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

Abstract

To improve the properties of the film formed on the substrate. [Solution] The method includes the steps of: (a) supplying an inhibitor to a substrate having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from a raw material but is not capable of adsorbing the raw material, and a second adsorption site that is capable of adsorbing the raw material and the intermediate, thereby adsorbing the inhibitor to the first adsorption site and the second adsorption site; (b) supplying the raw material to the substrate after the inhibitor has been adsorbed to the first adsorption site and the second adsorption site, generating the intermediate from the raw material, detaching the inhibitor adsorbed to the second adsorption site, and adsorbing the raw material and the intermediate to the second adsorption site to form a first layer; and (c) supplying a reactant to the substrate after the raw material and the intermediate have been adsorbed to the second adsorption site, thereby modifying the first layer into a second layer, and performing this cycle a predetermined number of times to form a film on the surface of the substrate.

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] With the miniaturization of semiconductor devices, there is a strong demand for improving the characteristics of films formed on substrates.

[0005] The present disclosure provides a technique capable of improving the characteristics of a film formed on a substrate.

Means for Solving the Problems

[0006] According to one aspect of the present disclosure, (a) supplying an inhibitor to a substrate having a first adsorption site on the surface capable of adsorbing an intermediate generated from a raw material and incapable of adsorbing the raw material, and a second adsorption site capable of adsorbing both the raw material and the intermediate, and adsorbing the inhibitor on the first adsorption site and the second adsorption site; (b) A step of supplying the raw material to the substrate after the inhibitor has been adsorbed on the first adsorption site and the second adsorption site, generating the intermediate from the raw material, desorbing the inhibitor adsorbed on the second adsorption site, and adsorbing the raw material and the intermediate on the second adsorption site to form the first layer, A technique is provided for forming a film on the surface of the substrate by performing a predetermined number of cycles including the above. [Effects of the Invention]

[0007] According to this disclosure, it is possible to improve the properties of the film formed on the substrate. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion in a vertical cross-sectional view. [Figure 2] Figure 2 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows the processing furnace 202 portion as a cross-sectional view along line AA in Figure 1. [Figure 3] Figure 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4] Figure 4 shows a processing sequence in one aspect of the present disclosure. [Figure 5]Figure 5(a) is a schematic cross-sectional view showing the surface state of a wafer having a first adsorption site capable of adsorbing an intermediate generated from the raw material but not the raw material itself, and a second site capable of adsorbing both the raw material and the intermediate. Figure 5(b) is a schematic cross-sectional view showing the surface state of a wafer after an inhibitor has been supplied to the wafer from the state shown in Figure 5(a). Figure 5(c) is a schematic cross-sectional view showing the surface state of a wafer after a raw material has been supplied to the wafer from the state shown in Figure 5(b). Figure 5(d) is a schematic cross-sectional view showing the surface state of a wafer after a reactant has been supplied to the wafer from the state shown in Figure 5(c). [Figure 6] Figure 6(a) is a schematic cross-sectional view showing the surface state of a wafer having a first adsorption site capable of adsorbing an intermediate generated from the raw material but not the raw material itself, and a second site capable of adsorbing both the raw material and the intermediate. Figure 6(b) is a schematic cross-sectional view showing the surface state of the wafer after the raw material has been supplied to the wafer from the state shown in Figure 6(b). Figure 6(c) is a schematic cross-sectional view showing the surface state of the wafer after the reactant has been supplied to the wafer from the state shown in Figure 6(b). [Figure 7] This is a schematic cross-sectional view showing the surface portion of a wafer with holes or trenches provided on its surface. [Modes for carrying out the invention]

[0009] <One aspect of this disclosure> The following description will explain one aspect of this disclosure, primarily with reference to Figures 1 to 4 and Figures 5(a) to 5(d). It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and proportions of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and proportions of the elements do not necessarily correspond between multiple drawings.

[0010] (1) Configuration of substrate processing apparatus As shown in Figure 1, the processing furnace 202 of the substrate processing apparatus has a heater 207 as a temperature control unit (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas with 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 (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The processing vessel (reaction vessel) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within this processing chamber 201.

[0012] Within the processing chamber 201, nozzles 249a to 249c, which serve as the first to third supply units, are provided so as to penetrate the side walls of the manifold 209. Nozzles 249a to 249c are also referred to as the first to third nozzles. Nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c, respectively. Nozzles 249a to 249c are all different nozzles, and nozzles 249a and 249c are each provided adjacent to nozzle 249b.

[0013] Gas supply pipes 232a to 232c are equipped with mass flow controllers (MFCs) 241a to 241c and valves 243a to 243c, respectively, in order from the upstream side of the gas flow. Gas supply pipe 232d is connected downstream of valve 243a of gas supply pipe 232a. Gas supply pipe 232e is connected downstream of valve 243b of gas supply pipe 232b. Gas supply pipe 232f is connected downstream of valve 243c of gas supply pipe 232c. Gas supply pipes 232d to 232f are equipped with MFCs 241d to 241f and valves 243d to 243h, respectively, in order from the upstream side of the gas flow. Gas supply pipes 232a to 232f are made of a metal material such as SUS.

[0014] As shown in FIG. 2, the nozzles 249a to 249c are respectively provided in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the upper part from the lower part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are respectively provided along the wafer arrangement area in a region on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounding the wafer arrangement area. In a plan view, the nozzle 249b is arranged so as to face the exhaust port 231a (to be described later) in a straight line across the center of the wafer 200 in 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 nozzle 249b and the center of the wafer 200. That is, it can also be said that the nozzle 249c is provided on the opposite side of the nozzle 249a across the straight line L. The nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as the axis of symmetry. 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 each opened so as to face (opposite) the exhaust port 231a in a plan view, and it is possible to supply gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0015] An inhibitor is supplied from the gas supply pipe 232a into the processing chamber 201 through the MFC241a, the valve 243a, and the nozzle 249a.

[0016] A raw material is supplied from the gas supply pipe 232b into the processing chamber 201 through the MFC241b, the valve 243b, and the nozzle 249b.

[0017] A reactant is supplied from the gas supply pipe 232c into the processing chamber 201 through the MFC241c, the valve 243c, and the nozzle 249c.

[0018] From the gas supply pipes 232d to 232f, an inert gas is supplied into the processing chamber 201 through the MFCs 241d to 241f, the valves 243d to 243f, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c, respectively. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0019] Mainly, the inhibitor supply system is constituted by the gas supply pipe 232a, the MFC 241a, and the valve 243a. Mainly, the raw material supply system is constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. Mainly, the reactant supply system is constituted by the gas supply pipe 232c, the MFC 241c, and the valve 243c. Mainly, the inert gas supply system is constituted by the gas supply pipes 232d to 232f, the MFCs 241d to 241f, and the valves 243d to 243f.

[0020] Among the above various supply systems, any one or all of the supply systems may be configured as an integrated supply system 248 in which the valves 243a to 243f, the MFCs 241a to 241f, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232f, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232f, that is, the opening and closing operations of the valves 243a to 243f and the flow rate adjustment operations by the MFCs 241a to 241f are configured to be controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integrated type or a split type, and can be attached and detached in units of the integrated unit to the gas supply pipes 232a to 232f, etc., and maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of the integrated unit.

[0021] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, the exhaust port 231a is located in a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between, in a plan view. The exhaust port 231a may also be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, which is a vacuum evacuation device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation in the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure in the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0022] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed outside the reaction tube 203 as a lifting mechanism. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0023] Below the manifold 209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. The opening and closing operation of the shutter 219s (such as lifting and lowering or rotating) is controlled by the shutter opening and closing mechanism 115s.

[0024] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in multiple layers, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. Below the boat 217, multiple layers of heat-insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported.

[0025] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0026] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0027] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing device, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe functions as a program, combining the procedures in the substrate processing described later so that the controller 121 causes the substrate processing device to execute them and obtain a predetermined result. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs." Similarly, process recipes will be referred to simply as "recipes." In this specification, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0028] I / O port 121d is connected to the MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotary mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0029] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241f, the opening and closing operation of valves 243a to 243f, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0030] The controller 121 can be configured by installing the above-mentioned program, recorded and stored in the external storage device 123, onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, and semiconductor memory such as USB memory and SSDs. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] (2) Substrate processing process Using the substrate processing apparatus described above, an example of a method for processing a substrate as one step in the manufacturing process of a semiconductor device, that is, a processing sequence for forming a film on the surface of a wafer 200 as a substrate, will be explained mainly using Figures 4 and 5(a) to 5(d). In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0032] In the processing sequence of this embodiment, (a) A step of supplying an inhibitor to a wafer 200 having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from the raw material but is not capable of adsorbing the raw material, and a second adsorption site that is capable of adsorbing both the raw material and the intermediate, thereby adsorbing the inhibitor to the first adsorption site and the second adsorption site (inhibitor supply step), (b) A step (raw material supply step) of supplying raw materials to the wafer 200 after inhibitors have been adsorbed at the first adsorption site and the second adsorption site, generating an intermediate from the raw materials, detaching the inhibitor adsorbed at the second adsorption site, and adsorbing the raw materials and the intermediate at the second adsorption site to form the first layer, Perform a predetermined number of cycles (n times, where n is 1 or an integer greater than or equal to 2) that include the specified operation.

[0033] Below, the above cycle is further extended to: (c) The case in which a reactant is supplied to the wafer 200 and the first layer is modified into the second layer (reactant supply step) will be described. As a typical example, the processing sequence shown in Figure 4 describes the case in which the inhibitor supply step, raw material supply step, and reactant supply step are performed in this order in the cycle described above.

[0034] In this specification, the processing sequence described above may also be shown as follows for convenience. The same notation will be used in the following descriptions of modifications and other embodiments.

[0035] (Inhibitor → Raw Material → Reactant) × n

[0036] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of the wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this specification, when it is stated that "a predetermined layer is formed on the wafer," it may mean that the predetermined layer is formed directly on the surface of the wafer itself or that the predetermined layer is formed on a layer already formed on the wafer. In this specification, the term "substrate" has the same meaning as when it is used with the term "wafer."

[0037] In this specification, terms such as "inhibitor," "raw material," "reactant," and "substance" include at least one of gaseous substances and liquid substances. Liquid substances include mist substances. That is, each of the inhibitor, raw material, and reactant may contain a gaseous substance, a liquid substance such as a mist, or both.

[0038] As used herein, the term “layer” includes at least one of continuous layers and discontinuous layers. For example, the first layer and the second layer may each contain a continuous layer, a discontinuous layer, or both.

[0039] (Wafer charge and boat load) When multiple wafers 200 are loaded into the boat 217 (wafer charging), the shutter 219s is moved by the shutter opening / closing mechanism 115s, opening the lower end opening of the manifold 209 (shutter opening). Then, as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the boat elevator 115 and transported into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared (provided) in the processing chamber 201.

[0040] Incidentally, the surface of wafer 200 has depressions on the molecular or atomic level, as shown in Figure 5(a). A first adsorption site is located at the bottom of the depression, and a second adsorption site is located at the top of the depression. These adsorption sites include, for example, NH terminations.

[0041] The atoms constituting the second adsorption site are separated at least partially, and the distance between the separated atoms (hereinafter also referred to as the separation distance D) is shorter than the width (molecular size, molecular diameter) of the raw material molecules supplied to the wafer 200 in the raw material supply step described later. In other words, the separation distance D is a distance that raw material molecules cannot pass through. The atoms constituting the second adsorption site constitute steric hindrance that prevents the adsorption (arrival) of the raw material to the first adsorption site in the raw material supply step described later.

[0042] Furthermore, the separation distance D described above is longer than the width (molecular size, molecular diameter) of the intermediate molecules generated from the raw materials in the raw material supply step described later, and is also longer than the width (molecular size, molecular diameter) of the inhibitor molecules supplied to the wafer 200 in the inhibitor supply step described later. In other words, the separation distance D is the distance that both the intermediate molecules and the inhibitor molecules can pass through. The atoms constituting the second adsorption site do not constitute steric hindrance that inhibits the adsorption (arrival) of the inhibitor to the first adsorption site in the inhibitor supply step described later, nor do they constitute steric hindrance that inhibits the adsorption (arrival) of the intermediate generated from the raw materials to the first adsorption site in the raw material supply step described later.

[0043] Based on these findings, both the first and second adsorption sites function as adsorption sites capable of adsorbing inhibitors in the inhibitor supply step described later. Furthermore, the first adsorption site functions as an adsorption site capable of adsorbing intermediates generated from the raw materials but not the raw materials themselves in the raw material supply step described later, while the second adsorption site functions as an adsorption site capable of adsorbing both the raw materials and the intermediates in the raw material supply step described later.

[0044] Furthermore, the surface of the wafer 200 may have three-dimensional structures such as holes or trenches, as shown in Figure 7. In this case as well, the entire surface of this three-dimensional structure has the surface condition described above. That is, the top, side, and bottom surfaces of the holes or trenches in Figure 7 each have depressions on the molecular or atomic level, as shown in Figure 5(a), with the first adsorption sites described above located on the bottom side of each of these depressions, and the second adsorption sites described above located on the upper side of each of these depressions.

[0045] (Pressure adjustment and temperature adjustment) After the boat loading is complete, the processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by a vacuum pump 246 to achieve the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245, and the APC valve 244 is feedback-controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by a heater 207 to reach the desired processing temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on the temperature information detected by a temperature sensor 263 to ensure that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0046] (Film deposition step) Subsequently, the inhibitor supply step, the raw material supply step, and the reactant supply step are performed in this order.

[0047] [Inhibitor supply step] In this step, an inhibitor is supplied to a wafer 200 having a first adsorption site and a second adsorption site on its surface.

[0048] Specifically, valve 243a is opened, and the inhibitor is allowed to flow into the gas supply pipe 232a. The inhibitor's flow rate is regulated by MFC 241a, and it is supplied into the processing chamber 201 via nozzle 249a and exhausted through exhaust port 231a. At this time, the inhibitor is supplied to the wafer 200 from the side of the wafer 200 (inhibitor supply). At this time, valves 243d to 243f may also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0049] By supplying inhibitor to the wafer 200 having the surface described above under the following processing conditions, it becomes possible to adsorb the inhibitor onto all of the adsorption sites on the surface of the wafer 200, namely the first adsorption sites located on the bottom side of the recess and the second adsorption sites located on the upper side of the recess. As a result, as shown in Figure 5(b), all of the adsorption sites on the surface of the wafer 200 are covered with inhibitor.

[0050] The processing conditions when supplying the inhibitor in the inhibitor supply step are as follows: Processing temperature: 300 to 850°C, preferably 500 to 750°C. Processing pressure: 1-5000 Pa Inhibitor supply flow rate: 0.05~10 slm Inhibitor supply time: 5-300 seconds Inert gas supply flow rate (per gas supply pipe): 0-20 slm Examples are given.

[0051] In this specification, numerical ranges such as "1 to 5000 Pa" mean that the lower and upper limits are included within that range. For example, "1 to 5000 Pa" means "1 Pa or more and 5000 Pa or less." The same applies to other numerical ranges. In this specification, processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure means the pressure inside the processing chamber 201. Processing time means the time during which the processing is continued. When 0 slm is included in the supply flow rate, 0 slm means the case in which the substance (gas) is not supplied. These also apply in the following explanations.

[0052] For example, a substance containing a halogen can be used as an inhibitor. Halogens include at least one of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Examples of inhibitors that can be used include fluorine (F2) gas, chlorine (Cl2) gas, bromine (Br2) gas, iodine (I2) gas, nitrogen fluoride (NF3) gas, chlorine fluoride (ClF3) gas, hydrogen fluoride (HF) gas, hydrogen chloride (HCl) gas, hydrogen bromide (HBr) gas, and hydrogen iodide (HI) gas. In other words, examples of inhibitors that can be used include elemental halogens, interhalogen compounds, nitrogen halides, and hydrogen halides.

[0053] Furthermore, as inhibitors, for example, substances containing amines can be used. Substances containing amines contain carbon (C), nitrogen (N), and hydrogen (H). Substances containing amines are also called amine-based substances (amine-based gases). As inhibitors, for example, chain-like amine-based substances (chain-like amine-based gases) such as triethylamine ((C2H5)3N) gas, diethylamine ((C2H5)2NH) gas, monoethylamine ((C2H5)NH2) gas, trimethylamine ((CH3)3N) gas, dimethylamine ((CH3)2NH) gas, and monomethylamine ((CH3)NH2) gas can be used.

[0054] One or more of these can be used as inhibitors.

[0055] The molecular size of the inhibitor is preferably smaller than the molecular size of the raw material used in the raw material supply step described later, and also preferably smaller than the molecular size of the intermediate produced from the raw material in the raw material supply step.

[0056] As the inert gas, nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, and other noble gases can be used. One or more of these can be used as the inert gas. This also applies to each of the steps described later.

[0057] After the inhibitor has been adsorbed onto all the adsorption sites on the surface of the wafer 200, valve 243a is closed to stop the supply of inhibitor into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any gaseous substances remaining inside the processing chamber 201. At this time, valves 243d to 243f are opened and inert gas is supplied into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201. It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the inhibitor.

[0058] [Raw material supply step] After the inhibitor supply step is completed, raw materials are supplied to the wafer 200, that is, the wafer 200 after the inhibitor has been adsorbed at the first adsorption site and the second adsorption site.

[0059] Specifically, valve 243b is opened and the raw material flows into the gas supply pipe 232b. The flow rate of the raw material is adjusted by MFC 241b and supplied into the processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, the raw material is supplied to the wafer 200 from the side of the wafer 200 (raw material supply). At this time, valves 243d to 243f may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0060] By supplying raw materials to a wafer 200 on which inhibitors have been adsorbed across the entire adsorption site under the processing conditions shown below, it becomes possible to thermally decompose the raw materials and generate intermediates from them. Furthermore, it becomes possible to react the raw materials and intermediates with the inhibitors adsorbed on the second adsorption site, thereby detaching and removing the inhibitors from the second adsorption site. Additionally, it becomes possible to adsorb the raw materials and intermediates onto the second adsorption site from which the inhibitors have been detached. As a result, as shown in Figure 5(c), it becomes possible to form a first layer containing the raw materials and intermediates on the surface of the wafer 200.

[0061] Here, the atoms constituting the second adsorption site constitute steric hindrance, as described above, which prevents the raw material from reaching the first adsorption site. Therefore, in the raw material supply step, it is possible to suppress the reaction between the inhibitor adsorbed at the first adsorption site and the raw material.

[0062] Furthermore, the molecular size of the intermediate is smaller than that of the raw material. As described above, if the separation distance D is longer than the width of the intermediate molecule and is a distance that the intermediate molecule can pass through, the atoms constituting the second adsorption site will no longer constitute steric hindrance that prevents the intermediate from reaching the first adsorption site. However, even in this case, the inhibitor adsorbed at the second adsorption site is located on the outermost surface of the wafer 200, while the inhibitor adsorbed at the first adsorption site is located in a recessed area at the bottom of the depression. Therefore, in the raw material supply step, the reaction probability between the inhibitor adsorbed at the first adsorption site and the intermediate can be made lower than the reaction probability between the inhibitor adsorbed at the second adsorption site and the intermediate. Therefore, in the raw material supply step, it is possible to suppress not only the reaction between the inhibitor adsorbed at the first adsorption site and the raw material, but also the reaction between the inhibitor adsorbed at the first adsorption site and the intermediate.

[0063] As a result, in the raw material supply step, it is possible to suppress the desorption of inhibitors from the first adsorption site, maintain at least a portion of the inhibitors adsorbed on the first adsorption site, and selectively desorb and remove the inhibitors adsorbed on the second adsorption site among the first and second adsorption sites. In the raw material supply step, by maintaining at least a portion of the inhibitors adsorbed on the first adsorption site, it is possible to suppress the adsorption of intermediates to the first adsorption site, and to make the amount (adsorption rate) of intermediates adsorbed on the second adsorption site greater than the amount (adsorption rate) of intermediates adsorbed on the first adsorption site. Consequently, in the raw material supply step, as shown in Figure 5(c), it is possible to selectively adsorb raw materials and intermediates on the second adsorption site among the first and second adsorption sites while maintaining a state in which the first adsorption site is filled (covered) with inhibitors.

[0064] The processing conditions when supplying raw materials in the raw material supply step are as follows: Processing temperature: 300-850°C, preferably 500-750°C Processing pressure: 1-2000 Pa Raw material supply flow rate: 0.05 to 3 slm, preferably 0.1 to 2 slm Raw material supply time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0-20 slm Examples are given.

[0065] As raw materials, for example, substances containing halogens and the main elements that make up the film can be used. The halogens include at least one of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). The main elements that make up the film include semiconductor elements such as silicon (Si).

[0066] As raw materials, for example, gases containing Si and halogens, i.e., halosilane gases, can be used. As raw materials, for example, fluorosilane gases such as difluorosilane (SiH2F2) gas, chlorosilane gases such as monochlorosilane (SiH3Cl) gas, dichlorosilane (SiH2Cl2) gas, trichlorosilane (SiHCl3) gas, hexachlorodisilane (Si2Cl6) gas, octachlorotrisilane (Si3Cl8) gas, bromosilane gases such as dibromosilane (SiH2Br2) gas, and iodosilane gases such as diiodosilane (SiH2I2) gas can be used.

[0067] Furthermore, as raw materials, for example, gases containing Si and amino groups, i.e., aminosilane gases, can be used. For example, aminosilane gases such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4) gas, tris(dimethylamino)silane (Si[N(CH3)2]3H) gas, bis(diethylamino)silane (Si[N(C2H5)2]2H2) gas, bis(tert-butylamino)silane (SiH2[NH(C4H9)]2) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2]) gas can be used as raw materials.

[0068] One or more of these can be used as raw materials.

[0069] Furthermore, when using, for example, the halosilane gas described above as a raw material, intermediates are produced that have molecular structures such as SiHF, SiF2, SiHCl, SiCl2, SiHBr, SiBr2, SiHI, and SiI2. In this case, it is preferable to use a substance containing a halogen as an inhibitor. Also, when using, for example, the aminosilane gas described above as a raw material, intermediates are produced that have molecular structures in which at least one of the following is removed from the raw material molecule: an amino group, a part of an amino group, or a hydrogen atom. In this case, it is preferable to use a substance containing an amine as an inhibitor.

[0070] After forming the first layer on the surface of the wafer 200, the valve 243b is closed to stop the supply of raw materials into the processing chamber 201. Then, any gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and conditions as the purging in the inhibitor supply step (purging). It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the raw materials.

[0071] [Reactant supply step] After the raw material supply step is completed, the reactant is supplied to the wafer 200, that is, the wafer 200 after the first layer has been formed by selectively adsorbing the raw material and intermediate on the second adsorption site among the adsorption sites on the surface of the wafer 200.

[0072] Specifically, valve 243c is opened, and the reactant is allowed to flow into the gas supply pipe 232c. The reactant's flow rate is adjusted by MFC 241c and supplied into the processing chamber 201 via nozzle 249c, and exhausted through exhaust port 231a. At this time, the reactant is supplied to the wafer 200 from the side of the wafer 200 (reactant supply). At this time, valves 243d to 243f may be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0073] By supplying the reactant to the wafer 200 after the first layer has been formed under the following processing conditions, it becomes possible to react at least a portion of the first layer with the reactant and modify the first layer into the second layer, as shown in Figure 5(d).

[0074] At this time, the action of the reactants makes it possible to remove the inhibitors remaining at the first adsorption site in the raw material supply step from the surface of the wafer 200. This makes it possible to suppress the residue of inhibitors in the film that is ultimately formed on the surface of the wafer 200. However, as shown in Figure 5(d), not all of the inhibitors may be removed from the surface of the wafer 200, and a small amount of inhibitors may remain in the film that is ultimately formed on the surface of the wafer 200. The areas from which the inhibitors have been removed may be filled by the adsorption of atoms and molecules that make up the reactants, or by the migration of atoms and molecules that make up the raw materials.

[0075] The processing conditions when supplying the reactants in the reactant supply step are as follows: Processing temperature: 300-850°C, preferably 500-750°C Processing pressure: 1-4000 Pa Reactor supply flow rate: 1-30 slm, preferably 2-20 slm Reactant supply time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0-20 slm Examples are given.

[0076] As the reactant, a substance containing at least one of nitrogen and oxygen can be used.

[0077] As reactants, for example, nitrogen (N) and hydrogen (H)-containing substances (N and H-containing gases) can be used. As N and H-containing substances, for example, hydrogen nitride-based gases such as diazene (N2H2) gas, hydrazine (N2H4) gas, ammonia (NH3) gas, and N3H8 gas can be used; ethylamine-based gases such as monoethylamine (C2H5NH2) gas, diethylamine ((C2H5)2NH) gas, and triethylamine ((C2H5)3N) gas can be used; methylamine-based gases such as monomethylamine (CH3NH2) gas, dimethylamine ((CH3)2NH) gas, and trimethylamine ((CH3)3N) gas can be used; and organic hydrazine-based gases such as monomethylhydrazine ((CH3)HN2H2) gas, dimethylhydrazine ((CH3)2N2H2) gas, and trimethylhydrazine ((CH3)2N2(CH3)H) gas can be used.

[0078] Furthermore, as reactants, for example, oxygen (O)-containing substances (O-containing gases) can be used. Examples of O-containing substances include oxygen (O2) gas, ozone (O3) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, deuterium (D2) gas + oxygen (O2) gas, and oxygen radicals (O2 * , O * ), atomic oxygen (O), etc., can be used. Note that in this specification, the joint description of two gases such as "H2 gas + O2 gas" means a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe and then supplied into the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0079] One or more of these can be used as reactants.

[0080] Furthermore, when using, for example, a N and H-containing substance as the reactant, it is preferable to use, for example, a halogen-containing substance as the inhibitor, and for example, a halosilane-based gas as the raw material. Also, when using, for example, an O-containing substance as the reactant, it is preferable to use, for example, an amine-containing substance as the inhibitor, and for example, an aminosilane-based gas as the raw material.

[0081] After the first layer formed on the surface of the wafer 200 is transformed into the second layer, the valve 243c is closed to stop the supply of the reactant into the processing chamber 201. Then, any gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and conditions as the purging in the inhibitor supply step (purging). It is preferable that the processing temperature when purging in this step is the same as the processing temperature when supplying the reactant.

[0082] [Perform the prescribed number of times] By performing the above-described inhibitor supply step, raw material supply step, and reactant supply step non-simultaneously, i.e., without synchronization, in this order, a cycle of n times (where n is 1 or an integer of 2 or more) can be performed to form a film having a desired composition on the surface of the wafer 200. When the above-described silane-based gas is used as the raw material and the above-described gas containing nitrogen is used as the reactant, a silicon nitride film (SiN film) is formed on the surface of the wafer 200. When the above-described silane-based gas is used as the raw material and the above-described gas containing oxygen is used as the reactant, a silicon oxide film (SiO film) is formed on the surface of the wafer 200. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired film thickness, and to repeat the above cycle multiple times until the film thickness formed by stacking the second layer reaches the desired film thickness.

[0083] (After-purge and return to atmospheric pressure) After the film deposition step is completed, inert gas is supplied as a purge gas into the processing chamber 201 from nozzles 249a to 249c and exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gases and reaction by-products (after-purging). Subsequently, the atmosphere inside the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0084] (Boat unloading and wafer discharge) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After boat unloading, the shutters 219s are moved, and the lower end opening of the manifold 209 is sealed by the shutters 219s via the O-ring 220c (shutter closing). After the processed wafer 200 has been unloaded from the reaction tube 203, it is removed from the boat 217 (wafer discharge).

[0085] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0086] (a) In the inhibitor supply step, the inhibitor is first adsorbed onto the entire adsorption site (first adsorption site and second adsorption site). Then, in the raw material supply step, the inhibitor adsorbed onto the second adsorption site is selectively desorbed and removed, and the raw material and intermediate are selectively adsorbed onto the second adsorption site. This makes it possible to reduce the amount of intermediate adsorbed onto the entire adsorption site (adsorption rate). As a result, the step coverage of the film formed on the wafer surface is greatly improved, and this film can be made conformal.

[0087] Here, since the intermediate is generated by a gas-phase reaction, the supply of the intermediate is greater in the upper part of trenches and holes, where the space is relatively larger, than in the central or bottom parts. Also, the intermediate is adsorbed without saturation, as in CVD reactions. In other words, the intermediate tends to be adsorbed in relatively large amounts in the upper part of trenches and holes, which is a factor that worsens step coverage. Furthermore, the greater the amount of intermediate adsorbed to the entire adsorption site such as trenches and holes, the more this tendency is exacerbated. In contrast, according to this disclosure, it is possible to reduce the amount of intermediate adsorbed (adsorption rate) to the entire adsorption site, including the upper part of trenches and holes, thereby suppressing the tendency for the intermediate to be adsorbed in relatively large amounts in the upper part of trenches and holes, and as a result, it is possible to significantly improve step coverage.

[0088] Furthermore, if the raw material supply step is performed without performing the inhibitor supply step, it becomes difficult to selectively adsorb the raw material and intermediate onto the second adsorption site among the first and second adsorption sites on the wafer surface, and the above-mentioned effects may not be obtained. This point will be explained below using Figures 6(a) to 6(c).

[0089] Figure 6(a) is a schematic cross-sectional view showing the surface state of a wafer having a first adsorption site and a second adsorption site on its surface. The surface state of the wafer shown in this figure is the same as the surface state of the wafer described above shown in Figure 5(a). If the raw material supply step is performed on a wafer having such a surface state without performing the inhibitor supply step, as shown in Figure 6(b), not only will the raw material and intermediate be adsorbed at the second adsorption site, but the intermediate may also be adsorbed at the first adsorption site. In other words, if the inhibitor supply step is not performed before the raw material supply step, it may be difficult to reduce the amount of intermediate adsorbed to the entire adsorption site (adsorption rate) compared to the method shown in this embodiment. In this case, the first layer formed on the surface of the wafer may contain a large amount of intermediate components. If the reactant supply step is performed in this state, as shown in Figure 6(c), the second layer formed on the surface of the wafer will contain a large amount of intermediate components, and the step coverage may be lower compared to the film formed on the surface of the wafer by the method shown in this embodiment, making it difficult to make this film conformal.

[0090] (b) By having the first adsorption site located at the bottom of the recess on the wafer surface and the second adsorption site located at the top, it is possible to make the reaction probability between the raw material and intermediate and the inhibitor adsorbed on the second adsorption site higher than the reaction probability between the raw material and intermediate and the inhibitor adsorbed on the first adsorption site during the raw material supply step. This makes it possible to effectively selectively desorb and remove the inhibitor adsorbed on the second adsorption site during the raw material supply step, and selectively adsorb the raw material and intermediate on the second adsorption site. As a result, the amount of intermediate adsorbed on the entire adsorption site (adsorption rate) can be reduced, the step coverage of the film formed on the wafer surface can be greatly improved, and the film can be made more conformal.

[0091] (c) By making the molecular size of the inhibitor smaller than that of the raw material, it becomes possible to uniformly adsorb the inhibitor not only on the upper side of the recess but also on the lower side of the recess where molecules are less likely to enter during the inhibitor supply step. This makes it possible to create a state in which the inside of the recess is filled with the inhibitor, that is, a state in which the inside of the recess is blocked with the inhibitor. As a result, it becomes possible to effectively bring about the above reaction.

[0092] (d) By making the molecular size of the inhibitor the smallest among the raw materials, intermediates, and inhibitor, it becomes possible to uniformly adsorb the inhibitor not only on the upper side of the recess but also on the lower side of the recess where molecules have difficulty entering during the inhibitor supply step. This makes it possible to create a state in which the inside of the recess is filled with inhibitor, that is, a state in which the inside of the recess is blocked with inhibitor. As a result, it becomes possible to effectively bring about the above reaction.

[0093] (e) The separation distance D described above is shorter than the width of the raw material molecules, and is a distance that the raw material molecules cannot pass through. As a result, the atoms constituting the second adsorption site constitute steric hindrance that inhibits the adsorption of the raw material to the first adsorption site. This makes it possible to enable the adsorption of the raw material to the second adsorption site while inhibiting the adsorption of the raw material to the first adsorption site during the raw material supply step. Consequently, the above reaction can be effectively brought about.

[0094] (f) Because the aforementioned separation distance D is longer than the width of the intermediate molecule and longer than the width of the inhibitor molecule, that is, because it is a distance that both the intermediate molecule and the inhibitor molecule can pass through, adsorption of the intermediate to the first and second adsorption sites becomes possible in the raw material supply step. Also, adsorption of the inhibitor to the first and second adsorption sites becomes possible in the inhibitor supply step. As a result, the above reaction can be effectively brought about.

[0095] (g) In the raw material supply step, by maintaining at least a portion of the inhibitor adsorbed on the first adsorption site and keeping the first adsorption site filled with inhibitor, it is possible to effectively promote the selective adsorption of the raw material and intermediate to the second adsorption site while suppressing the adsorption of the intermediate to the first adsorption site. In other words, in the raw material supply step, by making the amount of intermediate adsorbed to the second adsorption site greater than the amount of intermediate adsorbed to the first adsorption site, it is possible to effectively reduce the amount of intermediate adsorbed to the entire adsorption site (adsorption rate). As a result, it is possible to significantly improve the step coverage of the film formed on the surface of the wafer.

[0096] (h) In the reactant supply step, when the reactant is supplied to the wafer and the first layer is modified into the second layer, the inhibitors remaining at the first adsorption site in the raw material supply step can be removed by the action of the reactant. As a result, it is possible to suppress the retention of inhibitors in the film formed on the surface of the wafer.

[0097] (i) In the cycle described above, the inhibitor supply step, raw material supply step, and reactant supply step are carried out in this order, which makes it possible to effectively bring about the above reaction.

[0098] (j) The above reaction can be effectively brought about by the inhibitor containing a halogen and the raw materials containing a halogen and the main elements that constitute the film. Furthermore, the above reaction can be effectively brought about by the reactants containing at least one of nitrogen and oxygen.

[0099] (k) The above reaction can be made more effective by using a halogen-containing substance as an inhibitor, a halosilane-based gas as a starting material, and an N and H-containing substance as a reactant. Furthermore, the above reaction can be made more effective by using an amine-containing substance as an inhibitor, an aminosilane-based gas as a starting material, and an O-containing substance as a reactant.

[0100] (l) The effects described above can also be obtained when a predetermined substance is arbitrarily selected from the various raw materials, reactants, inhibitors, and inert gases described above.

[0101] <Other aspects of this disclosure> The embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the embodiments described above and can be modified in various ways without departing from its essence. Examples of other embodiments of this disclosure are described below. Unless otherwise specified, the processing procedures and processing conditions in each step of the following other embodiments may be the same as the processing procedures and processing conditions in each step of the processing sequence described above.

[0102] For example, after performing the above-described film deposition step, a predetermined post-treatment may be performed on the film formed on the surface of the substrate.

[0103] Post-treatment methods include, for example, heat treatment in an atmosphere containing a predetermined post-treatment substance (post-treatment gas), or plasma treatment using the post-treatment substance. As post-treatment substances, various reactants mentioned above, such as reactive gases like NH3 gas, O2 gas, H2 gas, and D2 gas, or inert gases like He gas, Ar gas, and N2 gas, or mixtures thereof, can be used. One or more of these can be used as the post-treatment substance. Post-treatment may be performed in the same treatment chamber as the film deposition step (in-situ), or in a different treatment chamber than the one used for the film deposition step (ex-situ).

[0104] The processing conditions when performing post-processing are as follows: Processing temperature: 300-1000°C, preferably 200-800°C Processing pressure: 1 to 4000 Pa, preferably 1 to 1000 Pa Post-treatment material supply flow rate: 0.01 to 10 slm, preferably 1 to 10 slm Post-treatment material supply time: 1 to 18,000 seconds, preferably 120 to 10,800 seconds Inert gas supply flow rate (per gas supply pipe): 0-20 slm RF power: 1 to 10,000W, preferably 10 to 5,000W This is an example. RF power refers to the power applied to generate plasma when performing plasma processing using post-processing materials.

[0105] In this embodiment, the same effects as in the embodiments described above can be obtained. Furthermore, by performing post-processing, it becomes possible to remove inhibitors remaining in the film formed on the surface of the substrate from the film.

[0106] Alternatively, for example, as shown in the processing sequence below, the above-described cycle may include performing the inhibitor supply step and a set including the raw material supply step and the reactant supply step a predetermined number of times (m times, where m is an integer of 1 or more). In this embodiment, the same effects as in the above-described embodiment can be obtained.

[0107] [Inhibitor → (Raw material → Reactant) × m] × n

[0108] Furthermore, for example, as shown in the processing sequence below, multiple types of reactants may be used to form a multi-component film on the surface of the substrate, such as a silicon oxynitride film (SiON film), silicon oxycarbide film (SiOC film), silicon oxycarbonite film (SiOCN film), silicon carbonitride film (SiCN film), silicon boronite film (SiBN film), silicon borocarbonite film (SiBCN film), silicon borooxynitride film (SiBON film), or silicon borate carbonitride film (SiBOCN film). In addition to the various reactants described above, carbon (C)-containing gases such as propylene (C3H6) gas and boron (B)-containing gases such as boron trichloride (BCl3) gas can be used as the first, second, and third reactants. The same effects as those described above can be obtained in this embodiment as well.

[0109] (Inhibitor → Raw Material → First Reactor → Second Reactor) × n (Inhibitor → Raw Material → First Reactor → Second Reactor → Third Reactor) × n [Inhibitor → (Raw material → First reactant → Second reactant) × m] × n [Inhibitor → (Raw material → First reactant → Second reactant → Third reactant) × m] × n

[0110] This disclosure is also suitably applicable when forming a film containing a metallic element, such as hafnium oxide (HfO film), zirconium oxide (ZrO film), aluminum oxide (AlO film), titanium oxide (TiO film), tungsten oxide (WO film), hafnium nitride (HfN film), zirconium nitride (ZrN film), aluminum nitride (AlN film), titanium nitride (TiN film), tungsten nitride (WN film), hafnium oxynitride (HfON film), zirconium oxynitride (ZrON film), aluminum oxynitride (AlON film), titan oxynitride (TiON film), or tungsten oxynitride (WON film), on the surface of a substrate. In this embodiment, the same effects as in the above-described embodiment can be obtained.

[0111] It is preferable that the recipes used for each process be prepared individually according to the processing content, recorded and stored in the storage device 121c via a telecommunications line or external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects the appropriate recipe from among the multiple recipes recorded and stored in the storage device 121c according to the processing content. This makes it possible to form films of various film types, composition ratios, film quality, and film thickness with good reproducibility using a single substrate processing device. Furthermore, it reduces the burden on the operator and allows each process to be started quickly while avoiding operational errors.

[0112] The above-mentioned recipes are not limited to newly created ones; they may also be prepared, for example, by modifying existing recipes already installed in the board processing device. When modifying a recipe, the modified recipe may be installed in the board processing device via a telecommunications line or a recording medium containing the recipe. Alternatively, existing recipes already installed in the board processing device may be directly modified by operating the input / output device 122 provided in the existing board processing device.

[0113] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0114] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0115] The above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above-described embodiments and modifications. [Explanation of Symbols]

[0116] 200 wafers (substrates)

Claims

1. (a) A step of supplying an inhibitor to a substrate having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from a raw material but is not capable of adsorbing the raw material itself, and a second adsorption site that is capable of adsorbing the raw material and the intermediate, and adsorbing the inhibitor to the first adsorption site and the second adsorption site, (b) A step of supplying the raw material to the substrate after the inhibitor has been adsorbed on the first adsorption site and the second adsorption site, generating the intermediate from the raw material, detaching the inhibitor adsorbed on the second adsorption site, and adsorbing the raw material and the intermediate on the second adsorption site to form the first layer, (c) A step of supplying a reactant to the substrate after the raw material and the intermediate have been adsorbed on the second adsorption site, thereby modifying the first layer into the second layer, A substrate processing method comprising the step of forming a film on the surface of the substrate by performing a predetermined number of cycles including the step.

2. The substrate processing method according to claim 1, wherein the surface of the substrate has a recess, the first adsorption site is located on the bottom side of the recess, and the second adsorption site is located on the upper side of the recess.

3. The substrate processing method according to claim 2, wherein the molecular size of the intermediate is smaller than the molecular size of the raw material, and the molecular size of the inhibitor is smaller than the molecular size of the raw material.

4. The substrate processing method according to claim 2, wherein the molecular size of the intermediate is smaller than the molecular size of the raw material, and the molecular size of the inhibitor is smaller than the molecular size of the intermediate.

5. The substrate processing method according to claim 3, wherein the atoms constituting the second adsorption site constitute steric hindrance that inhibits the adsorption of the raw material to the first adsorption site.

6. The substrate processing method according to claim 3, wherein at least a portion of the atoms constituting the second adsorption site are separated, and the distance between the separated atoms is shorter than the width of the molecule of the raw material.

7. The substrate processing method according to claim 6, wherein the distance between atoms is longer than the width of the intermediate molecule and longer than the width of the inhibitor molecule.

8. The substrate processing method according to claim 3, wherein at least some of the atoms constituting the second adsorption site are separated, and the distance between the separated atoms is such that the molecules of the raw material cannot pass through.

9. The substrate processing method according to claim 8, wherein the distance between atoms is the distance that each of the intermediate molecules and the inhibitor molecules can pass through.

10. The substrate processing method according to claim 3, wherein the raw material is supplied under conditions that allow at least a portion of the inhibitor adsorbed on the first adsorption site to be maintained and the inhibitor adsorbed on the second adsorption site to be detached.

11. The substrate processing method according to claim 3, wherein, in (b), at least a portion of the inhibitor adsorbed on the first adsorption site is maintained, thereby suppressing the adsorption of the intermediate onto the first adsorption site.

12. The substrate processing method according to claim 3, wherein, in (b), at least a portion of the inhibitor adsorbed on the first adsorption site is maintained so that the amount of the intermediate adsorbed on the second adsorption site is greater than the amount of the intermediate adsorbed on the first adsorption site.

13. The substrate processing method according to claim 1, wherein when the first layer is modified into the second layer in (c), the inhibitor remaining at the first adsorption site in (b) is removed.

14. The substrate processing method according to claim 1, wherein the cycle comprises performing (a) and performing a set including (b) and (c) a predetermined number of times.

15. The substrate processing method according to any one of claims 1 to 14, wherein each of the first adsorption site and the second adsorption site includes an NH termination.

16. The substrate processing method according to claim 15, wherein the reactant comprises nitrogen and hydrogen.

17. The substrate processing method according to claim 16, wherein the raw materials include a halogen and the main elements constituting the film.

18. The substrate processing method according to claim 17, wherein the inhibitor comprises a halogen.

19. (a) A step of supplying an inhibitor to a substrate having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from a raw material but is not capable of adsorbing the raw material itself, and a second adsorption site that is capable of adsorbing the raw material and the intermediate, and adsorbing the inhibitor to the first adsorption site and the second adsorption site, (b) A step of supplying the raw material to the substrate after the inhibitor has been adsorbed on the first adsorption site and the second adsorption site, generating the intermediate from the raw material, detaching the inhibitor adsorbed on the second adsorption site, and adsorbing the raw material and the intermediate on the second adsorption site to form the first layer, (c) A step of supplying a reactant to the substrate after the raw material and the intermediate have been adsorbed on the second adsorption site, thereby modifying the first layer into the second layer, A method for manufacturing a semiconductor device, comprising the step of forming a film on the surface of a substrate by performing a predetermined number of cycles including the above.

20. A raw material supply system that supplies raw materials to the substrate, An inhibitor supply system that supplies inhibitors to the substrate, A reactant supply system that supplies reactants to a substrate, A temperature control unit that adjusts the temperature of the circuit board, (a) A process of supplying the inhibitor to a substrate having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from the raw material but is not capable of adsorbing the raw material, and a second adsorption site that is capable of adsorbing the raw material and the intermediate, thereby adsorbing the inhibitor to the first adsorption site and the second adsorption site, and (b) supplying the raw material to the substrate after the inhibitor has been adsorbed to the first adsorption site and the second adsorption site, thereby generating the intermediate from the raw material, and the second adsorption site A control unit is configured to control the raw material supply system, the inhibitor supply system, the reactant supply system, and the temperature control unit so as to perform a process of forming a film on the surface of the substrate by performing a predetermined number of cycles including (c) a process of detaching the inhibitor adsorbed on the adsorption site and adsorbing the raw material and the intermediate on the second adsorption site to form a first layer, and (c) a process of supplying the reactant to the substrate after the raw material and the intermediate have been adsorbed on the second adsorption site to modify the first layer into a second layer, thereby forming a film on the surface of the substrate. A substrate processing apparatus having

21. (a) A procedure to supply an inhibitor to a substrate having a first adsorption site on its surface that is capable of adsorbing an intermediate generated from a raw material but is not capable of adsorbing the raw material itself, and a second adsorption site that is capable of adsorbing the raw material and the intermediate, thereby adsorbing the inhibitor to the first adsorption site and the second adsorption site, (b) A procedure to supply the raw material to the substrate after the inhibitor has been adsorbed on the first adsorption site and the second adsorption site, generate the intermediate from the raw material, detach the inhibitor adsorbed on the second adsorption site, and adsorb the raw material and the intermediate on the second adsorption site to form the first layer, (c) A procedure to supply a reactant to the substrate after the raw material and the intermediate have been adsorbed on the second adsorption site, thereby modifying the first layer into the second layer, A procedure for forming a film on the surface of the substrate by performing a predetermined number of cycles including the following, A program that causes a circuit board processing unit to execute commands via a computer.

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