Substrate processing methods, semiconductor device manufacturing methods, processes, substrate processing apparatus and gas supply systems

Abstract

The objective of this invention is to provide a technique for improving the stepped coverage of a film formed on a substrate. The solution of this invention comprises a step of forming a film on a substrate by performing a predetermined number of cycles including the following steps: (a) supplying an inhibitor to the substrate; (b) supplying a first raw material to the substrate from a first storage unit; (c) supplying a second raw material to the substrate from a second storage unit; and (d) supplying a reactant to the substrate.

Description

Technical Field

[0001] This invention relates to a substrate processing method, a semiconductor device manufacturing method, a process, a substrate processing apparatus, and a gas supply system. Prior Technology

[0002] As a step in the substrate processing step (the manufacturing step of a semiconductor device), there is a case where a film is formed on the substrate (for example, see Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2014-135475 Summary of the Invention

[0004] (The problem the invention aims to solve) The present invention provides a technique for improving the step coverage of films formed on a substrate. (Technical means to solve the problem)

[0005] According to one aspect of the present invention, a technique is provided that involves forming a film on a substrate by performing a cycle comprising the following steps a predetermined number of times: (a) The step of supplying an inhibitor to the above-mentioned substrate; (b) The step of supplying the first raw material to the aforementioned substrate by the first storage unit; (c) The step of supplying the second raw material to the aforementioned substrate by the second storage unit; and (d) The step of supplying the reactant to the above substrate. (Compared to the effectiveness of previous technologies)

[0006] According to the present invention, the stepped coverage of the film formed on the substrate can be improved. Simple Explanation of the Diagram

[0007] Figure 1 is a schematic configuration diagram of a longitudinal processing furnace suitable for use in a substrate processing apparatus according to one embodiment of the present invention, showing the processing furnace 202 portion in a longitudinal cross-sectional view. Figure 2 is a schematic configuration diagram of a longitudinal processing furnace suitable for use in a substrate processing apparatus according to one embodiment of the present invention. It is a cross-sectional view of the processing furnace 202 shown along line AA in Figure 1. Figure 3 is a schematic configuration diagram of the controller 121 of the substrate processing apparatus suitable for use in one embodiment of the present invention. It is a block diagram showing the control system of the controller 121. Figure 4 is a diagram showing the processing timing of a sample according to the present invention. Implementation

[0008] <One form of the invention> The following description mainly refers to Figures 1 to 4 to illustrate one aspect of the present invention. Furthermore, the figures used in the following description are schematic diagrams, and the dimensional relationships and ratios of the components in the figures may not necessarily be consistent with the actual figures. Also, the dimensional relationships and ratios of the components in multiple figures may not be consistent with each other.

[0009] (1) Composition of the substrate processing device As shown in Figure 1, the processing furnace 202 has a heater 207 that serves as a temperature regulator (heating unit). The heater 207 is cylindrical and is vertically erected, supported by a retaining plate. The heater 207 also functions as an activation mechanism (activation unit) that activates (excites) gases by heat.

[0010] 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 or silicon carbide (SiC) and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 (hereinafter referred to as MF209) is arranged concentrically with the reaction tube 203. The upper end of MF209 engages with the lower end of the reaction tube 203, thus supporting the reaction tube 203. An O-ring 220a is provided between MF209 and the reaction tube 203 as a sealing member. The reaction tube 203 is vertically erected, just like the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and MF209. A processing chamber 201 is formed in the hollow part of the cylindrical processing container. The processing chamber 201 is configured to accommodate a wafer 200, which serves as a substrate. The wafer 200 is processed in this processing chamber 201.

[0011] Inside the processing chamber 201, nozzles 249a to 249c, serving as the first to third supply sections, are respectively arranged to penetrate the sidewall of MF209. Nozzles 249a to 249c are also referred to as the first to third nozzles. Nozzles 249a to 249c are each made of heat-resistant materials such as quartz or SiC. Gas supply pipes 232a to 232c are connected to nozzles 249a to 249c respectively. Nozzles 249a to 249c are different nozzles.

[0012] Gas supply pipes 232a and 232b are sequentially configured from the upstream side of the gas flow, including mass flow controllers (MFCs) 241a and 241b (flow controllers), valves 243a and 243b (on / off valves), forming a first storage unit 240a and a second storage unit 240b for temporary gas storage, and valves 242a and 242b. Gas supply pipes 232d and 232f are connected downstream of valve 242a in gas supply pipe 232a. Gas supply pipes 232e and 232g are connected downstream of valve 242b in gas supply pipe 232b. MFCs 241d and 241g and valves 243d and 243g are sequentially configured from the upstream side of the gas flow in gas supply pipes 232d to 232g.

[0013] The first storage section 240a and the second storage section 240b are configured, for example, as gas tanks or spiral pipes with a gas capacity larger than that of conventional piping. By opening and closing valves 243a and 243b upstream of the first storage section 240a and the second storage section 240b, and valves 242a and 242b downstream of the first storage section 240a and the second storage section 240b, respectively, the gas supplied by gas supply pipes 232a and 232b can be used to fill the first storage section 240a and the second storage section 240b, or to supply the gas filled in the first storage section 240a and the second storage section 240b to the processing chamber 201. The conductivity between the first storage section 240a and the processing chamber 201 is preferably configured to be, for example, 1.5 × 10⁻³ m³ / s or higher. Furthermore, regarding the ratio of the volume of the processing chamber 201 to the volume of the first storage section 240a, when the volume of the processing chamber 201 is 100L (liters), the volume of the first storage section 240a is preferably set to, for example, 100~300 cc, and preferably to be, for example, 1 / 1000~3 / 1000 times the volume of the processing chamber 201. The same applies to the second storage section 240b.

[0014] By closing valves 242a and 242b and opening valves 243a and 243b, gas with flow rate adjusted via MFCs 241a and 241b can be filled into the first storage section 240a and the second storage section 240b, respectively. After filling the first storage section 240a and the second storage section 240b with predetermined amounts of gas, and after the pressure in the first storage section 240a and the second storage section 240b reaches predetermined pressures, by closing valves 243a and 243b and opening valves 242a and 242b, the high-pressure gas filled in the first storage section 240a and the second storage section 240b can be supplied to the processing chamber 201 in one go and for a short time (rapid supply) through gas supply pipes 232a and 232b and nozzles 249a and 249b. Furthermore, valves 243a and 243b can also be opened during rapid supply.

[0015] In gas supply pipe 232c, MFC 241c and valve 243c, which is a switching valve, are installed upstream of the airflow. Gas supply pipe 232h is connected downstream of gas supply pipe 232c, after valve 243c. In gas supply pipe 232h, MFC 241h and valve 243h are installed sequentially from upstream of the airflow.

[0016] As shown in Figure 2, nozzles 249a to 249c are respectively arranged in a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, rising from the lower part of the inner wall of the reaction tube 203 upwards and towards the arrangement direction of the wafer 200. That is, nozzles 249a to 249c are respectively arranged on the side of the wafer arrangement area arranged on the wafer 200, horizontally surrounding the wafer arrangement area, along the wafer arrangement area.

[0017] Nozzle 249a is positioned further away from exhaust port 231a than nozzles 249b and 249c. That is, nozzles 249b and 249c are positioned closer to exhaust port 231a than nozzle 249a. Furthermore, nozzles 249b and 249c, viewed from above, are arranged linearly symmetrical about the axis of symmetry of a line passing through the center of wafer 200 (i.e., through the center of reaction tube 203 and the center of exhaust port 231a) when wafer 200 has been placed in processing chamber 201. Moreover, nozzles 249a and 249b are positioned facing each other along a straight line, sandwiching the center of reaction tube 203. That is, nozzle 249b is positioned opposite nozzle 249a (opposite face).

[0018] Gas supply holes 250a-250c are respectively provided on the side of nozzles 249a-249c for supplying gas. Gas supply holes 250a-250c open toward the center of reaction tube 203, allowing gas to be supplied to wafer 200. Gas supply holes 250a and 250b open opposite each other in a straight line, sandwiching the center of wafer 200, i.e., the center of reaction tube 203. Gas supply holes 250a-250c are provided in multiples, extending from the lower part to the upper part of reaction tube 203.

[0019] The first raw material is supplied to the processing chamber 201 via gas supply pipe 232a, MFC 241a, valve 243a, first storage unit 240a, valve 242a, and nozzle 249a.

[0020] The second raw material is supplied to the processing chamber 201 via gas supply pipe 232b, MFC 241b, valve 243b, second storage unit 240b, valve 242b, and nozzle 249b.

[0021] The reactant is supplied to the processing chamber 201 via gas supply pipe 232c, MFC 241c, valve 243c, and nozzle 249c.

[0022] The first inhibitor (inhibitor) is supplied to the treatment chamber 201 via gas supply pipe 232d, MFC 241d, valve 243d, and nozzle 249a.

[0023] The second inhibitor (inhibitor) is supplied to the treatment chamber 201 via gas supply pipe 232e, MFC 241e, valve 243e, and nozzle 249b.

[0024] The inert gas system is supplied to the treatment chamber 201 via gas supply pipes 232f~232h, MFC 241f~241h, valves 243f~243h, gas supply pipes 232a~232c, and nozzles 249a~249c. The inert gas serves as a flushing gas, carrier gas, and dilution gas.

[0025] The first raw material supply system is mainly composed of gas supply pipe 232a, MFC 241a, valves 243a and 242a, and the first storage unit 240a. The second raw material supply system is mainly composed of gas supply pipe 232b, MFC 241b, valves 243b and 242b, and the second storage unit 240b. The reactant supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c. The first supply system (first inhibitor supply system, inhibitor supply system) is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d. The second supply system (second inhibitor supply system) is mainly composed of gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system is mainly composed of gas supply pipes 232f-232h, MFC 241f-241h, and valves 243f-243h. Furthermore, the nozzles connected to the gas supply pipes constituting the various supply systems described above can also be included in their respective supply systems. For example, a gas supply system may be constituted by a first raw material supply system, a second raw material supply system, a reactant supply system, a first supply system, a second supply system, an inert gas supply system, and a controller 121 belonging to the control unit described later.

[0026] In the aforementioned gas supply systems, any one or all of the supply systems can also be configured as a collection-type gas supply system 248, which is formed by accumulating valves 243a-243h, 242a, 242b, the first storage unit 240a, the second storage unit 240b, and MFCs 241a-241h. The collection-type gas supply system 248 is connected to gas supply pipes 232a-232h respectively, and the supply operations of various gases in the gas supply pipes 232a-232h, that is, the opening and closing operations of valves 243a-243h, 242a, 242b, or the flow adjustment operations of MFCs 241a-241g, are configured to be controlled by the controller 121 described later. The gas supply system 248 is configured as an integrated or segmented collection unit, and the gas supply pipes 232a to 232h can be installed and removed according to the collection unit unit, so that the gas supply system 248 can be maintained, replaced, or added according to the collection unit unit.

[0027] An exhaust port 231a is provided on the lower side wall of the reaction tube 203 to exhaust the environment inside the processing chamber 201. As shown in Figure 2, the exhaust port 231a is positioned, when viewed from above, opposite to the nozzles 249a~249c (gas supply holes 250a~250c) while holding the wafer 200. The exhaust port 231a is provided from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the wafer arrangement area. An exhaust pipe 231, which serves as the exhaust path, is connected to the exhaust port 231a. The exhaust pipe 231 is connected to a vacuum pump 246, which serves as a vacuum exhaust device, via a pressure sensor 245, which acts as a pressure detector (pressure detection unit), and an APC (Auto Pressure Controller) valve 244, which acts as a pressure regulator (pressure adjustment unit), to the vacuum exhaust device. The APC valve 244 is configured to switch on and off according to the operation of the vacuum pump 246, thereby enabling vacuum exhaust and stopping of vacuum exhaust within the processing chamber 201. Furthermore, based on the operation of the vacuum pump 246 and the pressure information detected by the pressure sensor 245, the valve opening is adjusted to regulate the pressure within 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 can also be considered as included in the exhaust system.

[0028] Below MF209, a sealing cover 219 (hereinafter referred to as SC219) is provided, which can airtightly seal the lower opening of MF209 as a furnace mouth cover. SC219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of SC219, an O-ring 220b is provided as a sealing member that abuts against the lower end of MF209. Below SC219, a rotation mechanism 267 is provided to rotate the crystal boat 217 (described later). The rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS and passes through SC219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. SC219 is configured to be raised and lowered in the vertical direction by a crystal boat lifter 115 (hereinafter referred to as BE115) provided outside the reaction tube 203 as a lifting mechanism. The BE115 system is configured as a conveying device (conveying mechanism) that moves the wafer 200 in and out of the processing chamber 201 by raising and lowering the SC219.

[0029] Below MF209, a baffle 219s, serving as a furnace opening cover, is positioned such that the lower opening of MF209 can be airtightly sealed when SC219 is lowered and the crystal boat 217 is removed from the processing chamber 201. The baffle 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c, acting as a sealing member, is provided on the upper surface of the baffle 219s, abutting against the lower end of MF209. The opening and closing action (lifting or rotating action, etc.) of the baffle 219s is controlled by a baffle opening and closing mechanism 115s.

[0030] The crystal boat 217, serving as a substrate support, is configured to support multiple wafers 200, for example, 25 to 200 wafers, arranged horizontally and aligned at their centers in a vertically aligned manner, in multiple segments, i.e., spaced apart. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. The lower part of the crystal boat 217 is supported by multiple segments of heat-insulating plates 218, such as those made of heat-resistant materials like quartz or SiC.

[0031] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. The energizing status of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature within the processing chamber 201 achieves the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0032] As shown in Figure 3, the controller 121, which belongs to the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a memory device 121c, and an I / O port 121d. The RAM 121b, memory 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, such as a touch panel, is connected to the controller 121. Furthermore, an external memory device 123 can be connected to the controller 121. Moreover, the board processing apparatus can be configured to have one control unit or multiple control units. That is, the control of the processing timing described later can be performed using one control unit or multiple control units. Furthermore, the multiple control units can also be configured as a control system interconnected by wired or wireless communication networks, or the entire control system can be used to control the timing of the processing described later. In this specification, the term "control unit" can refer to a single control unit, multiple control units, or a control system composed of multiple control units.

[0033] The memory device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The memory device 121c readablely stores control programs that control the operation of the board processing device, or process recipes that record the procedures or conditions for the board processing described later. A process recipe is a program that combines various procedures in the board processing described later, which are executed by the board processing device via the controller 121 to obtain a predetermined result. Hereinafter, the general term for process recipes or control programs is also simply referred to as a program. Sometimes, the process recipe is also simply referred to as a recipe. In this specification, the term "program" refers to the case containing only a recipe, the case containing only a control program, or the case containing both. RAM 121b is configured as a memory area (working area) for temporarily storing programs or data read by the CPU 121a.

[0034] I / O port 121d is connected to the aforementioned MFCs 241a~241h, valves 243a~243h, 242a, 242b, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, BE115, and gate switch mechanism 115s.

[0035] CPU 121a is configured to read and execute the control program from memory device 121c, and to read the recipe from memory device 121c in conjunction with the input of operation instructions from input / output device 122. CPU 121a is configured to control the flow adjustment of various substances (various gases) using MFC 241a~241h, the opening and closing of valves 243a~243h, 242a, 242b, the opening and closing of APC valve 244 and the pressure adjustment of APC valve 244 based on pressure sensor 245, the start and stop of vacuum pump 246, the temperature adjustment of heater 207 based on temperature sensor 263, the rotation and speed adjustment of crystal boat 217 by rotating mechanism 267, the raising and lowering of crystal boat 217 using BE115, and the opening and closing of gate 219s using gate switch mechanism 115s, etc., according to the content of the read recipe.

[0036] The controller 121 is configured to install the aforementioned program, recorded and stored in the external memory device 123, into a computer. The external memory device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, USB memory, and semiconductor memory such as SSDs. The memory device 121c or the external memory device 123 constitutes a recording medium that can be read by a computer. Hereinafter, these are collectively referred to as recording media. In this specification, the term "recording media" refers to the case containing only the memory device 121c, the case containing only the external memory device 123, or the case containing both. Furthermore, the provision of computer programs (program products) may also be carried out without the external memory device 123, using communication means such as networks or dedicated lines.

[0037] (2) Substrate processing steps As one of the manufacturing steps using the aforementioned substrate processing apparatus and semiconductor device, the method for processing the substrate, namely the processing sequence example of forming a film on a wafer 200, which is a substrate with three-dimensional structures such as channels, trenches, and holes formed on its surface, will be mainly described using FIG4. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0038] The processing sequence of this sample includes a step of forming a film on wafer 200 by performing the following steps a predetermined number of times (n times, where n is an integer of 1 or 2 or more): (a) Step A: Supplying inhibitors to wafer 200; (b) Step B, which involves supplying the first raw material to the wafer 200 via the first storage unit 240a; (c) Step C, which involves supplying the second raw material to the wafer 200 from the second storage unit 240b; and (d) Step D: Supplying reactants to wafer 200.

[0039] Furthermore, step A may also include at least one of the following steps: step a1, which supplies the first inhibitor to wafer 200 before step B, and step a2, which supplies the second inhibitor to wafer 200 before step C. Figure 4 illustrates an example of performing steps a1, B, a2, C, and D sequentially a predetermined number of times (n times).

[0040] That is, the processing timing shown in Figure 4 represents an example of a process in which a film is formed on wafer 200 by performing a cycle containing the following steps a predetermined number of times (n times, where n is an integer of 1 or 2 or more): Step a1: Supplying the first inhibitor to wafer 200; Step B involves supplying the first raw material to the wafer 200 via the first storage unit 240a; Step a2: Supplying the second inhibitor to wafer 200; Step C, which involves supplying the second raw material to the wafer 200 from the second storage section 240b; and Step D: Supplying reactants to wafer 200.

[0041] For convenience, the above processing sequence is represented as follows in this specification. The same notation is also used in the following descriptions of variations or other versions.

[0042] (Inhibitor 1 → Rinse → Raw Material 1 → Rinse → Inhibitor 2 → Rinse → Raw Material 2 → Rinse → Reactant → Rinse) n

[0043] In this specification, the term "wafer" is used to refer to the wafer itself, or to a laminate of a wafer and a predetermined layer or film formed on its surface. The term "wafer surface" is used to refer to the surface of the wafer itself, or to the surface of a predetermined layer formed on the wafer. The phrase "forming a predetermined layer on the wafer" is used to refer to forming a predetermined layer directly on the surface of the wafer itself, or to forming a predetermined layer on top of layers formed on the wafer. The term "substrate" is used in the same way as "wafer".

[0044] The term "agent" as used in this specification includes at least one of gaseous and liquid substances. Liquid substances include mist substances. That is, the inhibitor (first inhibitor, second inhibitor) may contain gaseous substances, mist substances or other liquid substances, or both.

[0045] The term "layer" as used in this specification includes at least one of continuous layers and discontinuous layers. For example, layers 1 through 3 described later may include continuous layers, discontinuous layers, or both.

[0046] In this specification, when the first inhibitor, the second inhibitor, the first raw material, the second raw material, and the reactant are described as adsorbing or reacting on the surface of wafer 200, it is not limited to the state in which the wafer surface is adsorbed or reacted in an undecomposed state. Sometimes it also includes the state in which the wafer surface is adsorbed or reacted by intermediates generated by such decomposition or by the detachment of their ligands (ligands).

[0047] (Wafer filling and crystal boat loading) After multiple wafers 200 are loaded (wafer filling) into the wafer boat 217, the gate 219s is moved by the gate switching mechanism 115s, opening the lower end of MF209 (gate opening). Then, as shown in Figure 1, the wafer boat 217 supporting the multiple wafers 200 is lifted and moved into the processing chamber 201 by BE115 (wafer boat loading). In this state, SC219 seals the lower end of MF209 via O-ring 220b.

[0048] (Pressure and temperature adjustment) After the wafer boat is loaded, vacuum pump 246 performs vacuum venting (pressure reduction venting) to bring the processing chamber 201, i.e., the space where the wafer 200 is located, to the required pressure (vacuum). At this time, the pressure within the processing chamber 201 is measured by pressure sensor 245, and the APC valve 244 is controlled based on the measured pressure information. Furthermore, the wafer 200 within the processing chamber 201 is heated by heater 207 to bring it to the required processing temperature. At this time, the energization level of heater 207 is controlled based on the temperature information detected by temperature sensor 263, according to the required temperature distribution within the processing chamber 201. Finally, the wafer 200 is rotated by rotation mechanism 267. Venting within the processing chamber 201, heating of the wafer 200, and rotation are all performed continuously, at least until the processing of the wafer 200 is completed.

[0049] (Film-forming steps) Then, proceed with the following steps in sequence: a1, B, a2, C, and D.

[0050] [Step a1] In this step, a first inhibitor is supplied to the wafer 200 in the processing chamber 201.

[0051] Specifically, valve 243d is opened, allowing the first inhibitor to flow into gas supply pipe 232d. The first inhibitor is supplied to processing chamber 201 via nozzle 249a through flow adjustment by MFC 241d and is exhausted through exhaust port 231a. At this time, the first inhibitor is supplied to wafer 200 (first inhibitor supply). At this time, valves 243f to 243h can also be opened to supply inert gas to processing chamber 201 through nozzles 249a to 249c.

[0052] Examples of treatment conditions for supplying the first inhibitor in step a1 include: Processing temperature: 250~800℃, preferably 600~700℃ Processing pressure: 1~3990Pa, preferably 10~1333Pa The first inhibitor supply flow rate is 0.005~5 slm, preferably 0.1~1 slm. First inhibitor administration time: 10-120 seconds, preferably 20-60 seconds Inert gas supply flow rate (per gas supply pipe): 0~10 slm

[0053] Furthermore, the notation of numerical ranges such as "250~800℃" in this specification means that the range includes both the lower and upper limits. Therefore, for example, "250~800℃" means "above 250℃ and below 800℃". The same applies to other numerical ranges. Also, the term "processing temperature" in this specification refers to the temperature of wafer 200 or the temperature inside processing chamber 201, and "processing pressure" refers to the pressure inside processing chamber 201. Furthermore, the term "processing time" refers to the duration of the processing. Furthermore, the term "supply flow rate" refers to the flow rate of gas supplied to processing chamber 201. Also, when the supply flow rate includes 0 slm, 0 slm means that no substance (gas) is supplied. This is also the same as in the following descriptions.

[0054] By supplying the first inhibitor to the wafer 200 under the aforementioned processing conditions, the first inhibitor can be adsorbed onto adsorption points on the surface of the wafer 200. Specifically, this allows the first inhibitor to be adsorbed onto at least a portion of the upper and inner surfaces (specifically, the inner side and bottom surfaces of the recess) of the recess formed on the surface of the wafer 200. More specifically, this allows the first inhibitor to preferentially adsorb onto the opening side (upper side) rather than the deeper side of the recess.

[0055] As the first inhibitor, a gas containing at least one of chlorine (Cl), fluorine (F), bromine (Br), and iodine (I), which are halogen elements, can be used. Examples of first inhibitors include monomeric gases of halogen elements such as Cl2, F2, Br2, and I2; interhalogen compound gases such as ClF3, BrCl, ICl, IF5, BrF3, and IBr; hydrogen halide compound gases such as HCl, HF, HBr, and HI; or combinations of these gases. Furthermore, halogen-containing free radicals (Cl*, F*, Br*, I*, etc.) generated by activating these gases through plasma excitation or the like can be used. One or more of these can be used as the first inhibitor.

[0056] Furthermore, as the first inhibitor, a gas containing an organic compound can be used. As a gas containing an organic compound, a gas containing at least one of the group consisting of ether compounds, ketone compounds, amine compounds, organohydrazine compounds, or compounds having a cyclic structure in their molecular structure can be used. As a gas containing an ether compound, a gas containing at least one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, piperan, tetrahydropiperan. As a gas containing a ketone compound, a gas containing at least one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl acetone, etc. can be used. As a gas containing an amine compound, a gas containing at least one of methylamine compounds such as monomethylamine, dimethylamine, trimethylamine; ethylamine compounds such as monoethylamine, diethylamine, triethylamine; or methylethylamine compounds such as dimethylethylamine, methyl diethylamine. As a gas containing an organohydrazine compound, a gas containing at least one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, trimethylhydrazine. As a gas containing a compound with a cyclic structure, gases such as methoxycyclopentane, anisole, and propylene oxide, which have a cyclic structure containing at least one of cycloalkyl, benzene ring, or carbon, can be used. One or more of these can be used as the first inhibitor.

[0057] Furthermore, alkyl-containing gases can also be used as the first inhibitor. Examples of first inhibitors include CH4 gas, C2H6 gas, and C3H8 gas.

[0058] As the inert gas, for example, N2 gas, or rare gases such as Ar, He, Ne, and Xe gas can be used. One or more of these can be used as the inert gas. This point also applies to the steps described below.

[0059] After the first inhibitor is adsorbed onto the surface of wafer 200, valve 243d is closed to stop the supply of the first inhibitor to the processing chamber 201. Then, a vacuum is vented from the processing chamber 201 to remove any gaseous substances remaining there. At this time, valves 243f to 243h are opened to supply inert gas to the processing chamber 201 through nozzles 249a to 249c. The inert gas system supplied by nozzles 249a to 249c acts as a flushing gas, thereby flushing the space where wafer 200 exists, that is, flushing the processing chamber 201 (flushing).

[0060] Furthermore, during step a1, valve 242a is closed, and valve 243a is opened to allow the first raw material to flow through gas supply pipe 232a. The first raw material is supplied to the first storage section 240a by adjusting the flow rate via MFC 241a. This fills the first storage section 240a with the first raw material (first tank feed). After filling (feeding) the first storage section 240a with a predetermined amount of the first raw material, valve 243a is closed, maintaining the first storage section 240a in a state of being filled with the first raw material. The first tank feed can also be performed before step a1.

[0061] [Step B] This step involves supplying the first raw material to the wafer 200 inside the processing chamber 201.

[0062] Specifically, valve 242a is opened, allowing the high-pressure first raw material filled in the first storage section 240a to flow into the processing chamber 201 in one go. This provides the wafer 200 with the first raw material in one go (rapid supply of the first raw material). During this rapid supply of the first raw material, due to the pressure difference between the first storage section 240a and the processing chamber 201, the first raw material ejected from nozzle 249a into the processing chamber 201 is accelerated to, for example, the speed of sound (340 m / sec), and the velocity of the first raw material on the wafer 200 also reaches approximately tens of m / sec. The rapid supply of the second raw material, described later, is similar. Furthermore, valve 243a is opened beforehand. At this time, valves 243f to 243h can also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c.

[0063] Examples of processing conditions for supplying the first raw material in step B include: Processing temperature: 250~800℃, preferably 600~700℃ Processing pressure: 1~2666Pa, preferably 1~1333Pa The first raw material supply flow rate is 0.001~5 slm, preferably 0.1~5 slm. The first raw material supply time is 0.1 to 20 seconds, preferably 0.5 to 5 seconds. Inert gas supply flow rate (per gas supply pipe): 0~10 slm

[0064] By supplying the first material to the wafer 200 under the above processing conditions, the first material is adsorbed at the adsorption points on the surface of the wafer 200 where the first inhibitor has not been adsorbed, that is, at the adsorption points remaining on the surface of the wafer 200, and a first layer can be formed.

[0065] Here, the first inhibitor is a substance that inhibits the adsorption of the first material onto the wafer 200. Specifically, the functional groups (e.g., halogen groups) contained in the first inhibitor and formed (exposed) on the upper and inner surfaces of the recess hinder the adsorption of the first material onto the wafer 200 (the upper and inner surfaces of the recess). As described above, since the first inhibitor preferentially adsorbs on the opening side of the recess, the adsorption of the first material is more inhibited on the opening side than on the deeper side of the recess. In this way, the first material can be preferentially adsorbed on the deeper side of the recess to form a first layer.

[0066] Furthermore, in this sample, by rapidly supplying the first material, a large flow rate of the first material can be supplied to wafer 200 within a short period of time after the supply of the first material begins. This allows for an increase in the amount of the first material reaching the deeper side of the recess within a short time after the supply of the first material begins. Therefore, the first material can be more preferentially adsorbed on the deeper side of the recess, forming the first layer.

[0067] As the first raw material, a silane-based gas, for example, containing silicon (Si), the main element constituting the film formed on wafer 200, can be used. As a silane-based gas, a gas containing Si and a halogen, i.e., a halosilane-based gas, can be used. Halogens include Cl, F, Br, I, etc. As a halosilane-based gas, a chlorosilane-based gas containing Si and Cl can be used, for example.

[0068] As the first raw material, chlorosilane-based gases such as SiH3Cl gas, SiH2Cl2 gas, SiHCl3 gas, SiCl4 gas, Si2Cl6 gas, Si3Cl8 gas, Si2Cl6 gas, Si3Cl8 gas, Si2H5Cl gas, Si2H4Cl2 gas, Si2H3Cl3 gas, Si2H2Cl4 gas, Si3H5Cl gas, and Si3H4Cl2 gas can be used. One or more of these gases can be used as the first raw material.

[0069] In addition to chlorosilane gases, other gases such as fluorosilane gases (e.g., SiF4, SiH2F2), bromosilane gases (e.g., SiBr4, SiH2Br2), or iodosilane gases (e.g., SiI4, SiH2I2) may be used as the first raw material. One or more of these gases may be used as the first raw material.

[0070] In addition to these, gases containing Si and amine groups, i.e., aminosilane gases, can also be used as the primary raw material. An amine group refers to a monovalent functional group formed by removing hydrogen (H) from ammonia, primary amines, or secondary amines, and can be represented as -NH2, -NHR, or -NR2. Furthermore, R represents an alkyl group, and the two Rs in -NR2 can be the same or different.

[0071] As the first raw material, amine silane gases (organoamine silane gases), such as (Si[N(CH3)2]4) gas, (Si[N(CH3)2]3H) gas, (Si[N(C2H5)2]2H2) gas, (SiH2[NH(C4H9)]2) gas, and (SiH3[N(C3H7)2]) gas, may also be used. One or more of these may be used as the first raw material.

[0072] After the first layer is formed on the surface of wafer 200, valves 243a and 242a are closed to stop the supply of the first raw material to the processing chamber 201. Then, the same process as described above (rinsing) is performed.

[0073] [Step a2] In this step, a second inhibitor is supplied to the wafer 200 in the processing chamber 201.

[0074] Specifically, valve 243e is opened, allowing the second inhibitor to flow into gas supply pipe 232e. The second inhibitor is supplied to processing chamber 201 via nozzle 249b through flow adjustment via MFC 241e and is exhausted through exhaust port 231a. At this time, the second inhibitor is supplied to wafer 200 (second inhibitor supply). At this time, valves 243f to 243h can also be opened to supply inert gas to processing chamber 201 through nozzles 249a to 249c.

[0075] Examples of treatment conditions for supplying the second inhibitor in step a2 include: Processing temperature: 250~800℃, preferably 600~700℃ Processing pressure: 1~3990Pa, preferably 10~1333Pa The second inhibitor supply flow rate is 0.005~5 slm, preferably 0.1~1 slm. Second inhibitor administration time: 10-120 seconds, preferably 20-60 seconds Inert gas supply flow rate (per gas supply pipe): 0~10 slm

[0076] By supplying the second inhibitor to the wafer 200 under the aforementioned processing conditions, the second inhibitor can be adsorbed onto areas on the surface of the wafer 200 where the first inhibitor has not been adsorbed. Specifically, this allows the second inhibitor to be adsorbed onto at least a portion of the upper and inner surfaces (specifically, the inner side and bottom surfaces of the recess) of the recess formed on the surface of the wafer 200 where the first inhibitor has not been adsorbed. More specifically, this allows the second inhibitor to be preferentially adsorbed onto the opening side rather than the deeper side of the recess.

[0077] As the second inhibitor, one or more gases, exemplified as the first inhibitor, may be used. The second inhibitor may be the same gas as the first inhibitor, or it may be a different gas from the first inhibitor.

[0078] After the second inhibitor is adsorbed onto the surface of wafer 200, valve 243e is closed to stop the supply of the second inhibitor to the processing chamber 201. Then, the same process as described above (rinsing) is performed.

[0079] Furthermore, during step a2, valve 242b is closed, and valve 243b is opened to allow the second raw material to flow through gas supply pipe 232b. The second raw material is supplied to the second storage section 240b by adjusting the flow rate via MFC 241b. This fills the second storage section 240b with the second raw material (second tank feed). After filling the second storage section 240b with a predetermined amount of the second raw material, valve 243b is closed, maintaining the second storage section 240b in a state of being filled with the second raw material. The second tank feed can also be performed before step a2.

[0080] [Step C] This step involves supplying the second raw material to the wafer 200 within the processing chamber 201.

[0081] Specifically, valve 242b is opened, allowing the high-pressure second raw material filled in the second storage section 240b to flow into the processing chamber 201 in one go. This provides the wafer 200 with the second raw material in one continuous flow (rapid supply of the second raw material). Valve 243b is opened beforehand. At this time, valves 243f to 243h can also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249c.

[0082] Examples of processing conditions for supplying the second raw material in step C include: Processing temperature: 250~800℃, preferably 600~700℃ Processing pressure: 1~2666Pa, preferably 1~1333Pa The second raw material supply flow rate is 0.001~5 slm, preferably 0.1~5 slm. The second raw material supply time is 0.1 to 20 seconds, preferably 0.5 to 5 seconds. Inert gas supply flow rate (per gas supply pipe): 0~10 slm

[0083] By supplying the second material to the wafer 200 under the above processing conditions, the second material is adsorbed on the surface of the wafer 200 at a location where at least one of the first inhibitor and the second inhibitor is not adsorbed (in other words, a location where neither the first inhibitor nor the second inhibitor is adsorbed), thereby forming a second layer.

[0084] Therefore, both the first inhibitor and the second inhibitor are substances that inhibit the adsorption of the second material onto the wafer 200. Specifically, the functional groups (e.g., halogen groups) contained in the first inhibitor or the second inhibitor and formed (exposed) on the upper and inner surfaces of the recess hinder the adsorption of the second material onto the wafer 200 (the upper and inner surfaces of the recess). As mentioned above, since both the first inhibitor and the second inhibitor preferentially adsorb onto the opening side of the recess, the adsorption of the second material is more suppressed on the opening side than on the deeper side of the recess. In this way, the second material can be preferentially adsorbed onto the deeper side of the recess to form a second layer.

[0085] Furthermore, in this sample, by rapidly supplying the second material, a large flow rate of the second material can be supplied to wafer 200 within a short period of time after the supply of the second material begins. This allows for an increase in the amount of the second material reaching the deeper side of the recess within a short time after the supply of the second material begins. Therefore, the second material can be more preferentially adsorbed on the deeper side of the recess, forming the second layer.

[0086] As the second raw material, one or more of the gases exemplified as the first raw material may be used. The second raw material may be the same raw material gas (same material) as the first raw material, or it may be a different raw material gas (different material) from the first raw material.

[0087] After the second layer is formed on the surface of wafer 200, valves 243b and 242b are closed to stop the supply of the second raw material to the processing chamber 201. Then, the same process as described above (rinsing) is performed.

[0088] [Step D] After step C is completed, the reactant is supplied to the wafer 200 in the processing chamber 201.

[0089] Specifically, valve 243c is opened to allow the reactant to flow into gas supply pipe 232c. The reaction system is flow-regulated by MFC 241c, supplied to processing chamber 201 via nozzle 249c, and vented through exhaust port 231a. At this time, reactant is supplied to wafer 200 (reactant supply). At this time, valves 243e-243g can also be opened to supply inert gas to processing chamber 201 via nozzles 249a-249c respectively.

[0090] Examples of processing conditions for supplying the reactants in step D include: Processing temperature: 400~800℃, preferably 650~700℃ Processing pressure: 10~10000Pa, preferably 20~5000Pa Reactant supply flow rate: 0.001~20 slm, preferably 1~10 slm Reactant supply time: 1~120 seconds, preferably 1~60 seconds Inert gas supply flow rate (per gas supply pipe): 0~10 slm

[0091] By supplying a reactant to the wafer 200 under the aforementioned processing conditions, at least a portion of the first and second layers formed on the wafer 200 can react with the reactant and be modified. As a result, a third layer, which is a modified layer belonging to at least one of the first and second layers, is formed on the inner surface of the recess on the wafer 200.

[0092] As reactants, nitrogen (N) and hydrogen (H) gases, such as those belonging to the nitriding gas family, can be used. The N- and H-containing gases can be either N-containing or H-containing gases. It is preferable that the N- and H-containing gases have NH bonds.

[0093] As reactants, hydrogen nitride gases such as NH3, N2H2, N2H4, and N3H8 can be used.

[0094] In addition to these, gases containing N, carbon (C), and H can also be used as reactants. For example, amine gases or organic hydrazine gases can be used as N, C, and H gases. The N, C, and H gases can be N-containing gases, C-containing gases, H-containing gases, or N and C-containing gases.

[0095] As reactants, ethylamine gases such as C2H5NH2, (C2H5)2NH, and (C2H5)3N, methylamine gases such as CH3NH2, (CH3)2NH, and (CH3)3N, or organic hydrazine gases such as (CH3)HN2H2, (CH3)2N2H2, and (CH3)2N2(CH3)H can be used.

[0096] One or more of these can be used as reactants.

[0097] After the third layer is formed on the surface of wafer 200, valve 243c is closed to stop the supply of reactants to the processing chamber 201. Then, the same process as described above (rinsing) is performed.

[0098] [Perform the predetermined number of times] By performing the above steps a1, B, a2, C, and D sequentially n times (n being an integer of 1 or 2 or higher), a film can be formed on the surface of wafer 200 (the inner surface of the recess). Furthermore, by setting this number of cycles n as the number of times the interior of the recess is filled with the film, the interior of the recess is filled with the film. For example, when using the above-mentioned Si-containing gas as the first or second raw material and the above-mentioned nitride gas as the reactant, a silicon nitride film (SiN film) is formed on the surface of wafer 200. The above cycle is preferably repeated multiple times. That is, it is preferable that the thickness of the third layer formed in each cycle is thinner than the required thickness, and the above cycle is repeated multiple times until the film thickness formed by stacking the third layer reaches the required film thickness. Furthermore, in subsequent cycles, it is preferable that the filling of the first raw material into the first storage section 240a in step B and the supply of the reactant in step D of the previous cycle are carried out in parallel.

[0099] (Post-rinse and atmospheric pressure recovery) After the film of the required thickness is formed on wafer 200, an inert gas, used as a rinsing gas, is supplied to the processing chamber 201 through nozzles 249a-249c and exhausted through exhaust port 231a. This rinsing process removes residual gases or reaction byproducts from the processing chamber 201. Subsequently, the environment within the processing chamber 201 is replaced with an inert gas, and the pressure within the processing chamber 201 is restored to atmospheric pressure.

[0100] (Crystal boat unloading and wafer removal) Subsequently, SC219 is lowered by BE115, opening the lower end of MF209. Then, the processed wafer 200, supported by the wafer boat 217, is moved from the lower end of MF209 to the outside of the reaction tube 203 (wafer boat unloading). After unloading, the stop gate 219s moves, sealing the lower opening of MF209 via O-ring 220c. The processed wafer 200, after being moved to the outside of the reaction tube 203, is removed by the wafer boat 217.

[0101] (3) Effects of the original state Based on this state, one or more of the following effects can be obtained.

[0102] The first and second inhibitors supplied in steps a1 and a2, respectively, are preferentially adsorbed onto the opening side of the recess compared to the deeper side. Therefore, the first and second raw materials supplied in steps B and C are more inhibited on the opening side than on the deeper side of the recess. Consequently, since the first and second raw materials can be preferentially adsorbed onto the deeper side of the recess, film formation can proceed at a uniform rate from the deeper side of the recess to the opening side. This improves the step coverage.

[0103] In steps B and C, the first raw material and the second raw material are pre-filled into the first storage section 240a and the second storage section 240b, respectively, before being supplied to the processing chamber 201. That is, a large flow rate of the first raw material and the second raw material are supplied simultaneously (rapid supply) within a short period. This increases the amount of the first and second raw materials reaching the deeper side of the recess within a short time after the initial supply. Therefore, since the first and second raw materials can be more preferentially adsorbed onto the deeper side of the recess, film formation can proceed at a more uniform speed from the deeper side of the recess to the opening side. This further improves the step coverage.

[0104] By using materials with different numbers of Si per molecule, or by using different materials such as an organic material in one and an inorganic material in the other, the materials (first and second materials) can be uniformly absorbed on wafer 200. This allows for more uniform adsorption of the first and second materials from the deep side of the recess to the opening side. As a result, the step coverage can be further improved.

[0105] Furthermore, by supplying both the first inhibitor, which inhibits the adsorption of the first raw material, and the first raw material through nozzle 249a, the adsorption of the first raw material on nozzle 249a can be avoided. Similarly, by supplying both the second inhibitor, which inhibits the adsorption of the second raw material, and the second raw material through nozzle 249b, the adsorption of the second raw material on nozzle 249b can be avoided.

[0106] (4) Variations The processing sequence of this sample can be changed as shown in the following variations. These variations can be combined arbitrarily. Unless otherwise specified, the processing procedures and conditions in each step of each variation can be set to be the same as those in each step of the above processing sequence.

[0107] (Variation Example 1) As shown in the following processing sequence, step a2 can also be omitted, and steps a1, B, C, and D can be performed in sequence.

[0108] (Inhibitor 1 → Rinse → Raw Material 1 → Rinse → Raw Material 2 → Rinse → Reactant → Rinse) n

[0109] In this variation, the same effect as the above-described state can be achieved. In this variation, the cycle time can be further shortened, thereby increasing the yield.

[0110] (Variation Example 2) As shown in the following processing sequence, step a1 can also be omitted, and steps B, a2, C, and D can be performed in sequence.

[0111] (First raw material → Rinse → Second inhibitor → Rinse → Second raw material → Rinse → Reaction body → Rinse) n

[0112] In this variation, the same effect as the above-described state can be achieved. In this variation, the cycle time can be further shortened, thereby increasing the yield.

[0113] (Variation Example 3) As shown in the following processing sequence, step a2 can also be omitted, and steps a1, B, and D can be performed in sequence. Step C is performed simultaneously with step B.

[0114] {Inhibitor 1 → Rinse → (Initial Material 1 + Initial Material 2) → Rinse → Reactant → Rinse} n

[0115] In this variation, the same effect as the above-described state can be achieved. In this variation, the cycle time can be further shortened, thereby increasing the yield.

[0116] (Variation Example 4) As shown in the following processing sequence, step a1 can also be omitted, and steps B, a2, C, and D can be performed in sequence. When performing step B, step C can also be performed, and when performing step C, step B can also be performed.

[0117] {(Ingredient 1 + Ingredient 2) → Rinse → Inhibitor 2 → Rinse → (Ingredient 1 + Ingredient 2) → Rinse → Reactant → Rinse} n

[0118] In this modified example, the same effect as the above-described state can be obtained. In this modified example, since the adsorption amount of the first and second raw materials on the wafer 200 is further increased in each cycle, the yield can be improved.

[0119] (Variation Example 5) As shown in the following processing sequence, step a1 can also be omitted, and steps B, a2, C, and D can be performed in sequence. Step C is also performed when step B is performed.

[0120] {(Ingredient 1 + Ingredient 2) → Rinse → Inhibitor 2 → Rinse → Ingredient 2 → Rinse → Reactant → Rinse} n

[0121] In this modified example, the same effect as described above can be obtained. In this modified example, in step B, a larger amount of the first raw material can be adsorbed onto the deeper side of the recess, and in step C, a larger amount of the second raw material can be adsorbed onto the open side of the recess. This allows film formation to proceed at a uniform rate from the deeper side of the recess to the open side, improving the uniformity of film thickness within the recess, especially the step coverage when forming the film in the recess. Furthermore, in this modified example, compared to modified example 4, which performs steps B and C twice simultaneously, the amount of raw material can be reduced.

[0122] (Variation Example 6) As shown in the following processing sequence, step a1 can also be omitted, and steps B, a2, C, and D can be performed in sequence. Step B can also be performed when step C is performed.

[0123] {First raw material → Rinse → Second inhibitor → Rinse → (First raw material + Second raw material) → Rinse → Reactant → Rinse} n

[0124] In this modified example, the same effect as the above-described example can be obtained. In this modified example, the cycle time can be further shortened and the yield increased. Furthermore, compared to modified example 4, which performs steps B and C twice simultaneously, the amount of raw materials can be reduced.

[0125] (Variation Example 7) As shown in the following processing sequence, steps a1, B, a2, C, and D can also be performed sequentially, with step C being performed while step B is being performed, and step B being performed while step C is being performed.

[0126] {Inhibitor 1 → Rinse → (Ingredient 1 + Ingredient 2) → Rinse → Inhibitor 2 → Rinse → (Ingredient 1 + Ingredient 2) → Rinse → Reactant → Rinse} n

[0127] In this modified example, the same effect as the above-described state can be obtained. In this modified example, since the adsorption amount of the first and second raw materials on the wafer 200 is further increased in each cycle, the yield can be improved.

[0128] (Variation Example 8) As shown in the following processing sequence, steps a1, B, a2, C, and D can also be performed sequentially, with step C performed while step B is being performed.

[0129] {Inhibitor 1 → Rinse → (Ingredient 1 + Ingredient 2) → Rinse → Inhibitor 2 → Rinse → Ingredient 2 → Rinse → Reactant → Rinse} n

[0130] In this modified example, the same effect as described above can be obtained. In this modified example, in step B, a larger amount of the first raw material can be adsorbed onto the deeper side of the recess, and in step C, a larger amount of the second raw material can be adsorbed onto the open side of the recess. This allows film formation to proceed at a uniform rate from the deeper side of the recess to the open side, improving the uniformity of film thickness within the recess, especially the step coverage when forming the film in the recess. Furthermore, in this modified example, compared to modified example 7 which performs steps B and C twice simultaneously, the amount of raw material can be reduced.

[0131] (Variation Example 9) As shown in the following processing sequence, steps a1, B, a2, C, and D can also be performed sequentially, with step B performed while step C is being performed.

[0132] {Inhibitor 1 → Rinse → Raw Material 1 → Rinse → Inhibitor 2 → Rinse → (Raw Material 1 + Raw Material 2) → Rinse → Reactant → Rinse} n

[0133] In this modified example, the same effect as the above-described state can be obtained. In this modified example, the adsorption amount of the first and second raw materials on the wafer 200 in each cycle is further increased, which can improve the yield. Also, compared with modified example 7, which performs steps B and C twice simultaneously, the raw materials can be reduced.

[0134] <Other forms of the invention> The present invention has been specifically described above. However, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from its spirit.

[0135] For example, by differentiating the amounts (gutter feed rate) of the first and second raw materials fed into the first storage section 240a and the second storage section 240b, the adsorption state of the first and second raw materials on the wafer 200 in steps B and C can be adjusted. For example, when the amount of the first raw material fed into the first storage section 240a is greater than the amount of the second raw material fed into the second storage section 240b, a larger flow rate of the first raw material is supplied to the wafer 200 in a shorter time than the second raw material. Therefore, the first raw material supplied in step B is adsorbed more deeply on the recessed side than the second raw material supplied in step C. In other words, in step B, more of the first raw material can be adsorbed on the deep side of the recess, and in step C, more of the second raw material can be adsorbed on the opening side of the recess. In this prototype, the same effect as described above can be obtained. On the other hand, when the amount of the second raw material fed into the second storage section 240b is greater than the amount of the first raw material fed into the first storage section 240a, a larger flow rate of the second raw material is supplied to the wafer 200 in a shorter time than the first raw material. Therefore, the second raw material supplied in step C is more adsorbed on the deeper side of the recess than the first raw material supplied in step B. In other words, in step B, more of the first raw material can be adsorbed on the opening side of the recess, and in step C, more of the second raw material can be adsorbed on the deeper side of the recess. In this prototype, the same effect as the above prototype can be obtained.

[0136] For example, by varying the supply amounts of the first and second inhibitors, the adsorption state of the first and second raw materials on the wafer 200 in steps B and C can be adjusted. For instance, when the supply amount of the first inhibitor is greater than that of the second inhibitor, the first inhibitor supplied in step a1 is adsorbed more on the opening side of the recess than the second inhibitor supplied in step a2. Therefore, compared to the second raw material supplied in step C, the adsorption of the first raw material supplied in step B on the opening side of the recess is more hindered, resulting in greater adsorption on the deeper side of the recess. In other words, in step B, more of the first raw material can be adsorbed on the deeper side of the recess, and in step C, more of the second raw material can be adsorbed on the opening side of the recess. The same effect as described above can also be obtained in this sample. On the other hand, when the supply amount of the second inhibitor is greater than that of the first inhibitor, the second inhibitor supplied in step a2 is adsorbed more onto the opening side of the recess than the first inhibitor supplied in step a1. Therefore, compared to the first material supplied in step B, the adsorption of the second material supplied in step C on the opening side of the recess is more hindered, and thus it is adsorbed more onto the deeper side of the recess. In other words, in step C, more of the second material can be adsorbed onto the deeper side of the recess, and in step B, more of the first material can be adsorbed onto the opening side of the recess. The same effect as the above-described sample can also be obtained in this state sample.

[0137] The above-described embodiments illustrate the case where the first raw material and the second raw material are rapidly supplied in either step B or C. However, the present invention is not limited to this. For example, the first raw material may be supplied to the processing chamber 201 via valve 243a, the first storage unit 240a, valve 242a, nozzle 249a, etc., without prior feeding into the first storage unit 240a before step B is performed (non-rapid supply, normal flow). Similarly, the second raw material may be supplied to the processing chamber 201 via valve 243b, the second storage unit 240b, valve 242b, nozzle 249b, etc., without prior feeding into the second storage unit 240b before step C is performed (non-rapid supply, normal flow). At least some of the effects described in the above-described embodiments can also be obtained in this embodiment.

[0138] The above-described embodiments illustrate the use of the first and second inhibitors to suppress the adsorption of the first and second raw materials on the surface of wafer 200. However, the present invention is not limited thereto. For example, the first and second inhibitors can also be used as modifiers, conditioning agents, accelerators, or admixtures. As an example, the first inhibitor can be used as an inhibitor in step a1, and the second inhibitor can be used as a conditioning agent or admixture in step a2. Here, when the second inhibitor is used as a conditioning agent, it can be, for example, a gas containing O and H, a gas containing O, a gas containing O and N, or a gas containing O and C. When the second inhibitor is used as an admixture, it can be, for example, trichloroborane (BCl3) gas or phosphine (PH3) gas. At least some of the effects described in the above-described embodiments can also be obtained in this embodiment.

[0139] Furthermore, in the above-described state sample, chlorosilane gas was used as an example of the first raw material. However, the present invention is not limited to this. For example, when using a first raw material containing metal elements such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), molybdenum (Mo), and tungsten (W), and forming films containing metal elements such as AlN film, TiN film, HfN film, ZrN film, TaN film, molybdenum nitride film (MoN), WN, AlO film, TiO film, HfO film, ZrO film, TaO film, MoO, WO film, TiON film, TiAlCN film, TiAlC film, and TiCN film on wafer 200 through the above-described processing sequence, the present invention can also be applied. The same effects as the above-described state sample can also be obtained in this state sample.

[0140] Furthermore, in the above-described state, the reactants are, for example, gases containing N and H. However, the present invention is not limited to this. For example, carbon (C) gases such as C2H4, C2H2, and C3H6, or boron (B) gases such as B2H6 and BCl3, or oxygen (O2), ozone (O3), plasma-excited O2 (O2*), O2 + hydrogen (H2), water vapor (H2O), H2O2, N2O, NO, NO2, CO, and CO2 are used. Moreover, in this specification, the combined description of two gases, such as "O2 + H2," refers to a mixture of H2 and O2 gases. When supplying the mixed gas, the two gases can be mixed (premixed) in the supply pipe before being supplied to the processing chamber 201; alternatively, the two gases can be supplied to the processing chamber 201 separately through different supply pipes, so that they are mixed in the processing chamber 201 (postmixed). One or more of these can be used as reactants. In this sample, the same effect as the above-described sample can also be obtained.

[0141] Furthermore, the above-described example illustrates the formation of a SiN film on wafer 200 during substrate processing. However, the present invention is not limited to this. In addition to SiN films, the present invention can also be applied to the formation of Si-containing films such as SiCN, SiON, SiOC, SiOCN, SiBCN, SiBN, and SiO films. The same effects as those described above can be obtained in this example.

[0142] Furthermore, in the above description, the control unit is illustrated using a physical controller (controller 121) as an example. However, the present invention is not limited to this. The control unit may also be a software program existing in the memory of the controller. In this embodiment, the same effect as described above can also be obtained.

[0143] Furthermore, in the above-described example, the gas supply system is described using the case where it is composed of a first raw material supply system, a second raw material supply system, a reactant supply system, a first supply system, a second supply system, an inert gas supply system, and a controller 121 belonging to the control unit (described later). However, the present invention is not limited to this. For example, the gas supply system may also be composed of a first raw material supply system, a second raw material supply system, a reactant supply system, a first supply system, a second supply system, an inert gas supply system, and software. Furthermore, the control unit may also be composed of software. Moreover, the gas supply system is configured to be controllable for performing the processing of the present invention.

[0144] The formulations used in each process are preferably prepared individually according to the processing requirements and pre-recorded and stored in memory device 121c via telecommunication channels or external memory device 123. Then, preferably, at the start of each process, CPU 121a selects the appropriate formulation from the multiple formulations recorded and stored in memory device 121c, based on the processing requirements. In this way, films of various types, compositions, qualities, and thicknesses can be formed with excellent reproducibility using a single substrate processing device. Furthermore, it reduces the operator's workload, avoids operational errors, and allows for the rapid initiation of each process.

[0145] The above-mentioned formula is not limited to novel formulations; for example, it can also be prepared by modifying an existing formula already installed in the substrate processing device. In the case of formula modification, the modified formula can be installed in the substrate processing device via a telecommunication channel or a recording medium containing the formula. Alternatively, the input / output device 122 of the existing substrate processing device can be used to directly modify an existing formula already installed in the substrate processing device.

[0146] The above examples illustrate film formation using a batch substrate processing apparatus that processes multiple substrates at a time. The present invention is not limited to these examples; for instance, it is also suitable for forming films using a single-sheet substrate processing apparatus that processes one or more substrates at a time. Furthermore, the above examples illustrate film formation using a substrate processing apparatus equipped with a hot-wall type furnace. The present invention is not limited to these examples; it is also suitable for forming films using a substrate processing apparatus equipped with a cold-wall type furnace. Furthermore, the above examples illustrate gas activation by heat. However, the present invention is not limited to this. For example, it is also suitable for activating gases by plasma generated inside or outside the processing chamber 201, or by irradiating gases with electromagnetic waves using lamps or the like.

[0147] When using such substrate processing apparatus, each processing procedure and processing condition can be performed in the same manner as the above-described sample or modified example, and the same effect as the above-described sample or modified example can be obtained.

[0148] The above-mentioned states or variations can be used in appropriate combinations. In this case, the processing procedures and conditions can be set to be the same as those in the above-mentioned states or variations.

[0149] 115: Crystal Boat Lift (BE) 115s: Door stop mechanism 121: Controller 121a: CPU 121b:RAM 121c: Memory device 121d: I / O port 121e: Internal bus 122: Input / output devices 123: External memory device 200: Wafer (substrate) 201: Processing Room 202: Processing Furnace 203: Reaction tube 207: Heater 209: Manifold (MF) 217: Crystal Boat 218: Insulation board 219: Sealing Cap (SC) 219s: Blocking the door 220a, 220b, 220c: O-rings 231: Exhaust pipe 231a: Exhaust port 232a, 232b, 232c, 232d, 232e, 232f, 232g, 232h: Gas supply pipes 240a: First Storage Unit 240b: Second Storage Unit 241a, 241b, 241c, 241d, 241e, 241f, 241g, 241h: Mass Flow Controller (MFC) 242a,242b,243a,243b,243c,243d,243e,243f,243g,243h: Valve 244: APC valve 245: Pressure sensor 246: Vacuum pump 248: Accumulated Gas Supply System 249a, 249b, 249c: Nozzles 250a, 250b, 250c: Gas supply ports 255: Rotation axis 263: Temperature sensor 267: Rotating mechanism

Claims

1. A substrate processing method comprising performing a predetermined number of cycles including the following steps to form a film on a substrate having recesses formed on its surface: (a) a step of supplying an inhibitor to the substrate; (b) a step of supplying a first raw material to the substrate from a first storage unit; (c) a step of supplying a second raw material to the substrate from a second storage unit; and (d) a step of supplying a reactant to the substrate after (a), (b), and (c); (a) comprising at least one of the following steps: (a-1) a step of supplying a first inhibitor as the inhibitor to the substrate before (b); and (a-2) a step of supplying a second inhibitor as the inhibitor to the substrate before (c).

2. The substrate processing method as described in claim 1, wherein, When (b) is being performed, (c) is also being performed; when (c) is being performed, (b) is also being performed.

3. The substrate processing method as described in claim 1, wherein, (c) is also performed while (b) is being performed.

4. The substrate processing method as described in claim 1, wherein, (b) is also performed while (c) is being performed.

5. The substrate processing method as described in claim 1, wherein, In (b), the following steps are performed: (b-1) storing the first raw material in the first storage section; and (b-2) supplying the first raw material stored in the first storage section to the substrate; in (c), the second raw material is not stored in the second storage section before it is supplied from the second storage section.

6. The substrate processing method as described in claim 1, wherein, In (b), before the first raw material is supplied via the first storage section, the first raw material is not stored in the first storage section. In (c), the following steps are performed: (c-1) storing the second raw material in the second storage section; and (c-2) supplying the second raw material stored in the second storage section to the substrate.

7. The substrate processing method as described in claim 1, wherein, In (b), the following steps are performed: (b-1) storing the first raw material in the first storage section; and (b-2) supplying the first raw material stored in the first storage section to the substrate; In (c), the following steps are performed: (c-1) storing the second raw material in the second storage section; and (c-2) supplying the second raw material stored in the second storage section to the substrate.

8. The substrate processing method as described in claim 1, wherein, The first raw material mentioned above and the second raw material mentioned above are the same materials.

9. The substrate processing method as described in claim 1, wherein, The first raw material mentioned above and the second raw material mentioned above are different materials.

10. The substrate processing method as described in claim 1, wherein, In (a), the inhibitor is adsorbed onto the opening side of the recess more preferentially than onto the deep side of the recess.

11. The substrate processing method as described in claim 1, wherein, Perform at least one of the following steps: In (a-1), supply the first inhibitor to the substrate via a first supply section having a first supply hole, the first supply hole being a gas supply hole configured to supply internal gas toward the substrate; and in (b), supply the first material to the substrate via the first supply section; and in (a-2), supply the second inhibitor to the substrate via a second supply section having a second supply hole, the second supply hole being a gas supply hole; and in (c), supply the second material to the substrate via the second supply section.

12. The substrate processing method as described in claim 7, wherein, The amount of the first raw material stored in the first storage section in (b-1) is different from the amount of the second raw material stored in the second storage section in (c-1).

13. The substrate processing method as described in claim 1, wherein, (a) comprises (a-1) and (a-2) such that the amount of the first inhibitor supplied to the substrate in (a-1) is different from the amount of the second inhibitor supplied to the substrate in (a-2).

14. The substrate processing method as described in claim 1, wherein, The first raw material and the second raw material mentioned above each contain atoms of a predetermined element, namely aluminum, silicon, titanium, hafnium, zirconium, tantalum, molybdenum, or tungsten, in their molecules. The number of the predetermined atoms contained in the molecules of the first raw material and the second raw material mentioned above are different.

15. The substrate processing method as described in claim 1, wherein, The first inhibitor and the second inhibitor mentioned above are the same gas.

16. The substrate processing method as described in claim 1, wherein, The first inhibitor mentioned above and the second inhibitor mentioned above are different gases.

17. A method for manufacturing a semiconductor device, comprising performing a predetermined number of cycles including the following steps to form a film on a substrate having recesses formed on its surface: (a) a step of supplying an inhibitor to the substrate; (b) a step of supplying a first raw material to the substrate from a first storage unit; (c) a step of supplying a second raw material to the substrate from a second storage unit; and (d) a step of supplying a reactant to the substrate after (a), (b), and (c); (a) comprising at least one of the following steps: (a-1) a step of supplying a first inhibitor as the inhibitor to the substrate before (b); and (a-2) a step of supplying a second inhibitor as the inhibitor to the substrate before (c).

18. A program for executing a program by a computer on a substrate processing apparatus, wherein a film is formed on a substrate having recesses on its surface by performing a predetermined number of cycles comprising the following processes: (a) a process of supplying an inhibitor to the substrate; (b) a process of supplying a first material to the substrate from a first storage unit; (c) a process of supplying a second material to the substrate from a second storage unit; and (d) a process of supplying a reactant to the substrate after (a), (b), and (c); wherein (a) comprises at least one of the following processes: (a-1) a process of supplying a first inhibitor as the inhibitor to the substrate before (b); and (a-2) a process of supplying a second inhibitor as the inhibitor to the substrate before (c).

19. A substrate processing apparatus comprising: a first supply system for supplying an inhibitor to a substrate having recesses formed on its surface; a first material supply system having a first storage unit for supplying a first material to the substrate; a second material supply system having a second storage unit for supplying a second material to the substrate; a reactant supply system for supplying a reactant to the substrate; and a control unit configured to enable the first supply system, the first material supply system, the second material supply system, and the reactant supply system to perform a cycle comprising the following processes a predetermined number of times to form a film on the substrate: (a) a process of supplying the inhibitor to the substrate; (b) a process of supplying the first material to the substrate; (c) a process of supplying the second material to the substrate; and (d) a process of supplying the reactant to the substrate after (a), (b), and (c); (a) comprising at least one of the following processes: (a-1) prior to (b), the substrate is supplied with a treatment as a first inhibitor of the inhibitor; and (a-2) prior to (c), the substrate is supplied with a treatment as a second inhibitor of the inhibitor.

20. A gas supply system comprising: a first supply system for supplying an inhibitor to a substrate having recesses formed on its surface; a first material supply system having a first storage unit for supplying a first material to the substrate; a second material supply system having a second storage unit for supplying a second material to the substrate; and a reactant supply system for supplying a reactant to the substrate; wherein the system is controlled to perform a cycle comprising the following processes a predetermined number of times to form a film on the substrate: (a) a process of supplying the inhibitor to the substrate; (b) a process of supplying the first material to the substrate; (c) a process of supplying the second material to the substrate; and (d) a process of supplying the reactant to the substrate after (a), (b), and (c); wherein (a) comprises at least one of the following processes: (a-1) a process of supplying the first inhibitor as the inhibitor to the substrate before (b); and (a-2) a process of supplying the second inhibitor as the inhibitor to the substrate before (c).

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