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

Abstract

According to the present invention, a film containing silicon and oxygen is formed on a substrate by performing a cycle a predetermined number of times, the cycle including: (a) a step for supplying a compound to the substrate, each molecule of the compound containing a silicon atom and an amino group bonded to the silicon atom, and containing an alkoxy group bonded to the silicon atom and / or a siloxane bond having the silicon atom; and (b) a step for supplying an excited reactant to the substrate, the reactant containing hydrogen or deuterium and not containing oxygen.

Description

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

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

[0002] As one step in the manufacturing process of a semiconductor device, a process of supplying raw materials to a substrate and supplying an oxidizing agent to the substrate are sometimes performed alternately to form an oxygen-containing film on the substrate (see, for example, Japanese Patent Application Publication No. 2021-039970).

[0003] This disclosure aims to improve the properties of oxygen-containing films formed on a substrate.

[0004] According to one aspect of the present disclosure, a technique is provided for forming a film containing silicon and oxygen on a substrate by performing a predetermined number of cycles comprising: (a) supplying a compound to a substrate, which contains a silicon atom and an amino group bonded to the silicon atom in one molecule, and also contains at least one of an alkoxy group bonded to the silicon atom and a siloxane bond having the silicon atom; and (b) supplying an excited reactant containing hydrogen or deuterium and free of oxygen to the substrate.

[0005] This disclosure makes it possible to provide a technology that can improve the properties of oxygen-containing films formed on a substrate.

[0006] 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, showing the processing furnace 202 portion in a vertical cross-sectional view. 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, showing the processing furnace 202 portion in a cross-sectional view along line A-A in Figure 1. Figure 3 is a schematic diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present disclosure, showing the control system of the controller 121 in a block diagram. Figure 4 is a schematic diagram showing the gas supply sequence in one embodiment of the present disclosure. Figure 5a is a schematic diagram showing the surface state of the substrate before starting the film deposition step. Figure 5b is a schematic diagram showing the surface state of the substrate after performing step 1. Figure 5c is a schematic diagram showing the surface state of the substrate after performing step 2.

[0007] <An Embodiment of the Disclosure> An embodiment of the disclosure will be described below, mainly with reference to Figures 1 to 3. Note that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements do not necessarily correspond between multiple drawings. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of that process is achieved. In this disclosure, numerical ranges indicated using "~" indicate a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages.

[0008] (1) As shown in the configuration diagram 1 of the substrate processing apparatus, the processing furnace 202 has a heater 207 as a temperature regulator (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 (thermal excitation unit) that activates (excites) the gas with heat.

[0009] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO₂ ２ The reaction tube 203 is made of a heat-resistant material such as ), 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 and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 is engaged 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 part of the processing vessel. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed inside this processing chamber 201, that is, inside this processing vessel.

[0010] Within the processing chamber 201, nozzles 249a and 249b, which serve as the first and second supply units, are provided so as to penetrate the side walls of the manifold 209. Nozzles 249a and 249b are also referred to as the first nozzle and the second nozzle, respectively. Nozzles 249a and 249b are each configured as common nozzles used for supplying multiple types of gases.

[0011] Nozzle 249a is connected to gas supply pipes 232a and 232c. Nozzle 249b is connected to gas supply pipe 232b. Gas supply pipes 232a, 232b, and 232c are each configured as shared piping used for supplying multiple types of gas. Gas supply pipes 232a, 232b, and 232c are provided, in order from the upstream side of the gas flow, with flow controllers (flow control units) such as mass flow controllers (MFCs) 241a, MFC241b, and MFC231c, and on-off valves such as valves 243a, 243b, and 243c, respectively.

[0012] As shown in Figure 2, nozzles 249a and 249b are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, extending from the lower to the upper part of the inner wall of the reaction tube 203, rising upward in the direction of wafer 200 arrangement. That is, nozzles 249a and 249b are provided in a region horizontally surrounding the wafer arrangement region, on the side of the wafer arrangement region where the wafers 200 are arranged, and are provided along the wafer arrangement region. Gas supply holes 250a and 250b are provided on the sides of nozzles 249a and 249b, respectively, for supplying gas. Gas supply holes 250a and 250b each open toward the center of the wafer 200 in plan view, making it possible to supply gas toward the wafer 200. Multiple gas supply holes 250a and 250b are provided extending from the lower to the upper part of the reaction tube 203. In Figure 2, the rest of the configuration is the same as that of the substrate processing apparatus shown in Figure 1. Elements that are substantially the same as those described in Figure 1 are given the same reference numerals, and their descriptions are omitted.

[0013] From the gas supply pipe 232a, the raw material gas is supplied into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a. The compound described later is a raw material for forming a film (SiO film) containing silicon (Si) and oxygen (O). The raw material gas containing the raw material is supplied into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a. The raw material gas refers to a raw material in a gaseous state, for example, a gas obtained by vaporizing or sublimating a raw material that is in a liquid or solid state at room temperature and pressure, or a gas that is in a gaseous state at room temperature and pressure. The raw material gas supply system, which is the raw material supply system, is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a.

[0014] From the gas supply pipe 232b, the reactant gas is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, the gas supply pipe 232b, and the nozzle 249b. The reactant gas is a gas of a reactant that contains hydrogen (H) or deuterium (D) and does not contain O. The reactant gas is, for example, a hydrogen-containing gas (H-containing gas) or a deuterium-containing gas (D-containing gas). Mainly, the MFC 241b, the valve 243b, the gas supply pipe 232b, the nozzle 249b, and a plasma excitation part as an excitation part described later constitute a reactant gas supply system which is a reactant supply system. That is, the reactant supply system is configured to supply the plasma-excited reactant gas to the wafer 200 arranged in the processing chamber 201. A gas supply system including the MFC 241b, the valve 243b, the gas supply pipe 232b, and the nozzle 249 that does not include an excitation part can also be regarded as the reactant gas supply system.

[0015] Among the above various gas supply systems, any one or all of the gas supply systems may be configured as an integrated gas supply system 248 in which the valves 243a, 243b, 243c and the MFCs 241a, 241b, 241c are integrated. The integrated gas supply system 248 is connected to each of the gas supply pipes 232a, 232b, 232c, and the supply operation of various gases into the gas supply pipes 232a, 232b, 232c, that is, the opening and closing operations of the valves 243a, 243b, 243c, the flow rate adjustment operations by the MFCs 241a, 241b, 241c, etc. are configured to be controlled by a controller 121 described later.

[0016] 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 and 249b (gas supply holes 250a and 250b) with the wafer 200 in between, in a plan view. The exhaust port 231a may 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 is configured to allow for vacuum evacuation and stopping of vacuum evacuation in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. 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.

[0017] Below the manifold 209, a seal cap 219 is provided, which serves as a furnace opening cover capable of airtightly closing the lower end opening of the manifold 209. An O-ring 220b is provided on the upper surface of the seal cap 219, which serves as a sealing member that contacts the lower end of the manifold 209. Below the seal cap 219, a rotating mechanism 267 is installed for rotating the boat 217, which will be described later. 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 a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that moves the wafer 200 in and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0018] Below the manifold 209, a shutter 219s is provided as a furnace port lid that can airtightly close the lower end opening of the manifold 209 in a state where the seal cap 219 is lowered and the boat 217 is carried out from the processing chamber 201. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that abuts against the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotation operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0019] The boat 217, which is a support for supporting the substrate, is configured to support a plurality of wafers 200 in a multi-stage manner by aligning them vertically in a horizontal posture and with their centers aligned with each other. That is, the boat 217 is configured to arrange a plurality of wafers 200 in a horizontal posture and at intervals in the vertical direction. The boat 217 is made of a heat-resistant material such as quartz, for example. Below the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz, for example, are supported in multiple stages.

[0020] A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0021] Outside the reaction tube 203, that is, outside the processing container (processing chamber 201), an electrode 300 for plasma generation is provided. By applying power to the electrode 300, it is possible to plasmaize and excite the gas inside the reaction tube 203, that is, inside the processing container (processing chamber 201), that is, to excite the reaction gas supplied into the processing chamber 201 into a plasma state. Hereinafter, exciting the gas into a plasma state is also simply referred to as plasma excitation. The electrode 300 is configured to generate a capacitively coupled plasma (abbreviation: CCP) inside the reaction tube 203, that is, inside the processing container (processing chamber 201), when power, that is, high-frequency power (RF power), is applied.

[0022] Specifically, as shown in Figure 2, a plurality of electrodes 300 and an electrode fixing device 301 for fixing the plurality of electrodes 300 are arranged between the heater 207 and the reaction tube 203. The electrode fixing device 301 is arranged inside the heater 207, the electrodes 300 are arranged inside the electrode fixing device 301, and the reaction tube 203 is arranged inside the electrodes 300.

[0023] Furthermore, as shown in Figures 1 and 2, the electrode 300 and electrode fixing device 301 are provided in an annular space in plan view between the inner wall of the heater 207 and the outer wall of the reaction tube 203, extending along the upper part of the outer wall of the reaction tube 203 from the lower part, in the direction of wafer 200 arrangement. The electrode 300 is provided parallel to the nozzles 249a and 249b.

[0024] As shown in Figure 2, the electrode 300 includes a first electrode 300a and a second electrode 300b. The first electrode 300a is connected to a high-frequency power supply (RF power supply) 320 via a matching unit 305. The second electrode 300b is grounded and at a reference potential (0V). The first electrode 300a is also referred to as the Hot electrode, and the second electrode 300b is also referred to as the Ground electrode. At least one first electrode 300a is provided, and at least one second electrode 300b is provided. Figure 2 shows an example in which multiple first electrodes 300a and second electrodes 300b are provided. By applying RF power from the RF power supply 320 via the matching unit 305 between the first electrode 300a and the second electrode 300b, plasma is generated in the region between the first electrode 300a and the second electrode 300b. This region is also referred to as the plasma generation region.

[0025] The plasma excitation section, which primarily consists of electrodes 300, a matching unit 305, and a high-frequency power supply 320, is configured as an excitation section for exciting the reactant gas. Electrodes 300 can also be considered as the plasma excitation section itself.

[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, a control program that controls the operation of the substrate processing device, a process recipe that describes the procedures and conditions for the processing described later, etc. The process recipe is a combination of steps in the processing described later that the controller 121 causes the substrate processing device to execute and obtain a predetermined result, and functions as a program. Hereinafter, the process recipe and control program etc. will be collectively referred to simply as "program." Similarly, the process recipe will be simply referred to as "recipe." In this disclosure, the term "program" may include only the recipe, only the control program, 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. The program, which is one embodiment of this disclosure, is also applicable to program products.

[0028] The I / O port 121d is connected to the aforementioned MFCs 241a and 241b, valves 243a and 243b, 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, RF power supply 320, matching unit 305, etc., enabling data input and output with these connected devices.

[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 gases by the MFCs 241a, 241b, and 241c, the opening and closing operation of valves 243a, 243b, and 243c, 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, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, the impedance adjustment operation of the matching unit 305, and the power supply to the RF power supply 320, etc., in accordance with the contents of the read recipe.

[0030] The controller 121 can be configured by installing the above-mentioned program 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, 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 disclosure, the term recording media may include only the storage device 121c, only the external storage device 123, or both. Note that the provision of programs to computers may be performed using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] The control unit is configured as described above and controls the raw material gas supply system and the reactant gas supply system to perform a process in which a film containing Si and O is formed on the substrate by performing a predetermined number of cycles including (A) a process of supplying the above compound to the substrate and (B) a process of supplying the excited reactant to the substrate.

[0032] (2) Substrate Processing Process An example of a substrate processing sequence in which an oxygen-containing film (oxide film) is formed on a wafer 200 as a substrate, using the substrate processing apparatus described above, as one step in the substrate processing process and as one step in the semiconductor device manufacturing process, will be explained mainly with reference to Figures 4 and 5(a) to 5(c). In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0033] (Raw Material Gas) The raw material gas used in the process will now be described. The raw material gas contains a compound in which one molecule contains a Si atom and an amino group bonded to the Si atom, and also contains at least one of the following: an alkoxy group bonded to the Si atom and a siloxane bond having the Si atom (i.e., a siloxane bond composed of the Si atom). The above compound is supplied to the substrate as a raw material gas.

[0034] An amino group is ammonia (NH ３ ), or a structure obtained by removing hydrogen (H) from either a primary amine or a secondary amine. An alkoxy group is a monovalent functional group in which an alkyl group (R) is bonded to an oxygen (O) atom, and is represented by the structural formula -OR. A siloxane bond is a bond containing an Si atom and an O atom, represented by Si-O-Si.

[0035] The compound contains a Si atom and an amino group bonded to this Si atom in one molecule. Furthermore, the compound contains at least one of the following: an alkoxy group bonded to this Si atom, and a siloxane bond having this Si atom. In the compound, there may be one or more amino groups, alkoxy groups, or siloxane bonds in one molecule. The compound containing an alkoxy group is also called compound A, and the compound containing a siloxane bond is also called compound B. The compound contains at least one of compound A and compound B. By using the above compound, it is possible to improve the properties of the oxygen-containing film formed on the substrate.

[0036] Compound A - Compound A preferably contains an alkoxy group bonded to a Si atom in one molecule. The Si atom is a Si atom bonded to an amino group. Compound A contains a Si atom, an amino group bonded to this Si atom, and an alkoxy group bonded to this Si atom in one molecule. There may be one or more amino groups or alkoxy groups. Compound A may also contain other ligands bonded to this Si atom that are neither an amino group nor an alkoxy group (for example, H or an organic group).

[0037] Here, when compound A is adsorbed onto the surface of wafer 200, the amino group bonded to the Si atom is detached, reducing the incorporation of carbon (C) and nitrogen (N) derived from the amino group into the film. In addition, the alkoxy group bonded to the Si atom adsorbed on the surface of wafer 200 reacts with an excited, hydrogen (H)-containing reactant, causing its O-C bond to be broken. At this time, the carbon contained in the alkoxy group is detached, thus reducing the incorporation of carbon derived from the alkoxy group into the film.

[0038] Compound A is more preferably composed of a single amino group bonded to a Si atom. That is, it is more preferable that compound A has one amino group bonded to a Si atom per molecule. It is more preferable that compound A does not contain a siloxane bond per molecule. By compound A not containing a siloxane bond per molecule, the incorporation of carbon bonded to a siloxane bond into the membrane can be suppressed, and the addition of carbon to the membrane can be suppressed.

[0039] Compound A more preferably contains one amino group bonded to a Si atom and three alkoxy groups bonded to this Si atom in one molecule. In this case, compound A contains one Si atom. In this case, the ratio of the number of amino groups to the number of alkoxy groups in one molecule of compound A is 1:3. In this case, the single amino group bonded to the Si atom is detached when adsorbed onto the surface of wafer 200, further suppressing the incorporation of C and N into the film derived from the amino group, and enabling the formation of a film that is substantially free of C and N. Furthermore, the film deposition rate can be increased. Note that "substantially free of C and N" includes cases where C and N are present in amounts at impurity levels.

[0040] Compound A is more preferably free of alkyl groups bonded to Si atoms in a single molecule. This allows for the suppression of the amount of C added to the film, or the formation of a film that is substantially free of C. Compound A is also preferably free of C atoms bonded to Si atoms. This allows for a further reduction in the concentration of C in the film.

[0041] The alkoxy groups mentioned above specifically include methoxy groups, ethoxy groups, n-propoxy groups, n-butoxy groups, and the like. The alkoxy groups may be not only these linear alkoxy groups, but also branched alkoxy groups such as isopropoxy groups, isobutoxy groups, secondary butoxy groups, and tertiary butoxy groups. The alkoxy groups may also be cyclic, such as phenoxides. Furthermore, the alkyl groups mentioned above include methyl groups, ethyl groups, n-propyl groups, and n-butyl groups. The alkyl groups may be not only these linear alkyl groups, but also branched alkyl groups such as isopropyl groups, isobutyl groups, secondary butyl groups, and tertiary butyl groups. The alkoxy group is preferably a methoxy group (-OMe).

[0042] Specifically, the amino group mentioned above is -NH ２It contains a monovalent functional group represented by any of the structural formulas of -NHR, and -NRR'. However, R or R' is an alkyl group including a methyl group, an ethyl group, a propyl group, a butyl group, etc. R or R' may be not only these linear alkyl groups but also branched alkyl groups such as an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, etc. R and R' are preferably methyl groups.

[0043] Compound A is preferably a compound represented by the following general formula (1).

[0044]

[0045] In general formula (1), R １ , R ２ , and R ３ each independently represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched. A plurality of R １ , R ２ , and R ３ may be the same or different from each other. R 4 and R ５ each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched. R 4 and R ５ may be the same or different. A plurality of R １ , R ２ , R ３ , R 4 , and R ５ may be the same or different from each other. Compound A is more preferably such that R １ , R ２ , R ３ , R 0000022, and R ５ are all methyl groups.

[0046] - Compound B - Compound B preferably contains a siloxane bond having a Si atom bonded to an amino group in one molecule. By containing a siloxane bond in one molecule of Compound B, the film formation rate can be improved. In addition, C or N can be added to the film. Compound B contains a Si atom, an amino group bonded to this Si atom, and a siloxane bond having this Si atom in one molecule. Compound B may contain one or more Si atoms, amino groups, and siloxane bonds. Compound B may also contain other ligands (e.g., H or organic groups) bonded to the Si atom constituting the siloxane bond, other than the siloxane bond and the amino group bonded to this siloxane bond.

[0047] Compound B is more preferably composed of a single amino group bonded to a Si atom within one molecule. In other words, it is more preferable that compound B has one amino group bonded to a Si atom within one molecule. This allows for a reduction in the amount of C and N added to the film.

[0048] Compound B preferably contains an alkyl group bonded to a Si atom in one molecule. This allows for the addition of C to the film, and if the amino group remains in the film without detaching from the Si atom, the amount of C added to the film can be further increased. Compound B preferably has a single amino group, an alkyl group, and O contained in the siloxane bond bonded to one Si atom. Compound B may contain one or more alkyl groups or siloxane bonds in one molecule. In this case, C can be added to the film, and if the amino group remains, the amount of C added can be further increased, and C and N can also be added to the film.

[0049] In compound B, it is preferable that the siloxane bond containing Si atoms constitutes a cyclic siloxane structure. This increases the number of Si and O atoms in the molecule, thereby improving the film deposition rate.

[0050] In compound B, it is preferable that the siloxane bond having a Si atom constitutes a linear siloxane structure. This allows for an increase in the number of Si and O atoms contained in the molecule, thereby improving the film formation rate. Compound B is an amino group-containing oligosiloxane compound having an amino group and a siloxane bond. In compound B, it is preferable that there are one to three siloxane bonds bonded to the Si atom. In compound B, it is preferable that the number of O atoms forming the siloxane bond is one to four.

[0051] Compound B is preferably a compound represented by the following general formula (2), general formula (3), or general formula (4).

[0052]

[0053]

[0054]

[0055] In general formulas (2), (3), and (4), R １１ Each of these is independently selected from the group consisting of hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, an alkynyl group having 3 to 10 carbon atoms, and an aryl group having 4 to 10 carbon atoms. １１ and R １２ They may be the same or different. １１ and R １２ They may or may not form a ring by bonding. １３ ~R １９Each of these is independently selected from the group consisting of hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and an aryl group having 4 to 10 carbon atoms. X is selected from the group consisting of hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, a carboxylate group having 2 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a trimethylsiloxy group, a dimethylsiloxy group, a methylsiloxy group, and a siloxy group.

[0056] In general formulas (2), (3), and (4), specific examples of linear alkyl groups and branched alkyl groups are the same as in the example in compound A. Examples of cyclic alkyl groups include cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. As for aryl groups, aromatic cyclic functional groups include phenyl group, benzyl group, chlorobenzyl group, tolyl group, o-xylyl group, 1,2,3-triazolyl group, pyrrolyl group, and furanyl group. As for alkoxy groups, -OR １１ Meaning, R １１ Specific examples are the same as those described above. Specific examples of alkoxy groups are the same as those in compound A. As for carboxylates, -OC(=O)R １１ Meaning, R １１ Specific examples are the same as those described above. Examples of carboxylates include acetate (-OC(=O)Me), ethyl carboxylate (-OC(=O)Et), isopropyl carboxylate (-OC(=O)iPr), and benzoate (-OC(=O)Ph).

[0057] Compound B is preferably, specifically, one of the following compounds. 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6,8,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,3,3,5,5,7,7,7-octamethyltetrasiloxane

[0058] It is preferable that compounds A and B do not contain halogen elements in each molecule. This helps to suppress the deterioration of film quality due to the residual halogen elements in the film.

[0059] (H-containing gas) The reactant used in the process will now be described. The reactant contains at least one of hydrogen (H) and deuterium (D), and does not contain oxygen (O). Here, "O-free" may include cases where O is present at an impurity level. In this embodiment, the reactant is supplied to the substrate as a gas containing at least one of H and D (hereinafter sometimes simply referred to as H-containing gas).

[0060] The reactants are hydrogen gas (H ２ gas) and deuterium gas (D ２ It is preferable that the gas contains at least one of the following. This allows excited H to be supplied compared to when an O-containing gas or its activated form is supplied. ２Hydrogen-active species (H) are activated (excited) H contained in the gas. ＊ ) and activated D ２ Deuterium-active species (D), which are activated D contained in the gas. ＊ This promotes the removal of impurities from the film, thereby improving and maximizing film quality such as the wet etching rate (WER). Furthermore, when forming a film containing at least one of C and N, the removal of C and N by O can be suppressed.

[0061] It is preferable that the reactant does not contain nitrogen. This makes it possible to suppress the addition of nitrogen to the membrane. Therefore, for example, a high-quality oxygen-containing membrane that does not contain nitrogen can be obtained.

[0062] The reactants are preferably excited by plasma. This allows for a sufficient amount of H under low-temperature conditions. ＊ Ya D ＊ This can supply the excited reactants, which contain active species. Furthermore, if permissible under the temperature conditions, thermal excitation may be applied. Because the reactants are excited by plasma, high-quality oxygen-containing films can be obtained at low temperatures.

[0063] (Substrate Processing Sequence) In the substrate processing sequence in this embodiment, a gas containing at least one of compound A and compound B as a raw material (hereinafter sometimes simply referred to as raw material gas) is supplied to the wafer 200 to form a first layer containing Si and O on the wafer 200 (a) and a gas containing at least one of H and D as a reactant (i.e., H-containing gas) is supplied to the wafer 200 in a plasma-excited state to modify the first layer and form a second layer containing Si (b) The cycle including the above steps is performed a predetermined number of times (n times, n is an integer of 1 or more) to form an oxygen-containing film containing Si, i.e., a film containing at least Si and O (SiO film, SiOC film, SiOCN film, etc.) on the wafer 200. The cycle including steps (a) and (b) is performed non-simultaneously.

[0064] In this disclosure, the gas supply sequence shown in Figure 4 may also be shown as follows for convenience. The same notation will be used in the following descriptions of variations and other embodiments.

[0065] (Raw material → Plasma-excited H-containing gas) × n ⇒ SiO, SiOC, or SiOCN

[0066] In this disclosure, 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 disclosure, the term "surface of a wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this disclosure, the phrase "form a predetermined layer on a wafer" may refer to directly forming a predetermined layer on the surface of the wafer itself or to forming a predetermined layer on top of a layer formed on the wafer. In this disclosure, the term "substrate" has the same meaning as the term "wafer."

[0067] (Wafer charging, boat loading) When multiple wafers 200 are loaded into the boat 217 (wafer charging), the shutter 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter open). 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.

[0068] (Pressure and Temperature Adjustment Step) The processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that it reaches the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on this measured pressure information (pressure adjustment). The wafer 200 inside the processing chamber 201 is also heated by the heater 207 so that it reaches the desired temperature. At this time, the amount of power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has the desired temperature distribution (temperature adjustment). The boat 217 and the wafer 200 are also rotated by the rotation mechanism 267. The operation of the vacuum pump 246, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0069] As shown in Figure 5(a), the surface of wafer 200 is terminated by hydroxyl groups (-OH) (OH termination). The OH terminations present on the surface of wafer 200 function as adsorption sites for molecules and atoms.

[0070] (Film formation process) Then, the following steps (a) and (b) are carried out in order.

[0071] [Step (a)] In this step, a raw material gas is supplied to the wafer 200 in the processing chamber 201 (raw material gas supply). Specifically, valve 243a is opened and the raw material gas flows into the gas supply pipe 232a. The flow rate of the raw material gas is adjusted by MFC 241a and supplied into the processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this time, compound A gas is supplied to the wafer 200. At this time, valve 243c may be opened and an inert gas supplied into the processing chamber 201 via nozzle 249a.

[0072] <When compound A is used as a raw material> When compound A is used as a raw material, by performing this step under the processing conditions described later, it becomes possible to remove the amino group from the Si atom contained in the gas of compound A without removing the alkoxy group. Furthermore, it becomes possible to adsorb (chemiadsorb) the Si atom, in a state where the amino group has been removed but the bond with the alkoxy group is maintained, onto the surface of wafer 200. That is, it becomes possible to adsorb the Si atom onto a part of the adsorption site (e.g., OH termination) on the surface of wafer 200 with the alkoxy group bonded to three of the four bonds of the Si atom. This is because the bond energy EO between the alkoxy group and the Si atom is higher than the bond energy EA between the amino group and the Si atom. In other words, the amino group is more likely to cause a substitution reaction with the terminations (especially the OH termination) on the surface of wafer 200 compared to the alkoxy group, and has active properties that make it easier to detach from the Si atom of compound A during adsorption to the surface. In this way, it becomes possible to form a first layer containing a component in which an alkoxy group is bonded to a Si atom on the outermost surface of wafer 200.

[0073] Furthermore, by performing this step under the processing conditions described later, it becomes possible to prevent the amino groups detached from the Si atoms contained in the gas of compound A from being re-adsorbed onto the surface of the wafer 200. As a result, it becomes possible to prevent the first layer formed on the wafer 200 from containing C and N derived from the amino groups detached from the Si contained in the gas of compound A.

[0074] In this step, the three bonds of the Si atoms adsorbed on the surface of the wafer 200 are filled with alkoxy groups, thereby inhibiting the adsorption of other atoms or molecules to the Si atoms adsorbed on the surface of the wafer 200. Furthermore, in this step, the alkoxy groups bonded to the Si atoms adsorbed on the surface of the wafer 200 act as steric hindrances, thereby inhibiting the adsorption of other atoms or molecules to adsorption sites (e.g., OH terminations) on the surface of the wafer 200 surrounding the Si atoms adsorbed on the surface of the wafer 200.

[0075] In this step, it is preferable to continue supplying the gas of compound A until the adsorption reaction of Si atoms to the surface of wafer 200 (chemiadsorption reaction) is saturated. Even if the supply of the gas of compound A is continued in this manner, the methoxy groups bonded to Si act as steric hindrance, making it possible to adsorb Si atoms discontinuously onto the surface of wafer 200. Specifically, it becomes possible to adsorb Si atoms onto the surface of wafer 200 to a thickness of less than one atomic layer.

[0076] As shown in Figure 5(b), when the adsorption reaction of Si atoms to the surface of the wafer 200 is saturated, the surface of the wafer 200 becomes covered with alkoxy groups (-OR) bonded to the Si atoms. Amino groups (NR ２ ) is eliminated. Note that R represents hydrogen or an organic group.

[0077] <When compound B is used as a raw material> When compound B is used as a raw material, by performing this step under the processing conditions described later, the siloxane bonds contained in the gas of compound B will not decompose (be cleaved), and the Si atoms constituting the siloxane bonds will be adsorbed onto a portion of the adsorption sites (e.g., OH terminations) on the surface of wafer 200. Here, the adsorption of Si atoms onto the surface of wafer 200 occurs, for example, when an amino group attached to a Si atom is detached, and that Si atom is adsorbed (substitution reaction) onto an OH termination, which is an adsorption site on the surface of wafer 200.

[0078] Furthermore, as will be described later, when compound B is used as a raw material, Si dangling bonds (unbonded bonds) and organic group terminations (e.g., hydrocarbon group terminations such as alkyl groups) may be formed on the surface of the wafer 200 after step (b). In this case, the amino group bonded to the Si atom does not detach, and the ligands (e.g., H or organic groups) bonded to the Si atom constituting the siloxane bond react with these Si dangling bonds and organic group terminations, so that a siloxane bond in which the bond with the amino group is maintained is adsorbed on the surface of the wafer 200.

[0079] Therefore, when compound B is used as a raw material, in this step it is possible to form a first layer on the outermost surface of the wafer 200 that includes siloxane bonds and amino groups whose bonds with the siloxane bonds are maintained. In other words, the first layer formed on the wafer 200 can be a layer that includes C derived from siloxane bonds and C and N derived from amino groups.

[0080] Even when compound B is used as a raw material, it is preferable to continue supplying the compound B gas in this step until the adsorption reaction of Si atoms to the surface of the wafer 200 is saturated, similar to when compound A is used.

[0081] After the first layer is formed, valve 243a is closed to stop the supply of raw material gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove any remaining gases (purging). At this time, valve 243c for the inert gas is opened, and the inert gas is supplied into the processing chamber 201 via nozzle 249a. The inert gas acts as a purging gas.

[0082] As an inert gas, N ２ Gases, or noble gases such as Ar gas, He gas, Ne gas, and Xe gas, can be used. This also applies to step (b) described later.

[0083] [Step b] After step a is completed, an excited reactant, an excited H-containing gas in a plasma state, is supplied to the wafer 200 in the processing chamber 201, i.e., the first layer formed on the wafer 200. The plasma-excited H-containing gas contains H-active species (H ＊ ) and D active species (D ＊) contains at least one of the following. Specifically, valve 243b is opened and H-containing gas flows into the gas supply pipe 232b. The H-containing gas is flow-controlled by MFC 241b and supplied into the processing chamber 201 via nozzle 249b and exhausted from exhaust port 231a. At this time, H-containing gas is supplied to the wafer 200. At this time, valve 243c may be opened and an inert gas supplied into the processing chamber 201 via nozzle 249a. However, in this step, especially when compound A is used as a raw material, the inert gas is N-containing gas. ２ It is preferable not to supply the gas. By not supplying the N-containing gas, the incorporation of N into the second layer formed in this step is suppressed, and an oxygen-containing film with a lower N concentration can be formed.

[0084] At this time, by applying RF power between the first electrode 300a and the second electrode 300b, plasma is generated in the region between the two electrodes. As a result, the H-containing gas is excited into the plasma state, and H * Ya D * Active species such as H are generated and supplied to the wafer 200 (plasma-excited H-containing gas supply). At this time, H * Ya D * A hydrogen-containing gas containing active species such as these will be supplied.

[0085] <When compound A is used as a raw material> When compound A is used as a raw material in step (a), by performing this step under the processing conditions described later, it becomes possible to detach the organic group (R) contained in the alkoxy group that is bonded to the Si atom contained in the first layer from the first layer. At this time, at least a portion of the O atoms constituting the alkoxy group remain bonded to the Si atom without being detached. Then, at least a portion of the first layer formed on the wafer 200 is modified in this way, and a silicon oxide layer (SiO layer), which is a layer containing Si and O, can be formed as the second layer. As shown in Figure 5(c), the second layer is a layer that does not contain the organic group that was contained in the alkoxy group, that is, a layer that does not contain impurities such as C.

[0086] Furthermore, when compound A is used, which contains at least one organic group bonded to a Si atom that is neither an alkoxy group nor an amino group, the organic group bonded to the Si atom may remain without being detached during this step. In this case, a silicon carbonate layer (SiOC layer) can be formed as the second layer, which contains Si, O, and C (where C originates from the remaining organic group).

[0087] Furthermore, the surface of the second layer becomes OH-terminated as a result of the modification treatment with excited H-containing gas. This allows the amino groups contained in compound A supplied to wafer 200 in step (a) of the next cycle to react with the OH-terminated surface of wafer 200, thereby promoting the desorption of amino groups contained in compound A and promoting the adsorption of Si atoms, thereby increasing the film deposition rate. Note that impurities such as C desorbed from the first layer are carbon dioxide (CO2). ２ These gaseous substances, such as those listed above, are discharged from within the processing chamber 201.

[0088] <When compound B is used as a raw material> When compound B is used as a raw material in step (a), by performing this step under the processing conditions described later, it becomes possible to detach at least one of the H and organic groups that are bonded to the Si atoms constituting the siloxane bond in the first layer from the first layer. At this time, at least a portion of the O atoms constituting the siloxane bond remain bonded to the Si atoms without being detached. Also, if an amino group is bonded to the siloxane bond in the first layer, at least a portion of the amino group remains bonded to the siloxane bond without being detached in this step.

[0089] Then, by modifying at least a portion of the first layer formed on the wafer 200 in this way, a silicon oxide layer (SiO layer), which contains Si and O, can be formed as a second layer. Furthermore, if an amino group is bonded to the siloxane bond in the first layer, a silicon carbonate nitride layer (SiOCN layer), which contains Si, O, C, and N, can be formed as a second layer. The N in the SiOCN layer mainly originates from the amino group. In addition to the C originating from the amino group, the C in the SiOCN layer may also include organic groups that were bonded to the siloxane bond in the first layer (those that remained without being removed in this step).

[0090] Furthermore, as a result of the reforming treatment with excited H-containing gas, Si dangling bonds and organic group terminations may be formed on the surface of the second layer in addition to OH terminations. This is because, for example, compared to the case where an O-C bond constituting an alkoxy group is cleaved to form an OH termination, the H supplied in this step ＊ This is thought to be because OH bonds are less likely to form between these atoms and the O atoms that constitute the siloxane bond, making it easier for Si-H bonds to be broken and Si-C bonds to be maintained.

[0091] After the second layer is formed, the supply of RF power to the electrode 300 is stopped, and the valve 243b is closed to stop the supply of H-containing gas into the processing chamber 201. The supply of H-containing gas may be stopped after a predetermined time has elapsed since the RF power supply was stopped. Then, any gas remaining in the processing chamber 201 is removed from the processing chamber 201 using a processing procedure similar to the purging in step A (purging).

[0092] [Performed a predetermined number of times] By performing steps (a) and (b) described above non-simultaneously, i.e., without synchronization, a predetermined number of times (n times, where n is an integer of 1 or more), it becomes possible to form a film of a predetermined composition and predetermined thickness on the wafer 200. Specifically, if the second layer is an SiO layer, an SiO film can be formed; if the second layer is an SiOC layer, an SiOC film can be formed; and if the second layer is an SiOCN layer, an SiOCN film can be formed. It is preferable to repeat the above cycle multiple times. That is, it is preferable to make the thickness of the second layer formed by performing the above cycle once smaller than the desired thickness, and to repeat the above cycle multiple times until the thickness of the film formed by stacking the second layer reaches the desired thickness.

[0093] The processing conditions in step (a) are as follows: <When compound A is used as the raw material> Gas supply flow rate of compound A: 0.01 to 2 slm, preferably 0.1 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing temperature (temperature of wafer 200): Room temperature to 250°C, preferably 100 to 250°C Processing pressure (pressure in processing chamber 201): 1 to 2666 Pa, preferably 67 to 1333 Pa <When compound B is used as the raw material> Gas supply flow rate of compound B: 0.01 to 2 slm, preferably 0.1 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing temperature (temperature of wafer 200): Room temperature to 250°C, preferably 100 to 250°C Processing pressure (pressure inside the processing chamber 201): Examples include 1 to 2666 Pa, preferably 67 to 1333 Pa.

[0094] In this specification, 0 slm means the case in which the target gas is not supplied. Furthermore, processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure refers to the pressure inside the processing chamber 201. Processing time refers to the duration for which the processing is continued.

[0095] Examples of processing conditions in step (b) include: H-containing gas supply flow rate: 0.1 to 10 slm; inert gas supply flow rate (per gas supply pipe): 0 to 10 slm; H-containing gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds; processing pressure: 1 to 300 Pa, preferably 1 to 100 Pa; RF power: 100 to 1000 W; RF frequency: 13.56 MHz or 27 MHz. Other processing conditions are the same as those in step (a).

[0096] If the processing temperature is below room temperature, in step (a), amino groups that have been detached from the Si contained in the raw material may be re-adsorbed onto the surface of the wafer 200. As a result, impurities such as C and N derived from amino groups are more likely to remain in the film formed on the wafer 200, and it may become difficult to control the concentration of these impurities in the film. Room temperature refers to 25°C.

[0097] By setting the processing temperature to a temperature above room temperature, it becomes possible to suppress the re-adsorption of amino groups detached from Si in the raw material onto the surface of wafer 200 in step (a). As a result, it becomes easier to control the concentration of impurities such as C and N in the film formed on wafer 200. The above effect can be further enhanced by setting the processing temperature to a temperature of 100°C or higher. In addition, since the probability of preferentially detaching amino groups over alkoxy groups during the raw material adsorption reaction can be increased, it becomes easier to form a film with fewer N and C derived from amino groups.

[0098] Furthermore, when the processing temperature exceeds 250°C, the raw material is more likely to undergo thermal decomposition in the gas phase during step (a), making it difficult to react with the surface of the wafer 200 while maintaining the bond between the Si atoms and the amino groups. In particular, when compound A is used as the raw material, the amino groups may detach from the Si atoms in the gas phase, making it difficult for the adsorption reaction (substitution reaction) between the amino groups and the surface of the wafer 200 to occur, thus making it difficult to obtain a practical adsorption rate (film deposition rate). In addition, in the temperature range above 250°C, especially when compound B is used as the raw material, the amount of change in the film deposition rate when the temperature is changed becomes smaller than in the range below 250°C, making it difficult to control the film deposition rate by adjusting the temperature.

[0099] By setting the processing temperature to 250°C or lower, in step (a), thermal decomposition of the raw material in the gas phase is suppressed, making it easier to react with the surface of the wafer 200 while maintaining the bond between Si atoms and amino groups. In particular, when compound A is used as the raw material, the detachment of amino groups from Si atoms in the gas phase is suppressed, and the adsorption reaction (substitution reaction) between the amino groups and the surface of the wafer 200 is easily generated, making it easy to obtain a practical adsorption rate (film deposition rate). Furthermore, in the temperature range of 250°C or lower, especially when compound B is used as the raw material, the film deposition rate can be increased by adjusting the temperature in the direction of decreasing it.

[0100] (After-purging and return to atmospheric pressure) After the formation of the film on the wafer 200 is completed, inert gas is supplied into the processing chamber 201 as a purge gas from nozzles 249a and 249b, respectively, 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 normal pressure (return to atmospheric pressure).

[0101] (Boat unloading, wafer discharge) The seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200, supported by the boat 217, are unloaded (boat unloaded) from the lower end of the manifold 209 to the outside of the reaction tube 203.

[0102] By obtaining the film in this way, the reactant containing O (O ２、 H ２ Compared to supplying oxygen-containing gases such as O, or oxygen-containing active species obtained by plasma excitation of these, hydrogen active species (H ＊ ) and deuterium-active species (D ＊ This promotes the detachment of impurities (especially H) from the film by O, thereby improving film quality such as WER. Furthermore, when forming films containing C and N, such as SiOC films and SiOCN films, it can suppress the excessive detachment of C and N by O.

[0103] As one embodiment of this disclosure, an example of film quality when compound A1 contained in compound A is used as a source gas is shown, and the atomic ratio (at%) of the SiO film obtained by measurement by XPS (X-ray photoelectron spectroscopy) was Si: 32.2 at%, O: 67.4 at%, C: less than 0.5 at%, and N: less than 0.5 at%. The atomic ratio (at%) obtained by measuring the content of C and N by SIMS (secondary ion mass spectrometry) was C: 1.0 × 10 －２１ at%, N: 8.0×10 －２０The value was at%. The WER was 55.6 A / min. As an example of the film quality when compound B1, contained in compound B, was used as the source gas, the atomic ratio (at%) of the SiOCN film obtained by XPS measurement was Si: 37.1 at%, O: 48.5 at%, C: 9.6 at%, N: 4.9 at%, the WER was 3.7 A / min, the WER after plasma ashing was 18.6 A / min, and the k value was 4.6. Furthermore, as an example of the film quality when compound B2, contained in compound B, was used as a raw material gas, the atomic ratio (at%) of the SiOCN film obtained by XPS measurement was Si: 39.8 at%, O: 52.3 at%, C: 4.1 at%, N: 3.8 at%, WER was 8.2 A / min, WER after plasma ashing was 15.0 A / min, and the k value was 4.4 or less.

[0104] (3) Modifications In one embodiment of the present disclosure described above, modifications can be made as shown below. Unless otherwise specified, the modifications can be the same as described above, except as described below. The modifications of the present disclosure have the following configuration.

[0105] In the above embodiments, examples were described in which a compound containing a Si atom and an amino group bonded to the Si atom, and at least one of an alkoxy group bonded to the Si atom and a siloxane bond having the Si atom, was used as the compound contained in the source gas. The present disclosure is not limited to the above embodiments, and for example, a compound containing an atom of another metal element or a predetermined element X which is a semiconductor element can be used instead of the Si atom. Examples of metal elements include group 13 elements such as aluminum (Al), group 4 elements such as titanium (Ti), zirconium (Zr), and hafnium (Hf), and group 5 elements such as niobium (Nb) and tantalum (Ta). Examples of semiconductor elements include boron (B), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0106] The above-described modifications are the same as the embodiments of the present disclosure, except that they contain a predetermined atom X instead of Si atoms, and the compounds are different. Therefore, the modifications of the present disclosure can be used by referring to the embodiments of the present disclosure. The modifications of the present disclosure provide the same effects as the embodiments of the present disclosure.

[0107] In the above-described embodiment, an example was given in which the reactant gas supplied into the processing chamber 201 is plasma-excited by applying high-frequency power to an electrode 300 provided on the outer circumference of the reaction tube 203. The present disclosure is not limited to the above-described embodiment, and for example, a plasma excitation unit (which may also be called a remote plasma unit) may be provided on the gas supply tube 232b, and the reactant gas plasma-excited in the plasma excitation unit may be supplied to the substrate in the processing chamber 201. According to this modification, the same effects as in the embodiment of the present disclosure can be obtained.

[0108] The above-described embodiments describe an example of forming a film using a batch-type processing apparatus that processes multiple wafers 200 at once. This disclosure is not limited to the above-described embodiments and can also be applied to forming a film using a single-wafer processing apparatus that processes one or more wafers 200 at once. Furthermore, the above-described embodiments describe an example of forming a film using a processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can also be applied to forming a film using a processing apparatus having a cold-wall type processing furnace.

[0109] Even when using these processing devices, each process can be performed using the same processing procedures and conditions as in the above embodiment, and the same effects as in the above embodiment can be obtained.

[0110] The above embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as those described above, for example.

[0111] 200 circuit boards

Claims

1. A substrate processing method for forming a film containing silicon and oxygen on a substrate by performing a predetermined number of cycles comprising: (a) supplying a compound to a substrate that contains a silicon atom and an amino group bonded to the silicon atom in one molecule, and at least one of an alkoxy group bonded to the silicon atom and a siloxane bond having the silicon atom; and (b) supplying an excited reactant containing hydrogen or deuterium and free of oxygen to the substrate.

2. The substrate treatment method according to claim 1, wherein the compound contains an alkoxy group in one molecule.

3. The substrate treatment method according to claim 2, wherein the compound does not contain a siloxane bond in one molecule.

4. The substrate treatment method according to claim 1, wherein the compound contains a siloxane bond in one molecule.

5. The substrate processing method according to claim 1, wherein the reactant is excited by plasma.

6. The substrate processing method according to claim 1, wherein the reactant comprises at least one of hydrogen gas and deuterium gas.

7. The substrate treatment method according to claim 1, wherein the reactant does not contain nitrogen.

8. The substrate processing method according to claim 1, wherein the compound has one amino group bonded to the silicon atom in one molecule.

9. The substrate processing method according to claim 1, wherein the compound comprises in one molecule one amino group bonded to the silicon atom and three alkoxy groups bonded to the silicon atom.

10. The substrate processing method according to claim 8, wherein the compound does not contain carbon atoms bonded to the silicon atom in one molecule.

11. The substrate processing method according to any one of claims 8 to 10, wherein the film containing silicon and oxygen is free from nitrogen and carbon.

12. The substrate processing method according to claim 1 or claim 4, wherein the compound further comprises an alkyl group bonded to the silicon atom in one molecule.

13. The substrate processing method according to claim 4 or claim 12, wherein the film containing silicon and oxygen contains nitrogen and carbon.

14. The substrate processing method according to claim 1, wherein the siloxane bond having silicon atoms constitutes a cyclic siloxane structure.

15. The substrate processing method according to claim 1, wherein the siloxane bond having silicon atoms constitutes a linear siloxane structure.

16. The substrate processing method according to claim 1, wherein the compound does not contain halogen elements.

17. The substrate processing method according to claim 1, wherein the temperature of the substrate in the cycle is 250°C or less.

18. A method for manufacturing a semiconductor device, comprising the steps of: (a) supplying a compound to a substrate, which contains a silicon atom and an amino group bonded to the silicon atom in one molecule, and also contains at least one of an alkoxy group bonded to the silicon atom and a siloxane bond having the silicon atom; and (b) supplying an excited reactant containing hydrogen or deuterium and free of oxygen to the substrate, by performing a predetermined number of cycles comprising these steps to form a film containing silicon and oxygen on the substrate.

19. A program that causes a substrate processing apparatus to perform the following steps via computer: (a) supplying a compound to a substrate, which in one molecule contains a silicon atom and an amino group bonded to the silicon atom, and also contains at least one of an alkoxy group bonded to the silicon atom and a siloxane bond having the silicon atom; and (b) supplying an excited reactant containing hydrogen or deuterium and free of oxygen to the substrate.

20. A substrate processing apparatus comprising: a raw material supply system for supplying a compound to a substrate, the compound having in one molecule a silicon atom and an amino group bonded to the silicon atom, and also containing at least one of an alkoxy group bonded to the silicon atom and a siloxane bond formed by the silicon atom; an excitation unit for exciting a reactant containing hydrogen or deuterium and free of oxygen, and supplying the excited reactant to the substrate; and a control unit configured to control the raw material supply system and the reactant supply system so as to perform a process of forming a film containing silicon and oxygen on the substrate by performing a predetermined number of cycles comprising: (A) supplying the compound to the substrate; and (B) supplying the excited reactant to the substrate.

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