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

Abstract

This invention provides a technique for suppressing the adhesion of byproducts generated during a reaction. The substrate processing method of this invention includes a step of sequentially performing (a), (b), and (c) a predetermined number of times to form a film containing elements contained in a raw material gas and elements contained in a reaction gas on a substrate, wherein (a) is a step of supplying a first gas containing NH₄⁻ to the substrate; (b) is a step of supplying the raw material gas to the substrate; and (c) is a step of supplying the reaction gas to the substrate.

Description

Technical Field

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

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

[0003] [Patent Document] Japanese Patent Application Laid-Open No. 2008-124184 Summary of the Invention

[0004] [Problems to be Solved by the Invention]

[0005] The present invention provides a technique capable of suppressing the adhesion of by-products generated by a reaction. [Technical Means for Solving the Problems]

[0006] According to one aspect of the present invention, there is provided a technique having a step of forming a film containing elements contained in a source gas and elements contained in a reaction gas on a substrate by sequentially performing the following (a), (b), and (c) a predetermined number of times, wherein, (a) a step of supplying a first gas containing NH- to the substrate; (b) a step of supplying the source gas to the substrate; (c) a step of supplying the reaction gas to the substrate. [Effects of the Invention]

[0007] According to the present invention, it is possible to suppress the adhesion of by-products generated by a reaction. Brief Description of the Drawings

[0008] FIG. 1(a) is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention, showing a cross-sectional view of a processing furnace 202; FIG. 1(b) is a cross-sectional view showing a furnace lid capable of hermetically closing a lower end opening of a manifold 209 shown in FIG. 1(a). FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present invention, and is a view showing a part of the processing furnace 202 in a sectional view taken along line A-A of FIG. 1(a). FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one aspect of the present invention, and is a diagram showing a control system of the controller 121 in a block diagram. FIG. 4 is a diagram showing a substrate processing flow in one embodiment of the present invention. FIG. 5 is a diagram showing a substrate processing program in one embodiment of the present invention. FIG. 6(a) is a diagram showing a modifier supply sequence in one aspect of the present invention, FIG. 6(b) is a diagram showing a raw material supply sequence in one aspect of the present invention, FIG. 6(c) is a diagram showing an oxidant supply sequence in one aspect of the present invention, FIG. 6(d) is a diagram showing a raw material supply sequence in one aspect of the present invention, FIG. 6(e) is a diagram showing a raw material supply sequence in one aspect of the present invention, and FIG. 6(f) is a diagram showing an oxidant supply sequence in one aspect of the present invention. FIG. 7(a) is a diagram showing a modifier supply sequence in one aspect of the present invention, FIG. 7(b) is a diagram showing a modifier supply sequence in another aspect of the present invention, FIG. 7(c) is a diagram showing a modifier supply sequence in yet another aspect of the present invention, FIG. 7(d) is a diagram showing a modifier supply sequence in yet another aspect of the present invention, and FIG. 7(e) is a diagram showing a modifier supply sequence in another aspect of the present invention. FIG. 8(a) is a diagram schematically showing film formation and adsorption in a concave structure in an example, and FIG. 8(b) is a diagram schematically showing film formation and adsorption in a concave structure in a comparative example. FIG. 9 is a diagram showing an example and a comparative example. Embodiment

[0009] <One aspect of the present invention> Hereinafter, one aspect of the present invention will be described mainly with reference to FIGS. 1(a), 1(b), and FIGS. 2 to 5. Furthermore, the drawings used in the following description are all schematic drawings, and the dimensional relationships of the respective elements shown in the drawings, the ratios of the respective elements, etc. are not necessarily the same as the actual ones. Also, among the plurality of drawings, the dimensional relationships of the respective elements, the ratios of the respective elements, etc. are not necessarily the same.

[0010] (1) Configuration of the substrate processing apparatus As shown in FIGS. 1(a) and 1(b), the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 has a cylindrical shape and is vertically installed while being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) a gas by heat.

[0011] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO) or silicon carbide (SiC), for example, and is formed in a cylindrical shape with an upper end closed and a lower end open. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), for example, and is formed in a cylindrical shape with both upper and lower ends open. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided as a sealing member between the manifold 209 and the reaction tube 203. The reaction tube 203 is vertically installed in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed inside the processing chamber 201.

[0012] Inside the processing chamber 201, nozzles 249a to 249c are respectively provided as the first to third supply portions so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also respectively referred to as the first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC, for example. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0013] On the gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c as flow controllers (flow control portions) and valves 243a to 243c as on-off valves are respectively provided in order from the upstream side of the gas flow. Gas supply pipes 232d to 232f are respectively connected to the gas supply pipes 232a to 232c on the downstream side of the valves 243a to 243c. On the gas supply pipes 232d to 232f, MFCs 241d to 241f and valves 243d to 243f are respectively provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232f are made of a metal material such as SUS, for example.

[0014] As shown in FIG. 2, the nozzles 249a to 249c are respectively arranged in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, in a manner of standing upright from the lower part of the inner wall of the reaction tube 203 along the upper part in the arrangement direction upward toward the wafer 200. That is, the nozzles 249a to 249c are respectively arranged in a region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region where the wafer 200 is arranged along the wafer arrangement region. In a plan view, the nozzle 249b is arranged so as to face the following exhaust port 231a in a straight line across the center of the wafer 200 carried into the processing chamber 201. The nozzles 249a and 249c are arranged so as to sandwich the straight line L passing through the centers of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer peripheral portion of the wafer 200). The straight line L is also a straight line passing through the centers of the nozzle 249b and the wafer 200. That is, the nozzle 249c can also be arranged on the side opposite to the nozzle 249a across the straight line L. The nozzles 249a and 249c are arranged symmetrically with respect to the straight line L. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened so as to face (face) the exhaust port 231a in a plan view, and can supply gas to the wafer 200. A plurality of the gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0015] A reforming agent (reforming gas) is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC241a, the valve 243a, and the nozzle 249a.

[0016] A raw material (raw material gas) is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC241b, the valve 243b, and the nozzle 249b. The raw material can be one of the film forming agents.

[0017] An oxidizing agent (oxidizing gas) is supplied into the processing chamber 201 from the gas supply pipe 232c via the MFC241c, the valve 243c, and the nozzle 249c. The oxidizing agent can be one of the film forming agents.

[0018] An inert gas is supplied into the processing chamber 201 from the gas supply pipes 232d to 232f via the MFC241d to 241f, the valves 243d to 243f, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c. The inert gas functions as a blowing gas, a carrier gas, a diluting gas, etc.

[0019] The reformer supply system (reformed gas supply system) is mainly composed of a gas supply pipe 232a, an MFC 241a, and a valve 243a. The raw material supply system (raw material gas supply system) is mainly composed of a gas supply pipe 232b, an MFC 241b, and a valve 243b. The oxidant supply system (oxidized gas supply system) is mainly composed of a gas supply pipe 232c, an MFC 241c, and a valve 243c. The inert gas supply system is mainly composed of gas supply pipes 232d to 232f, MFCs 241d to 241f, and valves 243d to 243f.

[0020] Any one or all of the above various supply systems may also be configured as an integrated supply system 248 integrating valves 243a to 243f, MFCs 241a to 241f, etc. The integrated supply system 248 is respectively connected to each of the gas supply pipes 232a to 232f, and is configured to control the supply operations of various substances (various gases) into the gas supply pipes 232a to 232f by the following controller 121, that is, the opening and closing operations of the valves 243a to 243f, or the flow rate adjustment operations based on the MFCs 241a to 241f, etc. The integrated supply system 248 is configured as an integrated unit of an integrated type or a split type, and can be loaded and unloaded for the gas supply pipes 232a to 232f, etc. in units of the integrated unit, and is configured to perform maintenance, replacement, addition, etc. of the integrated supply system 248 in units of the integrated unit.

[0021] An exhaust port 231a for exhausting the gas in the processing chamber 201 is provided below the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing (opposite to) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between when viewed from above. The exhaust port 231a may also be provided along the lower part to the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. To the exhaust pipe 231, a vacuum pump 246 as a vacuum exhaust device is connected 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 adjustment unit). The APC valve 244 is configured to be able to perform vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operating. Further, in a state where the vacuum pump 246 is operating, the valve opening degree is adjusted based on the pressure information detected by the pressure sensor 245, whereby the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also possible to consider including the vacuum pump 246 in the exhaust system.

[0022] A seal cover 219 as a furnace port cover body that can hermetically seal the lower end opening of the manifold 209 is provided below the manifold 209. The seal cover 219 is made of a metal material such as SUS, for example, and is formed in a disk shape. An O-ring 220b as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cover 219. A rotation mechanism 267 for rotating the following susceptor 217 is provided below the seal cover 219. The rotation shaft 255 of the rotation mechanism 267 penetrates the seal cover 219 and is connected to the susceptor 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The seal cover 219 is configured to be lifted and lowered in the vertical direction by a susceptor elevator 115 as a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is configured to be a transfer device (transfer mechanism) for loading and unloading (transferring) the wafer 200 into and out of the processing chamber 201 by lifting and lowering the seal cover 219.

[0023] Below the sealing cover 219, a rotating mechanism 267 for rotating the following susceptor 217 is provided. The rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the susceptor 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The sealing cover 219 is configured to move up and down in the vertical direction by a susceptor elevator 115 serving as a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is configured as a transfer device (transfer mechanism) for loading and unloading (transferring) the wafer 200 into and out of the processing chamber 201 by moving the sealing cover 219 up and down.

[0024] Below the manifold 209, a shutter 219s serving as a furnace port cover is provided, which can hermetically seal the lower end opening of the manifold 209 in a state where the sealing cover 219 is lowered and the susceptor 217 is unloaded from the processing chamber 201. The shutter 219s is made of a metal material such as SUS, for example, and is formed in a disk shape. An O-ring 220c serving as a sealing member is provided on the upper surface of the shutter 219s and abuts against the lower end of the manifold 209. The opening and closing operation (lifting operation or rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0025] The susceptor 217 serving as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers, in a horizontal posture and in a state where their centers are aligned with each other in the vertical direction and support them in multiple stages, that is, arrange them at intervals. The susceptor 217 is made of a heat-resistant material such as quartz or SiC, for example. Heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages at the lower part of the susceptor 217.

[0026] A temperature sensor 263 serving as a temperature detector is provided inside the reaction tube 203. By adjusting the energization condition of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0027] As shown in FIG. 3, the controller 121 as a control unit (control element) is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a memory device 121c, and an I / O port 121d. The RAM 121b, the memory device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as a touch panel or the like is connected to the controller 121. Further, an external memory device 123 can be connected to the controller 121. Furthermore, the substrate processing apparatus can be configured to include one control unit, or can be configured to include a plurality of control units. That is, the control for performing the following processing procedures can be implemented using one control unit, or the control for performing the following processing procedures can be implemented using a plurality of control units. Also, the plurality of control units can be configured as a control system connected to each other via a wired or wireless communication network, or the control for performing the following processing procedures can be implemented by the entire control system. When the term "control unit" is used in this specification, in addition to the case including one control unit, there are cases including a plurality of control units, or cases including a control system composed of a plurality of control units.

[0028] The memory device 121c is constituted by, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like. A control program for controlling the operation of the substrate processing apparatus, or a process recipe or the like that describes the procedures or conditions of the following substrate processing is stored in the memory device 121c in a readable manner. The process recipe is combined so that the substrate processing apparatus executes each of the following substrate processing procedures by the controller 121 and can obtain a prescribed result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively abbreviated as a program. Also, the process recipe is abbreviated as a recipe. In this specification, when the term "program" is used, it sometimes includes only the recipe alone, sometimes includes only the control program alone, or sometimes includes both of them. The RAM 121b is configured as a memory area (working area) that temporarily holds programs, data, etc. read by the CPU 121a.

[0029] The I / O port 121d is connected to the above-described MFCs 241a to 241f, valves 243a to 243f, pressure sensors 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, susceptor elevator 115, shutter opening / closing mechanism 115s, etc.

[0030] The CPU 121a is configured to be able to read and execute a control program from the memory device 121c, and to be able to read a recipe from the memory device 121c according to the input of an operation instruction from the input / output device 122 or the like. The CPU 121a is configured to be able to control the flow rate adjustment operation of various substances (various gases) based on the MFCs 241a to 241f, the opening and closing operations of the valves 243a to 243f, the opening and closing operation of the APC valve 244, the pressure adjustment operation using the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation of the susceptor 217 using the rotation mechanism 267 and the rotation speed adjustment operation, the lifting operation of the susceptor 217 using the susceptor elevator 115, the opening and closing operation of the shutter 219s using the shutter opening / closing mechanism 115s, etc.

[0031] The controller 121 can be configured by installing the above-mentioned program stored in the external memory device 123 on the computer. The external memory device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, semiconductor memories such as USB memories or SSDs, etc. The memory device 121c or the external memory device 123 is configured as a computer-readable recording medium. Hereinafter, these will be collectively referred to simply as recording media. In this specification, when using the term recording medium, it may sometimes include only the memory device 121c alone, sometimes only the external memory device 123 alone, or sometimes include both of them. Furthermore, when providing a program to the computer, it may also be performed using a communication path such as the Internet or a dedicated line without using the external memory device 123.

[0032] (2) Substrate processing step Regarding the processing procedure for forming a film on the wafer 200 as a substrate, as one of the manufacturing steps of a semiconductor device, using the above-mentioned substrate processing apparatus, it will be mainly described with reference to FIGS. 4 and 5. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121. Referring to FIG. 4, the substrate processing flow includes wafer loading, pressure adjustment and temperature adjustment, film formation, post-blowing, and wafer unloading.

[0033] The substrate processing step (substrate processing method) of the present embodiment has a step of sequentially performing the following (a), (b), and (c) a specified number of times to form a film containing the elements contained in the source gas and the elements contained in the reaction gas on the wafer 200, where, (a) A step of supplying a first gas containing NH- to the wafer 200; (b) Step of supplying a source gas to the wafer 200; (c) Step of supplying a reaction gas to the wafer 200.

[0034] In the processing procedure shown in FIG. 5, a cycle including the following steps A, B, and C is performed a specified number of times (n times, n is an integer of 1 or more). In step A, a modifier as a first gas is supplied to the wafer 200, and an adsorption layer containing the modifier physically adsorbed on the surface of the wafer 200 is formed on the wafer 200. Step B is a step of supplying a source containing a first element to the wafer 200, reacting the source with the surface of the wafer 200, and forming a first layer containing the first element on the wafer 200. Step C is a step of supplying an oxidant to the wafer 200, reacting the oxidant with the first layer, and modifying the first layer into a second layer containing the first element and oxygen.

[0035] Furthermore, in the processing procedure shown in FIG. 5, the adsorption layer suppresses the adsorption of by-products generated during the formation of the first layer to at least one of the first layer and the surface of the wafer 200. Also, as the first layer, a film that does not contain the element contained in the modifier can be used.

[0036] In this specification, for convenience, the above processing procedure may be shown as follows. In the description of the following modification examples or other aspects, the same notations are also used.

[0037] (Modifier → Source → Oxidant) × n

[0038] The term "wafer" used in this specification sometimes refers to the wafer itself and sometimes refers to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" used in this specification sometimes refers to the surface of the wafer itself and sometimes refers to the surface of a specified layer formed on the wafer. When it is described in this specification that "a specified layer is formed on the wafer", sometimes it means that the specified layer is directly formed on the surface of the wafer itself, and sometimes it means that the specified layer is formed on a layer formed on the wafer. The case of using the term "substrate" in this specification is also synonymous with the case of using the term "wafer".

[0039] The term "agent" used in this specification includes at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, each of the modifier and the film-forming agent (source, oxidant) may include a gaseous substance, may include a liquid substance such as a mist-like substance, or may include both.

[0040] (Wafer Loading and Cassette Loading) If a plurality of wafers 200 are loaded into the (wafer loading) cassette 217, the shutter 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter opening). After that, as shown in FIG. 1(a), the cassette 217 supporting the plurality of wafers 200 is lifted by the cassette elevator 115 and carried into the processing chamber 201 (cassette loading). In this state, the seal cover 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b. Furthermore, concave structures such as trenches and holes are formed on the surface of the wafer 200. The aspect ratio of the concave structure, that is, the ratio calculated by (depth of the internal space of the concave structure) / (width of the internal space of the concave structure) is, for example, 10 or more.

[0041] (Pressure Adjustment and Temperature Adjustment) After the cassette loading is completed, vacuum evacuation (pressure reduction evacuation) is performed by the vacuum pump 246 so that the inside of the processing chamber 201, that is, the space where the wafers 200 are present, becomes a desired pressure (vacuum degree). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and feedback control is performed on the APC valve 244 based on the measured pressure information. Also, the wafers 200 inside the processing chamber 201 are heated by the heater 207 so as to be at a desired processing temperature. At this time, based on the temperature information detected by the temperature sensor 263, feedback control is performed on the energization state of the heater 207 so that a desired temperature distribution is achieved inside the processing chamber 201. Also, the wafers 200 are started to rotate by the rotation mechanism 267. The evacuation inside the processing chamber 201, the heating of the wafers 200, and the rotation are all continuously performed at least until the processing of the wafers 200 is completed.

[0042] (Film Formation) After that, subsequent steps A to C are sequentially executed.

[0043] [Step A] In this step, a modifier is supplied to the wafers 200 inside the processing chamber 201.

[0044] Specifically, the valve 243a is opened so that the reformer flows into the gas supply pipe 232a The reformer utilizes MFC 241a for flow adjustment, is supplied through the nozzle 249a into the treatment chamber 201, and at this time, the wafer 200 is discharged from the exhaust port 231a Supply of the reformer (reformer supply) The reformer is sometimes supplied in a state diluted by dilute gases such as inert gas, again, the valves 243d ~ 243f may also be opened to supply the inert gas to the treatment chamber 201 respectively through the nozzles 249a ~ 249c.

[0045] By supplying the reformer to wafer 200 under the conditions described below, the conditioner is physically adsorbed on the surface of wafer 200. As a result, an adsorption layer comprising the reformer physically adsorbed on the wafer 200 surface can be formed on wafer 200. A portion of the adsorption sites present on the wafer 200 surface will be covered by the adsorption layer .

[0046] The thickness of the adsorbed layer is preferably that of not reaching the single molecular layer, i.e., the adsorbed layer is preferable to include a reformer adsorbed in such a way that it discontinuously covers the surface of wafer 200. The result is that a portion of the adsorption sites (OH groups) present on the wafer 200 surface become a sure exposed state In such a way that the thickness of the adsorbent layer is above the thickness of the single molecular layer so that the reformer is physically adsorbed on the surface of wafer 200 (i.e., a continuous layer is pre-utilized to cover the surface of wafer 200), in the following step A2, an adsorbent layer with less than a single molecular layer thickness is formed by removing a portion of the reformer contained in the adsorption layer from the surface of wafer 200 .

[0047] Furthermore, in that step, in the inner surface of the concave structure formed on the surface of the wafer 200 , at least on the surface near the opening (particularly the sidewall near the opening), an adsorption layer is formed, as described above, in that step, preferably further on the bottom and side of the inner surface of the concave structure The adsorption layer is also formed on the wall In other words, an adsorption layer is formed on a portion of the exposed surface (also called the adsorption site, exposed portion) of the wafer 200 Here, a portion of the exposed surface is, for example, a surface in the inner surface of the concave structure at least near the opening (particularly the sidewall near the opening).

[0048] After forming the adsorption layer on the wafer 200, close the valve 243a to stop supplying the modifier into the processing chamber 201.

[0049] After (and after stopping) the supply of the modifier to the wafer 200, as shown in FIG. 5, it is preferable to perform a step A2 of evacuating the inside of the processing chamber 201 in a state where the supply of the modifier into the processing chamber 201 is stopped, and exhausting the gas and the like remaining in the processing chamber 201 from the processing chamber 201. By continuing the step A2, a part of the modifier contained in the adsorption layer can be removed (detached) from the surface of the wafer 200, and the density (thickness) of the adsorption layer formed on the wafer 200 can be adjusted to a desired density (thickness). That is, in the step A2, the evacuation of the inside of the processing chamber 201 can be continued until the thickness of the adsorption layer becomes the desired density. As a result, the thickness of the first layer formed in each cycle can be optimized, and the film formation rate on the wafer 200 can be adjusted to a relatively large desired value. In the step A2, it is preferable to set the evacuation conditions in the processing chamber 201, such as the evacuation time and the evacuation speed, so that the film formation rate of the film formed on the wafer 200 becomes the desired value.

[0050] Furthermore, as shown in FIG. 5, in the step A2, it is preferable to open the valves 243d to 243f and supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c. That is, in the step A2, it is preferable to evacuate the inside of the processing chamber 201 while supplying the inert gas to the wafer 200. Also, it is preferable that, in the step A2, as shown in FIG. 6(a), a step of evacuating the inside of the processing chamber 201 while supplying the inert gas to the wafer 200 (inert gas blowing step) and a step of evacuating the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped (vacuum blowing step) can also be performed. Also, it is preferable that, in the step A2, a plurality of the following blowing cycles can also be performed, and the blowing cycle includes (not simultaneously): a step of evacuating the inside of the processing chamber 201 while supplying the inert gas to the wafer 200; and a step of evacuating the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped.

[0051] By performing the step A2 in any of the above-described manners, a part of the modifier physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the density (thickness) of the adsorption layer formed on the wafer 200 can be adjusted more reliably to the desired density (thickness). As a result, for example, the thickness of the first layer formed in each cycle can be further optimized, and the film formation on the wafer 200 can be adjusted to proceed at a higher rate.

[0052] As the processing conditions in the modifier supply of step A, examples are: Modifier supply flow rate (excluding dilution gas): 0.01 to 10 g / min, more preferably 0.1 to 5 g / min Dilution gas supply flow rate: 100 to 100000 sccm, more preferably 1000 to 50000 sccm Modifier supply time: 1 to 600 seconds, more preferably 10 to 300 seconds Inert gas supply flow rate (for each gas supply pipe): 0 to 50000 sccm, more preferably 5000 to 15000 sccm Processing temperature: 200 to 500 °C, more preferably 200 to 350 °C Processing pressure: 100 to 10000 Pa, more preferably 100 to 1000 Pa.

[0053] Furthermore, the expression of the numerical range of "100 to 100000 sccm" in this specification means that the lower limit value and the upper limit value are included in the range. Therefore, for example, "100 to 100000 sccm" means "100 sccm or more and 100000 sccm or less". The same applies to other numerical ranges. Furthermore, the case where the flow rate is 0 sccm means that the supply of the substance is not carried out.

[0054] As the processing conditions in step A2, examples are: Exhaust time: 1 to 600 seconds, more preferably 10 to 300 seconds Inert gas supply flow rate (for each gas supply pipe): 0 to 100000 sccm, more preferably 0 to 50000 sccm.

[0055] As a modifier, a gas containing an inorganic compound, a gas containing an organic compound, or a gas containing both an inorganic compound and an organic compound can be used. For example, a gas containing ammonia (NH3), hydrazine (N2H4), diazene (N2H2), etc. as the inorganic compound can be used. Furthermore, an inorganic compound is also referred to as a material that does not contain an organic ligand. As the gas containing an organic compound, a gas containing at least any one selected from the group consisting of amine compounds and organic hydrazine compounds can be used. As the gas containing an amine compound, a gas containing at least any one of methylamine compounds such as monomethylamine, dimethylamine, trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, triethylamine, and methylethylamine compounds such as dimethylethylamine and methyldiethylamine can be used. As the gas containing an organic hydrazine compound, a gas containing at least any one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As a modifier, various NH-group-containing gases shown in the present invention can be used. As a modifier, one or more of these can be used. Also, as a modifier, a gas that is not easily chemisorbed on the surface of the wafer 200 is preferably used. In order to form an adsorption layer containing a modifier physically adsorbed on the surface of the wafer 200, for example, a gas that does not substantially chemically react with the adsorption sites (OH groups) on the surface of the wafer 200 can be preferably used.

[0056] Also, as a modifier, a gas containing NH- and a gas containing an organic ligand and NH- can be supplied in such a way that at least a part of the supply periods overlaps, or the gas containing NH- and the gas containing an organic ligand and NH- can be supplied during different periods.

[0057] As a modifier, hydrazine-based inorganic compounds and NH3 can be used. From the viewpoint of the decomposition temperature, NH3 which is more stable is preferably used. When the temperature in the reaction vessel (the temperature of the substrate) is a low temperature of about 100 to 200 °C, hydrazine-based inorganic compounds can be used as the modifier. That is, by using hydrazine-based inorganic compounds, film formation under low temperature conditions can be carried out.

[0058] In the process from the supply of the modifier and the raw material to the supply of the subsequent reaction gas, from the viewpoint of the manufacturing productivity of the semiconductor device, no large temperature change is desirable. Using NH3 enables film formation without significant temperature change. However, when ozone (O3) is used as the reaction gas, it may be necessary to change the temperature from the temperature when the modifying gas is supplied to the temperature when the raw material gas / reaction gas is supplied. When the time for each temperature adjustment can be accepted, a high-quality film can be formed.

[0059] As an inert gas, nitrogen gas (N2), or rare gases such as argon gas (Ar), helium gas (He), neon gas (Ne), and xenon gas (Xe) can be used. As the inert gas, one or more of these can be used. The same applies to the following steps.

[0060] [Step B] After the completion of Step A, a raw material is supplied to the wafer 200 in the processing chamber 201, that is, to the wafer 200 having an adsorption layer formed on its surface.

[0061] Specifically, the valve 243b is opened to allow the raw material to flow into the gas supply pipe 232b. The flow rate of the raw material is adjusted by the MFC 241b, and it is supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the raw material is supplied to the wafer 200 (raw material supply). The raw material may be supplied in a state diluted with a diluent gas such as an inert gas. Also, at this time, the valves 243d to 243f can be opened to supply inert gases into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0062] By supplying the raw material to the wafer 200 under the following conditions, the raw material can react with the surface of the wafer 200. As described below, the raw material contains a molecule having a first element and a ligand bonded to the first element (hereinafter also referred to as a raw material molecule). When the raw material reaches the surface of the wafer 200, it reacts with the exposed surface of the wafer 200 that is not covered by the modified layer, that is, the adsorption sites (OH groups) exposed on the surface of the wafer 200. In other words, the molecules of the raw material gas are adsorbed on the portion of the exposed part (adsorption sites) existing on the surface of the wafer 200 that is not covered by the modified layer. The molecules of the raw material gas are adsorbed on other parts of the exposed part where the adsorption layer is not formed. During this reaction process, the ligand detaches from the first element contained in the raw material, and the first element having an unbonded species due to the detachment of the ligand chemisorbs (bonds) to the surface of the wafer 200. By the progress of this reaction, a first layer containing the first element is formed on the wafer 200, that is, on the exposed surface (exposed part) of the wafer 200 that is not covered by the adsorption layer.

[0063] Furthermore, during the formation of the first layer, specific by-products are generated. Regarding the by-products, their existence includes cases where ligands detach from the first element due to the reaction of the raw material with the adsorption sites exposed on the surface of the wafer 200. Also, for example, the by-products also include cases where molecules are formed by the detachment of a part of the ligand from a molecule having the first element and a ligand bonded to the first element. Furthermore, for a molecule formed by the detachment of a part of the ligand from a molecule having the first element and a ligand bonded to the first element, for example, it may be generated by the thermal decomposition of the raw material supplied into the processing chamber 201.

[0064] As described below, when the by-products include organic ligands (organic substances), the adsorption (attachment) of the by-products on the film surface formed on the wafer 200 or the residue of the by-products in the film is not ideal. The adsorption of the by-products on the film surface or the residue of the by-products in the film becomes a factor increasing the film thickness. Therefore, the adsorption amount or residue amount of the by-products becomes uneven within the wafer surface or on the inner surface (inner wall) of the concave structure on the wafer, and thus there are cases where it becomes a factor deteriorating the film thickness uniformity within the wafer surface of the film formed on the wafer 200 and the step coverage of the film formed on the inner surface of the concave structure. Also, the residue of the by-products in the film sometimes becomes a factor reducing the film quality due to the increase in impurities from the source of the by-products in the film.

[0065] Regarding such problems, according to this aspect, the adsorption (attachment) of the by-products generated during the formation of the first layer to at least either the first layer or the surface of the wafer 200 can be suppressed by the adsorption layer pre-formed in step A. Thereby, the uncontrolled uneven film thickness increase of the film formed on the wafer 200 caused by the adsorption of the by-products or the residue of the by-products in the film can be suppressed.

[0066] As one of the reasons for being able to suppress the adsorption of the by-products to the first layer and the surface of the wafer 200, it is considered that the reason is that the adsorption layer formed in step A reduces the exposure amount of the surface of the wafer 200, that is, the amount of adsorption sites exposed on the surface of the wafer 200 (density per unit area). Thereby, the reaction amount (degree) of the raw material with the surface of the wafer 200 is appropriately controlled, and as a result, the amount of ligands detached from the first element, that is, the generation amount of the by-products containing organic ligands, is reduced.

[0067] Also, as another reason for being able to suppress the adsorption of by-products to the surface of the first layer and the wafer 200, it is considered that, in addition to the reduction in the amount of by-products generated during the formation of the first layer as described above, the adsorption layer pre-formed in step A appropriately covers and hides a part of the surface of the wafer 200 in such a way that by-products do not adhere (physical adsorption), or the adsorption layer functions to suppress the adsorption (attachment) of by-products generated during the formation of the first layer to the first layer or the surface of the wafer 200. As one of the reasons for the adsorption layer to function in a way to suppress the adsorption of by-products to the first layer or the surface of the wafer 200, a modifier in a state of being physically adsorbed on the surface of the wafer 200, or a part of the modifier detached from the surface of the wafer 200 preferentially adsorbs to the by-products compared to the first layer or the surface of the wafer 200, thereby suppressing the adsorption of by-products to the first layer. By pre-forming the adsorption layer on the bottom surface and the side walls in the inner surface of the concave structure in step A, even near the bottom surface of the concave structure where it is difficult for the modifier to reach, the adsorption of by-products to the surface of the wafer 200 or the first layer can be sufficiently suppressed.

[0068] The by-products whose adsorption is suppressed are removed from the processing chamber 201 by exhaust. Also, the modifier adsorbed to the by-products is removed from the processing chamber 201 by the exhaust in this step or the exhaust in subsequent steps.

[0069] After the formation of the first layer on the wafer 200 is completed, the valve 243b is closed and the supply of the raw material to the processing chamber 201 is stopped.

[0070] After the supply of the raw material to the wafer 200 is completed (stopped), preferably as shown in FIG. 4, step B2 is performed, that is, the processing chamber 201 is exhausted in a state where the supply of the raw material to the processing chamber 201 is stopped, and the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201.

[0071] By performing step B2, it is possible to remove from the processing chamber 201 the gas containing the unreacted raw material remaining in the processing chamber 201 or the raw material that has contributed to the formation of the first layer, or the by-products whose adsorption is suppressed due to the adsorption layer.

[0072] Also, by performing step B2, it is possible to detach the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200, from the surface of the wafer 200. As a result, the residual of the modifier in the film formed on the wafer 200 can be suppressed, and the film can be made into a film with a lower impurity concentration of the modifier source.

[0073] Further, by performing Step B2, the by-products adhering to the adsorption layer and the modifier contained in the adsorption layer, i.e., the modifier physically adsorbed on the surface of the wafer 200, can be removed from the surface of the wafer 200 together. As a result, the residue of the by-products in the film formed on the wafer 200 can be suppressed, and the film can be made into a film having excellent in-plane film thickness uniformity or step coverage on the wafer surface and a low impurity concentration derived from the by-products.

[0074] Furthermore, as shown in FIG. 5, in Step B2, it is preferable to open valves 243d to 243f and supply an inert gas into the processing chamber 201 via nozzles 249a to 249c. That is, in Step B2, it is preferable to exhaust the inside of the processing chamber 201 while supplying the inert gas to the wafer 200. Further, it is preferable that in Step B2, as shown in FIG. 6(b), the following steps can be performed: the step of exhausting the inside of the processing chamber 201 while supplying the inert gas to the wafer 200; and the step of exhausting the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped. Further, it is preferable that in Step B2, the following blowing cycle can be performed a plurality of times, the blowing cycle including (not simultaneously): the step of exhausting the inside of the processing chamber 201 while supplying the inert gas to the wafer 200; and the step of exhausting the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped.

[0075] By performing Step B2 in any of the above-described manners, a part of the modifier physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above various effects can be obtained more surely.

[0076] As the processing conditions in the raw material supply of Step B, the following can be exemplified: Raw material supply flow rate (excluding the dilution gas): 0.1 to 10 g / min, more preferably 0.5 to 5 g / min Dilution gas supply flow rate: 100 to 100000 sccm, more preferably 1000 to 50000 sccm Raw material supply time: 10 to 600 seconds, more preferably 30 to 300 seconds Inert gas supply flow rate (for each gas supply pipe): 0 to 50000 sccm, more preferably 5000 to 15000 sccm. Other conditions can be set to be the same as the processing conditions in the modifier supply of Step A.

[0077] As the processing conditions in Step B2, they can be set to be the same as the processing conditions in Step A2.

[0078] As a raw material, a gas containing a molecule having a first element and a ligand bonded to the first element can be used. As the first element, a metal element can be mentioned, preferably a transition metal element, more preferably a Group 4 element such as zirconium (Zr), hafnium (Hf), titanium (Ti). Further, as the ligand bonded to the first element, an organic ligand can be mentioned, preferably a hydrocarbon group containing at least any one selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, butyl, amino group (at least NH-group), alkylamino group, cyclopentadienyl group, cyclohexadienyl group, cycloheptatrienyl group. More preferably, it contains a first element, an amino group and other groups.

[0079] As a raw material containing Zr as the first element, for example, a gas containing at least any one selected from the group consisting of zirconium tetramethylethylamine (Zr[N(CH3)C2H5]4), zirconium tetra-diethylamine (Zr[N(C2H5)2]4), zirconium tetra-dimethylamine (Zr[N(CH3)2]4), Zr(MMP)4, Zr(O-tBu)4, tris-dimethylaminocyclopentadienylzirconium ((C5H5)Zr[N(CH3)2]3) can be used. As the raw material, one or more of these can be used.

[0080] Further, as a raw material containing Hf as the first element, for example, a gas containing at least any one selected from the group consisting of hafnium tetramethylethylamine (Hf[N(CH3)C2H5]4), hafnium tetra-diethylamine (Hf[N(C2H5)2]4), hafnium tetra-dimethylamine (Hf[N(CH3)2]4), Hf(O-tBu)4, Hf(MMP)4, tris-dimethylaminocyclopentadienylhafnium ((C5H5)Hf[N(CH3)2]3) can be used. As the raw material, one or more of these can be used.

[0081] Further, as a raw material containing Ti as the first element, for example, a gas containing at least any one selected from the group consisting of titanium tetramethylethylamine (Ti[N(CH3)C2H5]4), titanium tetra-diethylamine (Ti[N(C2H5)2]4), titanium tetra-dimethylamine (Ti[N(CH3)2]4), Ti(O-tBu)4, Ti(MMP)4, tris-dimethylaminocyclopentadienyltitanium ((C5H5)Ti[N(CH3)2]3) can be used. As the raw material, one or more of these can be used.

[0082] [Step C] After the end of step B, a reaction gas such as an oxidizing agent is supplied to the wafer 200 in the processing chamber 201, that is, to the wafer 200 having a first layer containing a first element formed on its surface.

[0083] Specifically, the valve 243c is opened to allow the oxidizing agent to flow into the gas supply pipe 232c. The flow rate of the oxidizing agent is adjusted by the MFC241c, supplied into the processing chamber 201 via the nozzle 249c, and exhausted from the exhaust port 231a. At this time, the oxidizing agent is supplied to the wafer 200 (oxidizing agent supply). The oxidizing agent may be supplied in a state diluted with a diluting gas such as an inert gas or another oxygen-containing gas. Also, at this time, the valves 243d to 243f may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0084] By supplying the oxidizing agent to the wafer 200 under the following conditions, the oxidizing agent can react with the first layer to modify (oxidize) the first layer into a second layer containing the first element and oxygen (O).

[0085] Furthermore, when the second layer is formed, there are also cases where by-products are generated. The by-products may include ligands detached from the first layer due to the reaction of the oxidizing agent with the first layer. Similar to the by-products generated during the formation of the first layer, the by-products may sometimes include organic ligands (organic substances), and the re-adsorption (reattachment) of the by-products to the second layer, or the residue of the by-products formed in the film on the wafer 200 caused thereby, is not desirable.

[0086] Regarding this problem, according to this aspect, it is possible to suppress the adsorption of the by-products generated during the formation of the second layer to at least one of the second layer and the surface of the wafer 200 by the adsorption layer pre-formed in step A. It is considered that the reason is that, similar to step B, the adsorption layer pre-formed in step A appropriately covers and hides a part of the surface of the wafer 200, or the adsorption layer functions in a manner that inhibits (hinders) the re-adsorption (reattachment) of the by-products generated during the formation of the second layer to the second layer.

[0087] The by-products with suppressed re-adsorption are removed from the processing chamber 201 by exhaust. Also, it is considered that a part of the by-products with suppressed adsorption to the surface of the second layer and the wafer 200 is adsorbed (attached) to the adsorption layer.

[0088] After the formation of the second layer on the wafer 200 is completed, the valve 243c is closed to stop supplying the oxidizing agent into the processing chamber 201.

[0089] After the supply of the oxidizing agent to the wafer 200 is completed (stopped), preferably, as shown in FIG. 4, step C2 is performed, that is, the inside of the processing chamber 201 is evacuated in a state where the supply of the oxidizing agent to the processing chamber 201 is stopped, and the gas and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201.

[0090] By performing step C2, it is possible to exhaust from the processing chamber 201 the gas containing the unreacted oxidizing agent remaining in the processing chamber 201 or the oxidizing agent that has contributed to the formation of the second layer, or the by-products whose adsorption is inhibited by the adsorption layer.

[0091] Also, by performing step C2, it is possible to cause the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200, to desorb from the surface of the wafer 200. As a result, it is possible to suppress the residue of the modifier in the film formed on the wafer 200, and it is possible to make the film a film having a low concentration of impurities derived from the modifier.

[0092] Also, by performing step C2, it is possible to remove the by-products attached to the adsorption layer together with the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200, from the surface of the wafer 200. As a result, it is possible to suppress the residue of the by-products in the film formed on the wafer 200, and it is possible to form the film to have excellent in-plane film thickness uniformity or step coverage on the wafer surface and a low concentration of impurities derived from the by-products.

[0093] Furthermore, as shown in FIG. 4, in step C2, it is preferable to open the valves 243d to 243f and supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c. That is, in step C2, it is preferable to evacuate the inside of the processing chamber 201 while supplying the inert gas to the wafer 200. Also, preferably, in step C2, as shown in FIG. 6(c), it is also possible to perform the step of evacuating the inside of the processing chamber 201 while supplying the inert gas to the wafer 200; and the step of evacuating the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped. Also, preferably, in step C2, it is also possible to perform the following blowing cycle a plurality of times, the blowing cycle including (not simultaneously): the step of evacuating the inside of the processing chamber 201 while supplying the inert gas to the wafer 200; and the step of evacuating the inside of the processing chamber 201 in a state where the supply of the inert gas is stopped.

[0094] By performing step C2 in any of the above-described manners, a part of the modifier physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above various effects can be obtained more surely.

[0095] As the processing conditions in the supply of the oxidizing agent in step C, the following can be exemplified: Supply flow rate of the oxidizing agent: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Supply time of the oxidizing agent: 10 to 600 seconds, more preferably 30 to 300 seconds Supply flow rate of the inert gas (for each gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm. Other conditions can be set to be the same as the processing conditions in the supply of the modifier in step A.

[0096] As the processing conditions in step C2, they can be set to be the same as the processing conditions in step A2.

[0097] As the oxidizing agent, for example, an oxygen (O)-containing gas and a gas containing oxygen (O) and hydrogen (H) can be used. As the gas containing O and H, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen gas (H2) + oxygen gas (O2), hydrogen gas (H2) + ozone (O3) gas, etc. can be used. As the oxygen-containing gas, for example, oxygen gas (O2), ozone (O3) gas, etc. can be used. O3 can be generated from oxygen gas (O2) by an ozone generator, for example. Therefore, the nozzle of the ozone generator releases a gas containing O2 and O3. The thus-generated O3 is supplied to the processing container and the substrate. Specifically, the supply nozzle of the oxidizing agent supplies oxygen gas (O2) + O3 gas. Also, other nozzles can supply an inert gas, and the supply of the inert gas can prevent the O3 gas from entering the nozzle. In the case where neither the oxidizing agent nor the inert gas is supplied from the supply nozzle of the oxidizing agent, the supply nozzle of the oxidizing agent and other nozzles supply O3, O2, and the inert gas to the processing container and the substrate.

[0098] Furthermore, in this specification, the description of the combination of two gases such as "hydrogen gas (H2) + oxygen gas (O2)" means a mixed gas of hydrogen gas (H2) and oxygen gas (O2). When supplying the mixed gas, the two gases can be mixed in the supply pipe (pre-mixed) and then supplied into the processing chamber 201, or the two gases can be separately supplied into the processing chamber 201 from different supply pipes and mixed in the processing chamber 201 (post-mixed).

[0099] [Number of implementation regulations] By performing the cycles of the above steps A to C non-simultaneously, i.e., asynchronously, a specified number of times (n times, where n is an integer of 1 or more), a film containing the first element and O (an oxide film containing the first element) can be formed on the wafer 200, i.e., on the surface of the wafer 200 including the inner surface of the concave structure formed on the surface of the wafer 200. The above cycles are preferably repeated a plurality of times. That is, preferably, the thickness of the second layer formed in each cycle is made thinner than the desired thickness, and the above cycles are repeated a plurality of times until the thickness of the oxide film formed by laminating the second layer reaches the required thickness.

[0100] (Post-blowing and atmospheric pressure recovery) After the film formation on the wafer 200 is completed, an inert gas as a blowing gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c, and exhaust is performed from the exhaust port 231a. Thereby, the inside of the processing chamber 201 is blown, and gases or reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (post-blowing). Then, the gas inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0101] (Cassette unloading and wafer extraction) After that, the sealing lid 219 is lowered by the cassette elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out (cassette unloading) to the outside of the reaction tube 203 in a state of being supported by the cassette 217 from the lower end of the manifold 209. After the cassette unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the cassette 217 (wafer extraction).

[0102] (3) Effects of this aspect According to this aspect, one or more of the following effects can be obtained.

[0103] (a) When performing a cycle including steps A to C a specified number of times, by means of the adsorption layer, the adsorption of by-products generated during the formation of the first layer to at least one of the first layer and the surface of the wafer 200 is suppressed, and the film quality of the film formed on the wafer 200 can be improved. For example, the in-wafer-plane film thickness uniformity or step coverage of the film formed on the wafer 200 can be improved. Also, for example, the film formed on the wafer 200 can be made into a film with a lower concentration of impurities that are the source of by-products generated during the formation of the first layer. As an example, regarding the concentration of impurities contained in the film formed on the wafer 200, it is lower than the concentration of impurities contained in the film formed on the wafer 200 by performing the same specified number of cycles including steps B and C without including step A.

[0104] (b) When performing a cycle including steps A to C a specified number of times, the adsorption of by-products generated during the formation of the second layer to at least one of the second layer and the surface of the wafer 200 is suppressed by means of the adsorption layer, whereby the film quality of the film formed on the wafer 200 can be further improved. For example, the in-wafer-plane film thickness uniformity or step coverage of the film formed on the wafer 200 can be further improved. Also, for example, the film formed on the wafer 200 can be made into a film with an even lower concentration of impurities that are the source of by-products generated during the formation of the second layer.

[0105] (c) The modifier contained in the adsorption layer is physically adsorbed on the surface of the wafer 200, so during the process of performing a cycle including steps A to C, it is easily detached from the surface of the wafer 200. As a result, the film formation rate of the film formed on the wafer 200 can be adjusted to a desired value, and the productivity of the film formation process can be improved. Also, the residual of the modifier in the film formed on the wafer 200 can be suppressed, thereby improving the quality of the film.

[0106] For example, in step A, after supplying the modifier to the wafer 200, step A2 of exhausting the inside of the processing chamber 201 is performed, whereby a part of the modifier contained in the adsorption layer can be removed from the surface of the wafer 200. Thereby, the density (thickness) of the adsorption layer formed on the wafer 200 can be adjusted to a desired density (thickness). As a result, the film formation on the wafer 200 can be performed at a desired rate. Also, the residual of the modifier in the film formed on the wafer 200 can be suppressed, and the film can be made into a film with a lower concentration of impurities that are the source of the modifier.

[0107] Also, for example, in step B, after supplying the raw material to the wafer 200, step B2 of evacuating the processing chamber 201 is performed, whereby the modifier contained in the adsorption layer can be detached from the surface of the wafer 200. Thereby, the residue of the modifier in the film formed on the wafer 200 can be suppressed, and the film can be made into a film with a lower concentration of impurities from the modifier source. Also, by removing the by-products attached to the adsorption layer together with the modifier contained in the adsorption layer from the surface of the wafer 200, the residue of the by-products in the film formed on the wafer 200 can be suppressed. As a result, the film can be made into a film with excellent in-wafer surface uniformity or step coverage and a lower concentration of impurities from the by-products generated during the formation of the first layer.

[0108] Also, for example, in step C, after supplying the oxidant to the wafer 200, step C2 of evacuating the processing chamber 201 is performed, whereby the modifier contained in the adsorption layer can be detached from the surface of the wafer 200. Thereby, the residue of the modifier in the film formed on the wafer 200 can be suppressed, and the film can be made into a film with a lower concentration of impurities from the modifier source. Also, by removing the by-products attached to the adsorption layer together with the modifier contained in the adsorption layer from the surface of the wafer 200, the residue of the by-products in the film formed on the wafer 200 can be suppressed. As a result, the film can be made into a film with excellent in-wafer surface uniformity or step coverage and a lower concentration of impurities from the by-products generated during the formation of the second layer.

[0109] (d) In step A, by forming a discontinuous adsorption layer (an adsorption layer with a thickness less than a monolayer) on the wafer 200, that is, by exposing a part of the adsorption sites (OH groups) existing on the surface of the wafer 200 in advance, in step B, the first element contained in the raw material can be bonded to the adsorption sites existing on the surface of the wafer 200. As a result, the film can be formed on the wafer 200 at a desired rate.

[0110] (e) The above effects are particularly beneficial when a concave structure is formed on the surface of the wafer 200 and a film is desired to be formed on the inner surface of the concave structure.

[0111] This is because, when forming a film on the inner surface of the concave structure formed on the surface of the wafer 200, the by-products generated in the concave structure pass through the opening of the concave structure when being discharged from the concave structure. Therefore, compared with the vicinity of the bottom of the concave structure, the exposure amount of the by-products near the opening of the concave structure tends to be larger. Thus, it is easy to adsorb by-products near the opening of the concave structure. As a result, compared with the film formed near the bottom of the concave structure or the like, the film formed near the opening of the concave structure is likely to be a film with an easily increased film thickness and a relatively high concentration of impurities from the by-product source. Especially when the concave structure has an aspect ratio of 10 or more, the problems described herein will occur significantly.

[0112] According to this aspect, as described above, the adsorption layer can inhibit the adsorption of by-products generated during the formation of the first layer and the second layer to at least any one of the first layer, the second layer, and the surface of the wafer 200. Therefore, the problems described herein can be solved, and the step coverage of the film formed on the inner surface of the concave structure formed on the wafer 200 can be improved. Furthermore, in step A, when forming an adsorption layer on at least the bottom surface and the side wall of the inner surface of the concave structure, that is, when forming an adsorption layer on the entire inner surface of the concave structure not only at the opening, the adsorption of by-products can be inhibited not only at the opening of the concave structure but also on the bottom surface and the side wall. As a result, the step coverage of the film formed on the wafer 200 can be further improved, and a film with a relatively low concentration of impurities from the by-product source can be formed on the entire inner surface of the concave structure.

[0113] (f) When arbitrarily selecting a specified substance (gaseous substance, liquid substance) from the above-mentioned modifier group, raw material group, oxidant group, and inert gas group and using it, the above-mentioned effects can also be obtained in the same manner.

[0114] <Other aspects of the present invention> The aspects of the present invention have been specifically described above. However, the present invention is not limited to the above aspects, and various changes can be made without departing from the gist thereof.

[0115] The raw material gas may be, for example, a gas containing at least one of an amino group and an organic ligand group. NH- in the raw material gas containing an amino group is not easily adsorbed to the NH- terminus on the wafer 200, and the NH- on the wafer 200 functions as an inhibitor.

[0116] Also, the constituent elements of the first layer do not include the constituent elements of the modifying gas. The second layer may be, for example, a film containing the first element of the raw material and oxygen from the oxidant.

[0117] For example, as in the processing procedure shown in FIG. 7(a) and below, in step A, a first modifying gas containing NH- is supplied to the wafer 200. The first modifying gas can be supplied without supplying the second modifying gas, and the first modifying gas does not contain an organic ligand. The first modifying gas can contain, for example, NH 3. Regarding the supply of NH 3, since it does not contain C, CH, etc. in the NH 3 molecule, the possibility of C, CH, etc. remaining from the first modifying gas in the first layer deposited in the subsequent step can be reduced.

[0118] Also, in step A, as in the processing procedure shown below, in addition to supplying the first modifying gas, a second gas containing an organic ligand can also be supplied. Furthermore, the second gas can also contain an organic ligand and an NH- group. When further supplying the first modifying gas and the second gas, for example, as in the processing procedure shown in FIG. 7(b) and below, in step A, the first modifying gas can be supplied after supplying the second modifying gas. Or, as in the processing procedure shown in FIG. 7(c) and below, the second modifying gas can be supplied after supplying the first modifying gas. Furthermore, as in the processing procedure shown in FIG. 7(d) and below, a part of the period of supplying the first modifying gas and the period of supplying the second modifying gas can overlap. Or, as in the processing procedure shown in FIG. 7(e) and below, the first modifying gas and the second gas can be supplied during the same period.

[0119] Furthermore, at least one of the first modifying gas and the second gas can be supplied in a plurality of periods. This condition can be satisfied in any of the cases from FIG. 7(a) to FIG. 7(e). If a time-division process is used, it is easier to form an NH- capping mainly on the upper side of the concave structure. This division process can reduce the supply amount during one supply cycle. Also, in the subsequent supply cycles, NH 3 can be supplied to the sites that have not adsorbed the NH- group (for example, the wafer 200 and the first layer during film formation), and a uniform NH- termination can be formed near the opening of the concave structure of the wafer 200.

[0120] In step A, when the first modifying gas is supplied into the processing chamber 201 and to the wafer 200 in the processing chamber 201, it is supplied in a state that suppresses decomposition, preferably in a state that does not decompose (refer to these states as the "decomposition suppression state"). For example, when the temperature of the reaction vessel does not reach the decomposition temperature of the modifying gas, the decomposition suppression state is satisfied. This condition can be satisfied in any of the cases from FIG. 7(a) to FIG. 7(e) and in the case of the division process.

[0121] Gases containing NH—such as NH3—start to decompose from a low temperature of 100°C, and nearly all NH3 is decomposed near 400°C. If the reforming gas is supplied at a decomposition temperature, such as a temperature below 400°C or slightly lower than 400°C, such as 350°C, a decomposition inhibition state is satisfied. The decomposition inhibition state is related not only to the temperature but also to the flow rate, flow volume, pressure inside the processing container, etc. of the supplied gas. As an example, if the supplied gas is provided at a high flow rate, the time for the molecules in the flux of the supplied gas to be exposed to the above temperature can be shortened. As a result, the thermal energy imparted to the molecules of the supplied gas is reduced, and the amount of gas reaching the substrate surface before molecular decomposition can be increased.

[0122] For example, regarding the pressure conditions in the processing chamber 201, they can be set in such a way that the pressure in step A is higher than the pressure in step B, as in the processing procedure shown below. This pressure condition can be satisfied in any of the cases of FIGS. 7(a) to 7(e), the divided flow case, and the decomposition inhibition state case.

[0123] For example, the first supply conditions for the first reforming gas and the raw material gas can be set in such a way that the supply amount (e.g., flow rate) of the first reforming gas becomes less than the supply amount (e.g., flow rate) of the raw material gas, as in the processing procedure shown below. The pressure condition can be satisfied in any of the cases of FIGS. 7(a) to 7(e), the divided flow case, the decomposition inhibition state case, and the pressure condition case.

[0124] For example, the second supply conditions for the first reforming gas and the reaction gas can be set in such a way that the supply amount (e.g., flow rate) of the first reforming gas is less than the supply amount of the reaction gas, as in the processing procedure shown below. The supply condition can be satisfied in any of the cases of FIGS. 7(a) to 7(e), the divided flow case, the decomposition inhibition state case, the pressure condition, and the first supply condition case.

[0125] For example, as in the processing procedure shown in FIGS. 6(d) and below, in step B, the raw material supply cycle including the step of supplying the raw material to the wafer 200 and the step of exhausting the inside of the processing chamber 201 in a state where the raw material supply is stopped can be repeated a plurality of times (m times, where m is an integer of 2 or more). The processing conditions in each of these steps can be set to be the same as the raw material supply or the processing conditions in step B2 described in the above aspect.

[0126] (Reformative agent → (Raw material → Exhaust) × m → Oxidizing agent) × n

[0127] If the continuous supply time of the raw material becomes longer, the thermal decomposition of the raw material proceeds, and sometimes the amount of by-products generated by the thermal decomposition increases. In order to suppress the increase in the amount of by-products caused by such thermal decomposition, it is desirable to shorten the continuous supply time of the raw material. In this aspect, by supplying the raw material at different times, the continuous supply time can be shortened, and the formation of the first layer can be carried out while suppressing the generation (increase) of by-products.

[0128] Also, in such a case, every time the raw material supply cycle is repeated, the modifier contained in the adsorption layer can be detached from the surface of the wafer 200, and the residue of the modifier in the film can be further suppressed. Also, every time the raw material supply cycle is carried out, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, and the residue of the by-products in the film can be further suppressed. As a result, the film formed on the wafer 200 can be made to have better in-plane film thickness uniformity or step coverage, and a lower concentration of impurities from the modifier or by-products.

[0129] Furthermore, as shown in FIG. 6(d), in the exhaust step in the raw material supply cycle of this aspect, it is preferable to open the valves 243d to 243f and supply an inert gas as a blowing gas into the processing chamber 201 via the nozzles 249a to 249c.

[0130] Also, for example, as in the processing procedure shown in FIG. 6(e) and below, in the above raw material supply cycle, a step of supplying a modifier to the wafer 200 can be further carried out.

[0131] (Modifier → (Raw material → Exhaust → Modifier → Exhaust) × m → Oxidizer) × n Or (Modifier → (Raw material → Exhaust → Modifier) × m → Oxidizer) × n

[0132] When the raw material supply cycle is repeated as described above, every time it is repeated, the modifier contained in the adsorption layer will be detached from the surface of the wafer 200. As a result, there is a situation where the modifier constituting the adsorption layer is insufficient. In such a case, by supplying the modifier also in the raw material supply cycle, the insufficient modifier can be replenished. Thereby, it is possible to more surely suppress the adsorption of by-products generated every time the raw material supply cycle is carried out to at least one of the first layer and the surface of the wafer 200 by the adsorption layer, and the film quality of the film formed on the wafer 200 can be further improved.

[0133] Furthermore, as shown in FIG. 6(e), in the exhaust step of the raw material supply cycle of this aspect, it is preferable to open valves 243d to 243f and supply an inert gas as a blowing gas into the processing chamber 201 via nozzles 249a to 249c. Also, in the raw material supply cycle of this aspect, it is also possible not to perform the exhaust step after the step of supplying the modifier.

[0134] Also, for example, as in the processing procedure shown in FIG. 6(f) and below, in step C, it is also possible to perform the oxidant supply cycle a plurality of times (m times, m is an integer of 2 or more), and the oxidant supply cycle includes: a step of supplying an oxidant to the wafer 200; and a step of exhausting the inside of the processing chamber 201 in a state where the supply of the oxidant is stopped. The processing conditions in each of these steps can be set to be the same as the processing conditions described in the above aspect for the oxidant supply or step C2.

[0135] (Modifier → Raw material → (Oxidant → Exhaust) × m) × n

[0136] In this case, every time the oxidant supply cycle is repeated, the modifier contained in the adsorption layer can be detached from the surface of the wafer 200, and the residual of the modifier in the film can be further suppressed. Also, every time the oxidant supply cycle is performed, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, and the residual of the by-products in the film can be further suppressed. As a result, the film formed on the wafer 200 can have better in-wafer film thickness uniformity or step coverage, and a lower concentration of impurities from the modifier or by-products.

[0137] Furthermore, as shown in FIG. 6(f), in the exhaust step of the oxidant supply cycle of this aspect, it is preferable to open valves 243d to 243f and supply an inert gas as a blowing gas into the processing chamber 201 via nozzles 249a to 249c.

[0138] The recipe for each process is preferably prepared individually in advance according to the process content and stored in the memory device 121c via a telecommunications line or an external memory device 123. Moreover, when starting each process, it is preferable for the CPU 121a to appropriately select a suitable recipe from a plurality of recipes stored in the memory device 121c according to the process content. Thereby, it is possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using one substrate processing apparatus. Also, the burden on the operator can be reduced, and each process can be started quickly while avoiding operation errors.

[0139] The above-described recipe is not limited to newly created cases. For example, it can also be prepared by changing an existing recipe already installed in the substrate processing apparatus. In the case of changing the recipe, the changed recipe can be installed in the substrate processing apparatus via a telecommunications line or a recording medium on which the recipe is recorded. Also, the input / output device 122 provided in the existing substrate processing apparatus can be operated to directly change the existing recipe already installed in the substrate processing apparatus.

[0140] In the above aspect, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time has been described. The present invention is not limited to the above aspect. For example, it can also be appropriately applied to a case of forming a film using a single-wafer type substrate processing apparatus that processes one or a plurality of substrates at a time. Also, in the above aspect, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present invention is not limited to the above aspect, and can also be appropriately applied when using a substrate processing apparatus having a cold-wall type processing furnace to form a film.

[0141] In the above aspect, an example of forming an adsorption layer on a part of the exposed portion of the concave structure formed on the wafer 200 and adsorbing the molecules of the source gas on the other part of the exposed portion has been described. The present invention is not limited to the above aspect. For example, a modifier can also be supplied to the entire surface of the wafer 200, and then the source gas can be supplied to process the wafer 200. Thereby, the film formation rate (film deposition rate) on the entire surface of the wafer 200 can be reduced, and a dense film can be formed. Thereby, the film characteristics of the film formed on the wafer 200 can be improved. Here, the film characteristics refer to either or both of the film thickness uniformity within the plane of the wafer 200 and the film thickness uniformity of each wafer 200. Here, each wafer 200 refers to each time of processing in a single-wafer type substrate processing apparatus, or each wafer 200 among the plurality of wafers when a plurality of wafers are processed at once using one substrate processing apparatus. In particular, when gas is supplied from the side of the wafer 200, the film characteristics of each wafer 200 sometimes become non-uniform, so the processing of the present invention is more effective.

[0142] Also, in the above aspect, an example of performing the above-described processing procedure in the same processing container (in-situ) of the same processing apparatus has been described. The present invention is not limited to the above aspect. For example, any one step and any other step of the above-described processing procedure can be performed separately in different processing containers (ex-situ) of different processing apparatuses, or any one step and any other step of the above-described processing procedure can be performed separately in different processing containers of the same processing apparatus.

[0143] Further, in the above aspect, an example of forming an oxide film by supplying an oxidizing agent to the wafer 200 has been described. The present invention is not limited thereto, and it can also be applied to the case of forming a film of an elemental substance, a nitride film, an oxynitride film, or a carbide film on the wafer 200 (concave structure). In these cases, as the reaction gas, at least one of an oxidizing agent, a nitriding agent, a carbonizing agent, and a reducing agent can be used. The oxidizing agent can be the gas of the present invention. As the nitriding agent, at least one of NH3 gas, N2H4 gas, N2H2 gas, etc. can be used. As the carbonizing agent, at least one of a gas containing an alkane, a gas containing an alcohol such as methanol, ethanol, or propanol, etc. can be used. Further, as the reducing agent, at least one of hydrogen gas (H2), NH3 gas, silane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, borane (BH4) gas, diborane (B2H6) gas, triborane (B3H8) gas, etc. can be used.

[0144] When using these substrate processing apparatuses, each process can also be performed with the same processing procedure and processing conditions as in the above aspect, and the same effects as in the above aspect can be obtained.

[0145] The above aspects can be used in appropriate combinations. The processing procedure and processing conditions at this time can be set to be the same as the processing procedure and processing conditions of the above aspects, for example. [Examples] []

[0146] [] (Example) As an example, an example of forming a hafnium oxide film (HfO film) on a patterned wafer having a concave structure formed on its surface using the above-described substrate processing apparatus and the processing procedure shown in FIG. 5 is shown. As a modifier, a raw material, an oxidizing agent, and an inert gas, a predetermined substance is selected from the group of substances shown in the above aspect. The processing conditions for each step are set to predetermined conditions within the range of the processing conditions in each step shown in the above aspect. Referring to FIG. 8(a), a schematic structure of partial film formation (in this case, an Hf layer), a ligand, and adsorption of an inhibitor (in this case, an NH-group from NH3) near the concave structure is shown. In this structure, the step of supplying a raw material gas in the method of forming an HfO film and the adsorption after the step of supplying NH3 after supplying the raw material gas are shown. In FIG. 8(a), the symbol "AMN" represents an NH-group from NH3, the symbol "RGD" represents a ligand, and the symbol "MTL" represents the first element of the raw material (for example, a hafnium atom). In the supply of NH3 in the subsequent beats after the divided process, NH3 can be supplied to a portion where the NH-group has not been adsorbed (for example, the wafer 200 and the first layer being formed), and a uniform NH-termination can be formed near the opening of the concave structure of the wafer 200.

[0147] As a comparative example, using the above-described substrate processing apparatus, an HfO film is formed on a patterned wafer having a concave structure formed on its surface by using a processing procedure in which step A is not implemented in the processing procedure shown in FIG. 5. As a raw material, an oxidizing agent, and an inert gas, the same substances as those used in the example are selected. The processing conditions for each step are set to predetermined conditions within the range of the processing conditions in each step of the example. Referring to FIG. 8(b), a schematic structure of partial film formation (in this case, an Hf layer) and adsorption of a ligand near the concave structure is shown. In this structure, the adsorption after the step of supplying a raw material gas in the method of forming an HfO film is shown. The symbols in FIG. 8(b) are the same as those in FIG. 8(a). The NH-group from NH3 does not appear in FIG. 8(b). The ligand is adsorbed near the opening of the concave structure.

[0148] Then, for the example and the comparative example, the film thickness of the HfO film formed in the concave structure is measured. The film thickness measurement is performed at two locations, the periphery of the opening (TOP) and the periphery of the bottom (BTM) within the concave structure. Then, the deposition rate at each measurement site, that is, the thickness of the HfO film formed per one cycle (Å / cycle), is calculated. Further, as an index indicating whether the step coverage is good, the value obtained by (deposition rate at BTM / deposition rate at TOP) × 100 (%) (Step Coverage) is calculated.

[0149] The results are shown in Fig. 9. The left vertical axis in Fig. 9 represents the cycling rate (Å / cycle), and the right vertical axis represents the step coverage rate (%). The horizontal axis in Fig. 9 represents the comparative examples and the examples in sequence. The "◆" mark in the figure represents the cycling rate at the TOP, the "■" mark represents the cycling rate at the BTM, and the bar graph represents the step coverage rate (%).

[0150] As shown in Fig. 9, it can be seen that compared with the comparative examples, the cycling rate at the TOP part in the examples is appropriately suppressed, and as a result, the step coverage rate (%) is increased. The reason is considered to be that, as described in the above aspect, by forming an adsorption layer by performing step A at a specified time, the adsorption layer hinders the adsorption of the ligand and successfully suppresses the entry of by-products into the HfO film.

[0151] The above aspects or variation examples can be appropriately combined and used. The processing procedures and processing conditions at this time can be set to be the same as those of the above aspects or variation examples, for example.

[0152] 115: Wafer elevator 115s: Shutter opening and closing mechanism 121: Controller 121a: CPU 121b: RAM 121c: Memory device 121d: I / O port 121e: Internal bus 122: Input / output device 123: External memory device 200: Wafer (substrate) 201: Processing chamber 202: Processing furnace 203: Reaction tube 207: Heater 209: Manifold 217: Boat 218: Heat insulation plate 219: Sealing cover 219s: Shutter 220a~220c: O-ring 231: Exhaust pipe 231a: Exhaust port 232a~232f: Gas supply pipe 241a~241f: MFC 243a~243f: Valve 244: APC valve 245: Pressure sensor 246: Vacuum pump 248: Integrated supply system 249a~249c: Nozzle 250a~250c: Gas supply hole 255: Rotating shaft 263: Temperature sensor 267: Rotating mechanism

Claims

1. A substrate processing method comprising: (a) supplying a first gas containing NH- without an organic ligand to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reaction gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reaction gas on the substrate.

2. The substrate processing method of claim 1, wherein the above-mentioned raw material gas system contains an amine-based gas.

3. The substrate processing method of claim 2, wherein the aforementioned raw material gas further comprises an organic ligand.

4. A substrate processing method comprising: (a) supplying a first gas containing NH- to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film on the substrate containing elements contained in the raw material gas and elements contained in the reactant gas; wherein the film does not contain elements contained in the first gas.

5. The substrate processing method of claim 4, wherein in (a), a second gas comprising an organic ligand and NH- is further supplied.

6. The substrate processing method of claim 5, wherein in (a), the first gas is supplied after the second gas is supplied.

7. The substrate processing method of claim 5, wherein in (a), the second gas is supplied after the first gas is supplied.

8. The substrate processing method of claim 5, wherein in (a), there is a period during which the period of supplying the first gas overlaps with the period of supplying the second gas.

9. The substrate processing method of claim 1, wherein in (a), the gas containing NH- is supplied a plurality of times.

10. A substrate processing method comprising: (a) supplying a first gas containing NH- to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate; wherein in (a), the first gas is supplied in a state where it does not decompose.

11. The substrate processing method of claim 1, wherein (a) is performed under a pressure higher than that in (b).

12. A substrate processing method comprising: (a) supplying a first gas containing NH- to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate; wherein the amount of the first gas supplied is lower than the amount of the raw material gas supplied.

13. A substrate processing method comprising: (a) supplying a first gas containing NH- to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film on the substrate containing elements contained in the raw material gas and elements contained in the reactant gas; wherein the amount of the first gas supplied is lower than the amount of the reactant gas supplied.

14. A method for manufacturing a semiconductor device, comprising: (a) supplying a first gas containing NH- without an organic ligand to a substrate; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

15. A program that, by means of a computer, causes a substrate processing apparatus to perform: (a) a process of supplying a first gas containing NH- without an organic ligand to a substrate; (b) a process of supplying a raw material gas to the substrate; (c) a process of supplying a reactant gas to the substrate; and (d) a process of performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

16. A substrate processing apparatus comprising: a first gas supply system for supplying a first gas containing NH- without an organic ligand to a substrate; a second gas supply system for supplying a raw material gas to the substrate; a third gas supply system for supplying a reactant gas to the substrate; and a control unit configured to control the first gas supply system, the second gas supply system, and the third gas supply system in a manner that performs the following processes: (a) supplying the first gas to the substrate; (b) supplying the raw material gas to the substrate; (c) supplying the reactant gas to the substrate; and (d) performing (a), (b), and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

17. A method for manufacturing a semiconductor device, comprising: (a) supplying a first gas containing NH- to a substrate in a state where the first gas does not decompose; (b) supplying a raw material gas to the substrate; (c) supplying a reactant gas to the substrate; and (d) performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

18. A program that, by means of a computer, causes a substrate processing apparatus to perform: (a) a process of supplying a first gas containing NH- to a substrate in a state where the first gas does not decompose; (b) a process of supplying a raw material gas to the substrate; (c) a process of supplying a reactant gas to the substrate; and (d) a process of performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

19. A substrate processing apparatus comprising: a first gas supply system for supplying a first gas containing NH- to a substrate; a second gas supply system for supplying a raw material gas to the substrate; a third gas supply system for supplying a reactant gas to the substrate; and a control unit configured to control the first gas supply system, the second gas supply system, and the third gas supply system in a manner that performs the following processes: (a) supplying the first gas to the substrate in a state where the first gas does not decompose; (b) supplying the raw material gas to the substrate; (c) supplying the reactant gas to the substrate; and (d) performing (a), (b), and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate.

20. A method for manufacturing a semiconductor device, comprising: (a) a step of supplying a first gas containing NH- to a substrate; (b) a step of supplying a raw material gas to the substrate; (c) a step of supplying a reactant gas to the substrate; and (d) a step of performing (a), (b) and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate; wherein the amount of the first gas supplied is lower than the amount of the raw material gas supplied.

21. A program that, by means of a computer, causes a substrate processing apparatus to perform: (a) a process of supplying a first gas containing NH- to a substrate; (b) a process of supplying a raw material gas to the substrate; (c) a process of supplying a reactant gas to the substrate; (d) a process of sequentially performing (a), (b) and (c) a predetermined number of times to form a film on the substrate containing elements contained in the raw material gas and elements contained in the reactant gas; and (e) a process of making the supply amount of the first gas lower than the supply amount of the raw material gas.

22. A substrate processing apparatus comprising: a first gas supply system supplying a first gas containing NH- to a substrate; a second gas supply system supplying a raw material gas to the substrate; a third gas supply system supplying a reactant gas to the substrate; and a control unit configured to control the first gas supply system, the second gas supply system, and the third gas supply system in a manner that performs the following processes: (a) supplying the first gas to the substrate; (b) supplying the raw material gas to the substrate; (c) supplying the reactant gas to the substrate; (d) performing (a), (b), and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate; and (e) reducing the supply amount of the first gas to a lower amount than the supply amount of the raw material gas.

23. A method for manufacturing a semiconductor device, comprising: (a) a step of supplying a first gas containing NH- to a substrate; (b) a step of supplying a raw material gas to the substrate; (c) a step of supplying a reactant gas to the substrate; and (d) a step of performing (a), (b) and (c) sequentially a predetermined number of times to form a film on the substrate containing elements contained in the raw material gas and elements contained in the reactant gas; wherein the amount of the first gas supplied is lower than the amount of the reactant gas supplied.

24. A program that, by means of a computer, causes a substrate processing apparatus to perform: (a) a process of supplying a first gas containing NH- to a substrate; (b) a process of supplying a raw material gas to the substrate; (c) a process of supplying a reactant gas to the substrate; (d) a process of sequentially performing (a), (b) and (c) a predetermined number of times to form a film on the substrate containing elements contained in the raw material gas and elements contained in the reactant gas; and (e) a process of supplying a lower amount of the first gas than the amount of the reactant gas.

25. A substrate processing apparatus comprising: a first gas supply system supplying a first gas containing NH- to a substrate; a second gas supply system supplying a raw material gas to the substrate; a third gas supply system supplying a reactant gas to the substrate; and a control unit configured to control the first gas supply system, the second gas supply system, and the third gas supply system in a manner that performs the following processes: (a) supplying the first gas to the substrate; (b) supplying the raw material gas to the substrate; (c) supplying the reactant gas to the substrate; (d) performing (a), (b), and (c) sequentially a predetermined number of times to form a film containing elements contained in the raw material gas and elements contained in the reactant gas on the substrate; and (e) reducing the supply amount of the first gas to a lower amount than the supply amount of the reactant gas.

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