (C4H8). As halogenated hydrocarbons, for example, trifluoromethane (CHF3), difluoromethane (CH2F2), fluorinated methyl ether (CH3F), chloroform (CHCl3), dichloromethane (CH2Cl2), and methyl chloride (CH3Cl) can be used. As halogenated carbons, for example, carbon tetrafluoride (CF4) and carbon tetrachloride (CCl4) can be used. As hydrocarbons, for example, ammonia (NH3) can be used. As alcohols, for example, methanol (CH3OH), ethanol (C2H5OH), and propanol (C3H7OH) can be used. As additives, one or more of these can be used.

[0095] - Inert gas -

[0096] As the inert gas, for example, nitrogen (N2) gas, or rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This is also the same in step B described later.

[0097] -Reaction process for producing the second raw material-

[0098] Hereinafter, schemes (1) to (4) will be used to describe an example of a reaction process in which a second raw material that is chemically more stable than the first raw material is generated by supplying a first raw material and an additive to the wafer 200. In the following example, a case where a compound containing Si as a main element constituting a film is used as the first raw material will be described.

[0099] -Options (1) and (2)-

[0100] Under the above-mentioned treatment conditions (especially the treatment temperature), by using a specific first raw material and a specific additive, a reaction between the first raw material and the additive, such as exemplified in the following scheme (1), can be produced, so that a second raw material that is more chemically stable than the first raw material can be produced. In addition, under the above-mentioned treatment conditions (especially the treatment temperature), by using a specific first raw material and a specific additive, a reaction between an intermediate produced by decomposing a part of the first raw material and the additive, such as exemplified in the following scheme (2), can be produced, so that a second raw material that is more chemically stable than the first raw material, or than the intermediate and the first raw material, can be produced. In addition, in this step, there is a case where the reaction shown in scheme (1) and the reaction shown in scheme (2) occur simultaneously.

[0101] [Chemistry 1]

[0102] Solution (1)

[0103] SiA (4-X) B X +Z

[0104] →SiA(4-X) B (X-Y) Z′ Y +B′

[0105] Solution (2)

[0106] SiA( 4-X) B X +Z

[0107] →SiA (4-X) B (X-Y) +B′+Z

[0108] →SiA (4-X) B (X-Y) Z′ Y +B′

[0109] In scheme (1), “SiA (4-X) B X " indicates the first raw material, "Z" indicates an additive, "SiA (4-X) B (X-Y) Z' Y " represents the second raw material, X represents an integer of 1 to 3, and Y represents an integer satisfying 1≤Y≤X. In addition, in the scheme (2), "SiA (4-X) B X " indicates the first raw material, "Z" indicates an additive, "SiA (4-X) B (X-Y) " indicates an intermediate, "SiA (4-X) B (X-Y) Z' Y ” represents the second raw material, X represents an integer of 1 to 3, and Y represents an integer satisfying 1≤Y≤X.

[0110] Schemes (1) and (2) are divided into a first embodiment using a first raw material of a compound containing Si and a halogen (e.g., halosilanes, alkylhalosilanes), and a second embodiment using a first raw material of a compound containing Si and an amino group (e.g., aminosilanes, alkoxyaminosilanes, silylamines). In addition, the second embodiment is further divided into an embodiment using a first raw material of a compound containing Si and an amino group and having a Si-H bond (embodiment 2-1), and an embodiment using a first raw material of a compound containing Si and an amino group and not having a Si-H bond (embodiment 2-2).

[0111] ··Method 1

[0112] First, the case of the first embodiment is described. In the case of the first embodiment, in schemes (1) and (2), A represents a halogen atom or an alkyl group, B represents a hydrogen atom (H), Z represents a halogen monomer, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon or a halogenated carbon, Z' represents a group containing a portion of a Z molecule, and B' represents a product generated by cutting the Si-B bond, or a product generated by bonding a portion of a B molecule to a portion of a Z molecule. Among them, at least one of A is a halogen atom. In addition, when X is 1 or 2, and the first raw material and the second raw material have multiple A, the multiple A may be different or all the same. When Y is 2 or 3, and the second raw material has multiple Z', the multiple Z' may be different or all the same.

[0113] The first raw material used in the first embodiment has a Si-H bond as a Si-B bond. The Si-H bond has a lower bond energy than other chemical bonds (e.g., Si-halogen bonds, etc.). That is, the Si-H bond can be said to have a characteristic of being more easily cut than other chemical bonds (e.g., Si-halogen bonds, etc.) under the above-mentioned processing conditions.

[0114] In the case of scheme (1), under the above-mentioned treatment conditions, the first raw material reacts with the additive Z, and the Si-H bond portion with lower bond energy reacts with the additive Z to generate a second raw material having a Si-Z' bond obtained by bonding a part of the Z molecule to Si.

[0115] In the case of scheme (2), under the above-mentioned treatment conditions, the Si-H bond H contained in the first raw material is cut, thereby generating an intermediate "SiA" containing Si having Y dangling bonds. (4-X) B (X-Y) ". The generated intermediate is an unstable substance in which the Si-H bond of the first raw material is partially radicalized. Therefore, the dangling bond of the intermediate is bonded to a part of the Z molecule as an additive to generate a second raw material having a Si-Z' bond.

[0116] The bond energy of the Si-Z' bond (e.g., Si-N bond, Si-halogen bond, Si-C bond, etc.) in the second raw material thus generated is higher than that of the Si-H bond in the first raw material. Thus, in the first mode, a part of the first raw material reacts with the additive, so that the first bond (here, Si-H bond) contained in a part of the first raw material is changed into a second bond (here, Si-N bond, Si-halogen bond, Si-C bond, etc. which is a Si-Z' bond) having a higher bond energy than the first bond, thereby changing a part of the first raw material into the second raw material. Thus, a second raw material which is more chemically stable than the first raw material can be generated.

[0117] In addition, the Si-H bonds of the first raw material may be partially or completely changed to Si-Z' bonds. That is, the second raw material may have Si-H bonds (remaining Si-H bonds) or may not have Si-H bonds.

[0118] In the case of the first embodiment, among the above-mentioned treatment conditions, the treatment temperature is preferably set to 400 to 800° C. By selecting such a treatment temperature, the reactions shown in the above schemes (1) and (2) can be performed more efficiently.

[0119] ··Method 2-1

[0120] Next, the case of embodiment 2-1 is described. In the case of embodiment 2-1, in schemes (1) and (2), A represents an amino group, an alkyl group or an alkoxy group, B represents a hydrogen atom, Z represents hydrogen, nitride, alcohol, hydrocarbon, halogenated hydrocarbon or halogenated carbon, Z' represents a group containing a part of the Z molecule, and B' represents a product generated by cutting the Si-B bond, or a product generated by bonding a part of the B molecule to a part of the Z molecule. Among them, at least one of A is an amino group. The amino group represented by A may be any of an unsubstituted amino group and a substituted amino group, and a substituted amino group is particularly preferred. As a substituted amino group, for example, a substituted amino group substituted by an alkyl group having 1 to 4 carbon atoms and a substituted amino group substituted by SiH3 can be used. In addition, when X is 1 or 2 and the first raw material and the second raw material have multiple A's, the multiple A's may be different or all the same. When Y is 2 or 3 and the second raw material has multiple Z's, the multiple Z's may be different or all the same.

[0121] The first raw material used in the second embodiment has a Si-H bond as a Si-B bond. The bond energy of the Si-H bond is lower than that of other chemical bonds (e.g., Si-N bond, Si-O bond, etc.). That is, the Si-H bond can be said to have the characteristic of being more easily cut than other chemical bonds (e.g., Si-N bond, Si-O bond, etc.) under the above-mentioned processing conditions.

[0122] In the case of solution (1), under the above-mentioned treatment conditions, the Si-H bond portion having a lower bond energy than that of the first raw material reacts with the additive Z to generate a second raw material having a Si-Z' bond in which a part of the Z molecule is bonded to Si.

[0123] In the case of scheme (2), under the above-mentioned treatment conditions, H is cut from the Si-H bond of the first raw material, thereby generating an intermediate "SiA" containing Si having Y dangling bonds. (4-X) B (X-Y)". The generated intermediate is an unstable substance in which the Si-H bond portion of the first raw material is radicalized. The intermediate, which is an unstable substance, reacts rapidly with the additive Z, bonds a part of the additive Z molecule to the dangling bond portion, and generates a second raw material having a Si-Z' bond.

[0124] The bond energy of the Si-Z' bond (for example, Si-N bond, Si-halogen bond, Si-C bond, etc.) in the second raw material generated as described above is higher than that of the Si-H bond in the first raw material. Thus, in the 2-1 mode, a part of the first raw material reacts with the additive, so that the first bond (here, Si-H bond) contained in a part of the first raw material is changed into a second bond (here, Si-N bond, Si-halogen bond, Si-C bond, etc. which is Si-Z' bond) having a higher bond energy than the first bond, thereby changing a part of the first raw material into the second raw material. Thus, in the 2-1 mode, a second raw material which is more chemically stable than the first raw material can be generated.

[0125] In the embodiment 2-1, part of the Si-H bonds in the first raw material may be changed to Si-Z' bonds, or all of them may be changed to Si-Z' bonds. That is, the second raw material may have Si-H bonds (remaining Si-H bonds) or may not have Si-H bonds.

[0126] In addition, in the first raw material used in the 2-1st mode, there is a case where A is a substituted amino group substituted by an alkyl group (for example, a dimethylamino group, a diethylamino group, a dipropylamino group, etc.). At this time, depending on the processing conditions or additives, there is also a case where A, which is a substituted amino group substituted by an alkyl group, reacts with an additive Z (for example, NH3) and changes into an unsubstituted amino group (-NH2). That is, in this case, A, which is a substituted amino group substituted by an alkyl group in the first raw material, becomes an unsubstituted amino group (-NH2) in the second raw material. The bond energy (Bond Energy) of the NH bond of the unsubstituted amino group is higher than the NC bond of the amino group substituted by an alkyl group. Therefore, when the above-mentioned change occurs in A, a second raw material that is more chemically stable than the first raw material can be generated compared to the case where the change does not occur.

[0127] In the case of the 2-1 embodiment, among the above-mentioned treatment conditions, the treatment temperature is preferably set to 400 to 700° C. By selecting such a treatment temperature, the reactions shown in the above schemes (1) and (2) can be more efficiently performed.

[0128] ··Method 2-2

[0129] Next, the case of embodiment 2-2 is described. In the case of embodiment 2-2, in schemes (1) and (2), A represents an alkyl group or an alkoxy group, B represents an amino group, Z represents nitride, alcohol, hydrocarbon, halogenated hydrocarbon or halogenated carbon, Z' represents a group containing a part of the Z molecule, and B' represents a product generated by cutting the Si-B bond, or a product generated by bonding a part of the B molecule to a part of the Z molecule. Among them, at least one of B is a substituted amino group substituted by an alkyl group (for example, dimethylamino, diethylamino, dipropylamino, etc.). When the second raw material has multiple Z's, the multiple Z's may be different or all the same.

[0130] The first raw material used in the embodiment 2-1 has a substituted amino group substituted with an alkyl group at B. The substituted amino group substituted with an alkyl group has a NC bond with a lower bond energy than other chemical bonds (e.g., Si-O bond, Si-C bond, OC bond, CH bond, etc.).

[0131] In the case of scheme (1), under the above-mentioned treatment conditions, B having a NC bond with a relatively low bond energy in the first raw material reacts with the additive Z to produce a second raw material having Z' having a bond (eg, NH bond) with a higher bond energy than the NC bond.

[0132] In the case of scheme (2), under the above-mentioned treatment conditions, B having a NC bond of the first raw material is cut to generate an intermediate "SiA" containing Si having Y dangling bonds. (4-X) B (X-Y) ". The generated intermediate is an unstable substance in which the Si-B bond portion of the first raw material is radicalized. The intermediate, which is an unstable substance, reacts rapidly with the additive Z, bonds a part of the molecule of the additive Z to the dangling bond portion of Si, and generates a second raw material having a Si-Z' bond.

[0133] The bond energy of the bond (e.g., NH bond, etc.) contained in Z' in the second raw material generated as described above is higher than the bond (e.g., NC bond) contained in B in the first raw material. Thus, in the 2-2 embodiment, a portion of the first raw material reacts with the additive, so that the first bond (here, NC bond) contained in a portion of the first raw material is changed into a second bond (here, NH bond, etc.) having a higher bond energy than the first bond, thereby changing a portion of the first raw material into the second raw material. Thus, in the 2-2 embodiment, a second raw material that is more chemically stable than the first raw material can be generated.

[0134] In the case of the 2-2 embodiment, among the above-mentioned treatment conditions, the treatment temperature is preferably set to 450 to 800° C. By selecting such a treatment temperature, the reactions shown in the above schemes (1) and (2) can be more efficiently performed.

[0135] -Options (3) and (4)-

[0136] Furthermore, under the above-mentioned treatment conditions (especially the treatment temperature), by using a specific first raw material and a specific additive, a reaction between the first raw material and the additive, such as exemplified by the following scheme (3), can be produced, thereby producing a second raw material that is more chemically stable than the first raw material. Furthermore, under the above-mentioned treatment conditions (especially the treatment temperature), by using a specific first raw material and a specific additive, a reaction between an intermediate produced by decomposing a part of the first raw material and the additive, such as exemplified by the following scheme (4), can be produced, thereby producing a second raw material that is more chemically stable than the first raw material, or than the intermediate and the first raw material, respectively. Furthermore, in this step, there is a case where the reaction shown in scheme (3) and the reaction shown in scheme (4) occur simultaneously.

[0137] [Chemistry 2]

[0138] Solution (3)

[0139] A3Si-SiA3+Z

[0140] →(SiA3Z′+SiA3Z′)or(SiA4+SiA2Z′2)

[0141] Solution (4)

[0142] A3Si-SiA3+Z

[0143] →SiA4+SiA2+Z

[0144] →SiA4+SiA2Z′2

[0145] In scheme (3), "A3Si-SiA3" represents the first raw material, "Z" represents an additive, and "(SiA3Z'+SiA3Z')" or "(SiA4+SiA2Z'2)" represents the second raw material. In addition, in scheme (4), "A3Si-SiA3" represents the first raw material, "Z" represents an additive, "SiA2" represents an intermediate, and "SiA4" and "SiA4+SiA2Z'2" represent the second raw material.

[0146] In the schemes (3) and (4), A represents a halogen atom or an alkyl group, Z represents a halogen monomer, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon or a halogenated carbon, and Z' represents a group containing a part of the molecule of Z. When the second raw material has a plurality of Z's, the plurality of Z's may be different or all the same.

[0147] The bond energy of the Si-Si bond in the first raw material represented by "A3Si-SiA3" is lower than that of the Si-A bond (for example, Si-halogen bond, Si-C bond).

[0148] In the case of scheme (3), under the above-mentioned treatment conditions, the first raw material reacts with the additive Z to generate two molecules of "SiA3Z'" or two molecules of "SiA4" and "SiA2Z'2".

[0149] In the case of scheme (4), under the above-mentioned treatment conditions, the Si-Si bond of the first raw material is cut, and one molecule of the intermediate "SiA2" containing Si having two dangling bonds (hanging bonds) is generated. At this time, the second raw material represented by SiA4 is also generated. The generated intermediate is an unstable substance in which the Si-Si bond part of the first raw material is radicalized. The intermediate as an unstable substance reacts rapidly with the additive Z, and a part of the molecule of the additive Z is bonded to the dangling bond part of Si to generate "SiA2Z'2" as the second raw material.

[0150] The bond energy of the Si-Z' bond (for example, Si-halogen bond, Si-H bond, Si-C bond, etc.) in the second raw material thus generated is higher than that of the Si-Si bond in the first raw material. In this way, a part of the first raw material reacts with the additive, so that the first bond (here, Si-Si bond) contained in a part of the first raw material is changed into a second bond (here, Si-halogen bond, Si-H bond, Si-C bond, etc.) having a higher bond energy than the first bond, thereby changing a part of the first raw material into the second raw material. In this way, a second raw material that is more chemically stable than the first raw material can be generated.

[0151] In the case of the reaction shown in the above schemes (3) and (4), among the above treatment conditions, the treatment temperature is preferably set to 350 to 800° C. By selecting such a treatment temperature, the reaction shown in the above schemes (3) and (4) can be carried out more efficiently.

[0152] [Step B]

[0153] After step A is completed, the reactant is supplied to the wafer 200 , that is, to the wafer 200 on which the first layer is formed.

[0154] Specifically, valve 243c is opened to allow the reactant to flow through gas supply pipe 232c. The reactant is flow-regulated by MFC241c, supplied to processing chamber 201 through nozzle 249c, mixed in processing chamber 201, and exhausted from exhaust port 231a. At this time, the reactant is supplied to wafer 200 from the side of wafer 200 (reactant supply). At this time, valves 243d to 243f may also be opened to supply inert gas to processing chamber 201 through nozzles 249a to 249c, respectively.

[0155] The treatment conditions when supplying the reactant in step B may be exemplified as follows:

[0156] Processing temperature: 350-800°C, preferably 350-650°C

[0157] Processing pressure: 1~4000Pa, preferably 1~931Pa

[0158] Reactant supply flow rate: 1-20slm, preferably 1-10slm

[0159] Inert gas supply flow rate (per gas supply pipe): 0~10slm

[0160] Supply time of each substance: 1 to 120 seconds, preferably 1 to 60 seconds.

[0161] Since the reactant is supplied to the wafer 200 under the above-mentioned processing conditions, the first layer can be changed into the second layer. Specifically, in this step, since the reactant is supplied to the wafer 200 under the above-mentioned processing conditions, the elements contained in the reactant can be added to the first layer, so that the composition of the first layer is changed. Thus, the first layer can be changed (converted) into the second layer having a composition different from that of the first layer.

[0162] After the first layer is changed (converted) to the second layer, the valve 243c is closed to stop the supply of the reactant in the processing chamber 201. Then, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing sequence and processing conditions as those in the purging in step A. In addition, the processing temperature during purging in this step is preferably set to the same temperature as the processing temperature during the supply of the reactant.

[0163] - Reactor -

[0164] As a reactant, for example, an oxidant can be used. As an oxidant, for example, an O-containing gas or a H and O-containing gas can be used. As an O-containing gas, for example, oxygen (O2) gas, ozone (O3) gas, etc. can be used. As a H and O-containing gas, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, H2 gas+O2 gas, H2 gas+O3 gas, etc. can be used. That is, as a H and O-containing gas, a H-containing gas+O-containing gas (reducing gas+oxidizing gas) can also be used. In this case, as a H-containing gas, that is, a reducing gas, a deuterium (D2) gas can also be used instead of the H2 gas. As a reactant, one or more of these can be used.

[0165] In addition, the combined description of two gases such as "H2 gas + O2 gas" in this specification means a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 from different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0166] As a reactant, a nitriding agent, for example, can be used. As a nitriding agent, a gas containing N and H can be used. As a gas containing N and H, for example, ammonia (NH3) gas, diazene (N2H2) gas, hydrazine (N2H4) gas, N3H8 gas and other nitride-based gases can be used. In addition, as a gas containing N and H, for example, a gas containing C, N and H can be used. As the gas containing C, N and H, for example, ethylamine gases such as monoethylamine (C2H5NH2) gas, diethylamine ((C2H5)2NH) gas, triethylamine ((C2H5)3N) gas, or methylamine gases such as monomethylamine (CH3NH2) gas, dimethylamine ((CH3)2NH) gas, trimethylamine ((CH3)3N) gas, or organic hydrazine gases such as monomethylhydrazine ((CH3)HN2H2) gas, dimethylhydrazine ((CH3)2N2H2) gas, trimethylhydrazine ((CH3)2N2(CH3)H) gas can be used. As the reactant, one or more of these can be used.

[0167] As a reactant, for example, a gas containing C and H or a gas containing boron (B) can also be used. As a gas containing C and H, for example, hydrocarbon gases such as ethylene (C2H4) gas, acetylene (C2H2) gas, and propylene (C3H6) gas can be used. As a gas containing B, for example, trichloroborane (BCl3) gas, diborane (B2H6) gas, triethylborane ((C2H5)3B) gas, etc. can be used. As a reactant, one or more of these can be used.

[0168] [Scheduled number of implementations]

[0169] The cycle of performing the above-mentioned step A and step B alternately and non-simultaneously, i.e., asynchronously, is performed a predetermined number of times (n times, where n is an integer greater than 1 or 2), so that a film of a desired thickness can be formed (grown) on the surface of the wafer 200. The above-mentioned cycle is preferably repeated a plurality of times. That is, it is preferred that the thickness of the second layer formed in each cycle is thinner than the desired thickness, and the above-mentioned cycle is repeated a plurality of times until the thickness of the film formed by laminating the second layer reaches the desired thickness.

[0170] In addition, by using the above-mentioned various first raw materials, various additives, and various reactants, Si-containing films such as silicon oxide film (SiO film), silicon nitride film (SiN film), carbon oxynitride silicon film (SiOCN film), silicon oxygen carbide film (SiOC film), silicon oxynitride film (SiON film), silicon carbon nitride film (SiCN film), silicon carbide film (SiC film), silicon borocarbon nitride film (SiBCN film), silicon boronitride film (SiBN film), silicon carbide film (SiBC film), silicon borocarbon nitride film (SiBOCN film), silicon boronitride film (SiBON film), silicon borocarbide film (SiBOC film) can be formed on the surface of the wafer 200.

[0171] (Post-purge and atmospheric pressure recovery)

[0172] After the film formation on the wafer 200 is completed, an inert gas as a purge gas is supplied into the processing chamber 201 from the nozzles 249a to 249c, respectively, and exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the gas or reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0173] (Wafer boat unloading and wafer discharge)

[0174] After that, the sealing cover 219 is lowered by the wafer boat lifter 115 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After the wafer boat is unloaded, the baffle 219s is moved, and the lower end opening of the manifold 209 is sealed by the baffle 219s via the O-ring 220c (baffle closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer boat 217 (wafer unloading).

[0175] (3) Effects of this method

[0176] According to this aspect, one or more of the following effects can be obtained.

[0177] In step A, a second raw material that is more chemically stable than the first raw material is generated, and the first raw material and the second raw material are exposed and adsorbed on the surface of the wafer 200, thereby forming the first layer. Since the second raw material is more chemically stable than the first raw material, the proportion of raw materials (first raw material, second raw material) that have not been decomposed and have not undergone a gas phase reaction that contributes to the formation of the first layer becomes higher than when only the first raw material is used. Raw materials (first raw material, second raw material) that have not been decomposed and have not undergone a gas phase reaction are supplied to various locations in the recess of the wafer 200 to form a first layer with a small difference in thickness between the bottom and top of the recess. Since such a first layer is formed, the step coverage of the film formed on the wafer 200 (the film formed by laminating the second layer formed by changing the first layer) is improved.

[0178] In step A, the following combination is preferred: the first raw material contains a compound containing a main element constituting the film and a halogen, and the additive contains at least one of a halogen monomer, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon, and a halogenated carbon. When the first raw material and the additive are used in this combination, a second raw material that is more chemically stable than the first raw material can be effectively generated. As a result, the effect of improving the step coverage of the film formed on the wafer 200 can be more significantly obtained.

[0179] In step A, the following combination is preferred: the first raw material contains at least one of a compound containing a main element constituting a film and an amino group, a compound containing a main element constituting a film and an alkoxy group, and a silylamine, and the additive contains at least one of hydrogen, hydrogen nitride, alcohol, hydrocarbon, halogenated hydrocarbon, and halogenated carbon. When the first raw material and the additive are used in this combination, a second raw material that is more chemically stable than the first raw material can be effectively generated. As a result, the effect of improving the step coverage of the film formed on the wafer 200 can be more significantly obtained.

[0180] In step A, a compound containing a main element constituting a film and an alkoxy group, such as alkoxysilane, is preferably used as the first raw material, and the compound preferably further contains an amino group. That is, as the first raw material, a compound containing a main element constituting a film, an alkoxy group, and an amino group, such as alkoxyaminosilane, is preferably used. When the first raw material is a compound having such a structure, the effect of improving the step coverage of the film formed on the wafer 200 can be more significantly obtained.

[0181] In particular, in the compound containing the main element, alkoxy group and amino group constituting the film used as the first raw material, the number of alkoxy groups in one molecule is preferably greater than the number of amino groups, and more preferably greater than the number of amino groups. In addition, the number of chemical bonds between the atoms of the main element and the alkoxy group is preferably greater than the number of chemical bonds between the atoms of the main element and the amino group, and more preferably greater than the number of chemical bonds between the atoms of the main element and the amino group. When the first raw material is a compound having such a structure, the effect of improving the step coverage of the film formed on the wafer 200 can be more significantly obtained.

[0182] (4) Modification

[0183] The substrate processing sequence of this embodiment can be changed as shown in the following modified examples. Unless otherwise specified, the processing order and processing conditions in each step of the modified example can be set to be the same as the processing order and processing conditions in each step of the above-mentioned substrate processing sequence.

[0184] (Variant 1)

[0185] As shown in the following processing sequence, step B can also be a step of non-simultaneously supplying different types of reactants (for example, the first reactant, the second reactant, and the third reactant shown below). Here, n is an integer greater than 1 or an integer greater than 2, and m is an integer greater than 1 or an integer greater than 2. In addition, the first reactant, the second reactant, and the third reactant shown below are reactants with different molecular structures. As the first reactant, the second reactant, and the third reactant, any of the various reactants described above can be used.

[0186] (first raw material + additive → first reactant → second reactant) × n

[0187] (first raw material + additive → first reactant → second reactant → third reactant) × n

[0188] [(first raw material + additive → first reactant) × m → second reactant] × n

[0189] [(first raw material + additive → first reactant) × m → second reactant → third reactant] × n

[0190] [(first raw material + additive → first reactant → second reactant) × m → third reactant] × n

[0191] In this modification, the same effect as in the above-mentioned method can be obtained. In addition, according to this modification, elements contained in different types of reactants can be added to the first layer, so that the composition of the first layer can be changed in stages and with good controllability. Thus, the first layer can be changed (converted) into the second layer having the desired composition, and as a result, a film having the desired composition can be formed with good controllability. In addition, in this modification, the above-mentioned various films can be formed.

[0192] <Other aspects of the present invention>

[0193] The embodiments of the present disclosure have been specifically described above. However, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the gist of the invention.

[0194] In the above-mentioned method, as the first raw material, an example of using a compound containing Si as the main element constituting the film is described, but the main element constituting the film is not limited to Si. For example, as the main element constituting the film, in addition to Si, semiconductor elements such as germanium (Ge), or metal elements such as titanium (Ti), tantalum (Ta), molybdenum (Mo), tungsten (W), ruthenium (Ru), aluminum (Al), zirconium (Zr), and hafnium (Hf) can be exemplified. Even in the case of using a compound containing an element other than Si as the main element constituting the film as the first raw material, the same effect as in the above-mentioned method can still be obtained. In addition, in these cases, in addition to the Si-containing film, a film containing a semiconductor element such as Ge, or a film containing a metal element such as Ti, Ta, Mo, W, Ru, Al, Zr, and Hf can be formed.

[0195] The process used for each treatment is preferably prepared individually according to the treatment content, recorded and stored in the storage device 121c via the telecommunication path or the external storage device 123. Then, preferably, when starting each treatment, the CPU 121a appropriately selects a suitable process from the multiple processes recorded and stored in the storage device 121c according to the treatment content. Thus, a film of various film types, composition ratios, film qualities, and film thicknesses can be achieved with good reproducibility by using one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each treatment can be started quickly.

[0196] The above process is not limited to the case of newly making, and can also be prepared by changing an existing process installed in a substrate processing device, for example. When changing the process, the changed process can be installed in the substrate processing device via a telecommunication path or a recording medium recording the process. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing process installed in the substrate processing device.

[0197] In the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and for example, it can also be applied to the case where a film is formed using a single-type substrate processing device that processes one or more substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and it can also be applied to the case where a film is formed using a substrate processing device having a cold-wall type processing furnace.

[0198] When these substrate processing apparatuses are used, each process can be performed according to the same processing sequence and processing conditions as those in the above-mentioned embodiment or modified example, and the same effects as those in the above-mentioned embodiment or modified example can be obtained.

[0199] The above-mentioned aspects or modifications may be used in combination as appropriate. The processing order and processing conditions in this case may be, for example, the same as those in the above-mentioned aspects or modifications.

[0200] 200 wafers (substrates).

Claims

1. A substrate processing method, characterized in that: A film is formed on a substrate by performing a cycle including the following steps a predetermined number of times: (a) supplying a first raw material and an additive to a substrate to generate a second raw material that is chemically more stable than the first raw material, and exposing and adsorbing the first raw material and the second raw material to a surface of the substrate to form a first layer; (b) supplying a reactant to the substrate to change the first layer into a second layer.

2. The substrate processing method according to claim 1, characterized in that: In (a), a portion of the first raw material is reacted with the additive to change a first bond contained in a portion of the first raw material into a second bond having a higher bond energy than the first bond, thereby changing a portion of the first raw material into the second raw material.

3. The substrate processing method according to claim 1, characterized in that: The bond with the lowest bond energy contained in the second raw material has a higher bond energy than the bond with the lowest bond energy contained in the first raw material.

4. The substrate processing method according to claim 1, characterized in that: In (a), a portion of the first raw material is decomposed to generate an intermediate, and the intermediate is reacted with the additive to generate the second raw material which is chemically more stable than the first raw material, or than the intermediate and the first raw material, respectively.

5. The substrate processing method according to claim 4, characterized in that: The activation energy required for the reaction of the second raw material with the second layer is greater than the activation energy required for the reaction of the first raw material with the second layer, and the activation energy required for the reaction of the first raw material with the second layer is higher than the activation energy required for the reaction of the intermediate with the second layer.

6. The substrate processing method according to claim 1, characterized in that: In (a), the total exposure amount of the first raw material to the surface of the substrate and the exposure amount of the second raw material to the surface of the substrate is set to be greater than the exposure amount of the first raw material to the surface of the substrate after decomposition, or the exposure amount of the second raw material to the surface of the substrate is set to be greater than the total exposure amount of the first raw material to the surface of the substrate and the exposure amount of the first raw material to the surface of the substrate after decomposition, or the exposure amount of the first raw material to the surface of the substrate is set to be greater than the total exposure amount of the second raw material to the surface of the substrate and the exposure amount of the first raw material to the surface of the substrate after decomposition.

7. The substrate processing method according to claim 1, characterized in that: In (a), the total amount of the first raw material adsorbed on the surface of the substrate and the amount of the second raw material adsorbed on the surface of the substrate is set to be greater than the amount of the first raw material adsorbed on the surface of the substrate after decomposition, or the amount of the second raw material adsorbed on the surface of the substrate is set to be greater than the total amount of the first raw material adsorbed on the surface of the substrate and the amount of the first raw material adsorbed on the surface of the substrate after decomposition, or the amount of the first raw material adsorbed on the surface of the substrate is set to be greater than the total amount of the second raw material adsorbed on the surface of the substrate and the amount of the first raw material adsorbed on the surface of the substrate after decomposition.

8. The substrate processing method according to claim 1, characterized in that: In (a), the ratio of the total amount of the first raw material adsorbed on the surface of the substrate and the second raw material adsorbed on the surface of the substrate to the total amount of the first raw material adsorbed on the surface of the substrate, the second raw material adsorbed on the surface of the substrate and the first raw material adsorbed on the surface of the substrate after decomposition is set to be greater than 50%.

9. The substrate processing method according to claim 1, characterized in that: In (a), the ratio of the total amount of the first raw material adsorbed on the surface of the substrate and the second raw material adsorbed on the surface of the substrate to the total amount of the first raw material adsorbed on the surface of the substrate, the second raw material adsorbed on the surface of the substrate and the first raw material adsorbed on the surface of the substrate after decomposition is set to less than 95%.

10. The substrate processing method according to any one of claims 1 to 9, characterized in that: The first raw material includes a compound containing a main element constituting the film and a halogen, and the additive includes at least one of a halogen element, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon, and a halogenated carbon.

11. The substrate processing method according to any one of claims 1 to 9, characterized in that: The first raw material includes at least one of a compound containing the main element constituting the film and an amino group, a compound containing the main element and an alkoxy group, and silylamine, and the additive includes at least one of hydrogen, hydrogen nitride, alcohol, hydrocarbon, halogenated hydrocarbon, and halogenated carbon.

12. The substrate processing method according to any one of claims 1 to 9, characterized in that: The first raw material includes a compound containing a main element constituting the film and an alkoxy group.

13. The substrate processing method according to claim 12, characterized in that: The above compounds further contain an amino group.

14. The substrate processing method according to claim 13, characterized in that: The number of alkoxy groups in one molecule of the above compound is equal to or greater than the number of amino groups.

15. The substrate processing method according to claim 13, characterized in that: In the compound, the number of chemical bonds between the atom of the main element and the alkoxy group is greater than the number of chemical bonds between the atom of the main element and the amino group.

16. The substrate processing method according to claim 12, characterized in that: The above compound is an alkoxysilane.

17. The substrate processing method according to claim 13, characterized in that: The above compound is an alkoxyaminosilane.

18. A method for manufacturing a semiconductor device, characterized in that: A film is formed on a substrate by performing a cycle including the following steps a predetermined number of times: (a) supplying a first raw material and an additive to a substrate to generate a second raw material that is chemically more stable than the first raw material, and exposing and adsorbing the first raw material and the second raw material to a surface of the substrate to form a first layer; (b) supplying a reactant to the substrate to change the first layer into a second layer.

19. A substrate processing device, characterized in that: have: a processing chamber that processes the substrate; a first raw material supply system for supplying a first raw material to the substrate in the processing chamber; an additive supply system for supplying additives to the substrate in the processing chamber; a reactant supply system for supplying reactants to the substrate in the processing chamber; and A control unit is configured to control the first raw material supply system, the additive supply system and the reactant supply system so that a film is formed on the substrate in the processing chamber by performing a cycle including the following processes for a predetermined number of times: (a) supplying the first raw material and the additive to the substrate to generate a second raw material that is chemically more stable than the first raw material, exposing the first raw material and the second raw material to and adsorbing them on the surface of the substrate to form a first layer; and (b) supplying the reactant to the substrate to change the first layer into a second layer.

20. A program, characterized in that The step of forming a film on the substrate by causing a substrate processing apparatus to perform a cycle including the following steps a predetermined number of times by a computer: (a) supplying a first raw material and an additive to a substrate to generate a second raw material that is chemically more stable than the first raw material, and exposing and adsorbing the first raw material and the second raw material to a surface of the substrate to form a first layer; (b) supplying a reactant to the substrate to change the first layer into a second layer.

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