Processing method, processing device, program, and high-purity raw material composition

Abstract

The present invention has: (a) a step for preparing a substrate having a recessed portion on the surface thereof; and (b) a step for forming a film on the surface of the substrate and within the recessed portion by supplying, to the substrate, a raw material that contains a halogeno group and an alkyl group and contains a silicon-silicon bond, and a reactant that contains oxygen and hydrogen, under conditions in which, if the raw material is present alone, the physical adsorption of the raw material occurs dominantly among the thermal decomposition of the raw material, the chemical adsorption of the raw material, and the physical adsorption of the raw material.

Description

Processing method, processing device, program, and high-purity raw material composition

[0001] The present disclosure relates to a processing method, a processing device, a program, and a high-purity raw material composition.

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a process of forming a film using a plurality of types of gases so as to fill a recess provided on the surface of a substrate is sometimes performed (see, for example, Patent Document 1).

[0003] International Publication No. 2021 / 171466

[0004] The present disclosure provides a technique for improving the properties of a film formed to fill a recess provided on the surface of a substrate.

[0005] According to one aspect of the present disclosure, there is provided a technology comprising: (a) preparing a substrate having a recess on its surface; and (b) supplying to the substrate a raw material that contains a halogeno group and an alkyl group and that contains a silicon-silicon bond, and a reactant that contains oxygen and hydrogen, under conditions in which, when the raw material exists alone, physical adsorption of the raw material predominates among thermal decomposition of the raw material, chemisorption of the raw material, and physical adsorption of the raw material, thereby forming a film on the surface of the substrate and in the recess.

[0006] According to the present disclosure, it is possible to improve the properties of a film formed to fill a recess provided on the surface of a substrate.

[0007] FIG. 1 is a schematic diagram of a vertical processing furnace of a processing apparatus suitable for use in one embodiment of the present disclosure, showing a vertical cross-sectional view of the processing furnace 202. FIG. 2 is a schematic diagram of a vertical processing furnace of a processing apparatus suitable for use in one embodiment of the present disclosure, showing a cross-sectional view of the processing furnace 202 along line A-A in FIG. 1. FIG. 3 is a schematic diagram of a controller 121 of a processing apparatus suitable for use in one embodiment of the present disclosure, showing a block diagram of the control system of the controller 121. FIG. 4(a) is a diagram showing a processing sequence in one embodiment of the present disclosure, FIG. 4(b) is a diagram showing a processing sequence in another embodiment of the present disclosure, and FIG. 4(c) is a diagram showing a processing sequence in another embodiment of the present disclosure. FIG. 5(a) is a TEM image showing a surface portion of a wafer in evaluation sample 1 of Example 1 of the present disclosure, and FIG. 5(b) is a TEM image showing a surface portion of a wafer in evaluation sample 2 of Example 2 of the present disclosure.

[0008] <One Aspect of the Present Disclosure> One aspect of the present disclosure will be described below, mainly with reference to Figures 1 to 3 and 4(a). Note that all drawings used in the following description are schematic, and the dimensional relationships between elements, the ratios of elements, etc. shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships between elements, the ratios of elements, etc. do not necessarily match between multiple drawings.

[0009] (1) Configuration of the Processing Apparatus As shown in Fig. 1, the processing furnace 202 of the processing apparatus has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0010] A reaction tube 203 is disposed inside the heater 207 concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO ２The reaction tube 203 is made of a heat-resistant material such as silicon carbide (SiC) or silicon carbide (SiC) and has a cylindrical shape with a closed top and an open bottom. A manifold 209 is disposed concentrically below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and has a cylindrical shape with open top and bottom ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a serving as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to accommodate wafers 200 as substrates. In this processing chamber 201, processing of the wafer 200 is carried out.

[0011] Nozzles 249a and 249b serving as a first supply unit and a second supply unit are provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209, respectively. The nozzles 249a and 249b are also referred to as a first nozzle and a second nozzle, respectively. The nozzles 249a and 249b are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively. The nozzles 249a and 249b are different nozzles, and the nozzles 249a and 249b are provided adjacent to each other.

[0012] The gas supply pipes 232a and 232b are respectively provided with mass flow controllers (MFCs) 241a and 241b, which are flow rate control devices (flow rate control parts), and valves 243a and 243b, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232c and 232d are connected to the gas supply pipe 232a downstream of the valve 243a. Gas supply pipe 232e is connected to the gas supply pipe 232b downstream of the valve 243b. The gas supply pipes 232c to 232e are respectively provided with MFCs 241c to 241e and valves 243c to 243e in order from the upstream side of the gas flow. The gas supply pipes 232a to 232e are made of a metal material, such as SUS.

[0013] As shown in FIG. 2 , the nozzles 249 a and 249 b are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, extending from the bottom to the top of the inner wall of the reaction tube 203 and rising upward in the arrangement direction of the wafers 200. That is, the nozzles 249 a and 249 b are provided in regions horizontally surrounding the wafer arrangement region on the sides of the wafer arrangement region where the wafers 200 are arranged, extending along the wafer arrangement region. Gas supply holes 250 a and 250 b for supplying gas are provided on the side surfaces of the nozzles 249 a and 249 b, respectively. The gas supply holes 250 a and 250 b are each open toward the center of the wafer 200 in a plan view, allowing gas to be supplied toward the wafer 200. A plurality of gas supply holes 250 a and 250 b are provided from the bottom to the top of the reaction tube 203.

[0014] From the gas supply pipe 232a, a raw material is supplied into the processing chamber 201 via an MFC 241a, a valve 243a, and a nozzle 249a.

[0015] A reactant is supplied from the gas supply pipe 232b into the processing chamber 201 via an MFC 241b, a valve 243b, and a nozzle 249b.

[0016] A modifying agent (treatment gas) is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, the gas supply pipe 232a, and the nozzle 249a.

[0017] Inert gas is supplied from the gas supply pipes 232d and 232e into the processing chamber 201 via the MFCs 241d and 241e, the valves 243d and 243e, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b, respectively. The inert gas acts as a purge gas, a carrier gas, a dilution gas, a modifier, etc.

[0018] A raw material supply system is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a. A reactant supply system is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b. A modifying agent supply system (treatment gas supply system) is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c. An inert gas supply system is mainly composed of the gas supply pipes 232d and 232e, MFCs 241d and 241e, and valves 243d and 243e. The inert gas supply system may be included in the modifying agent supply system.

[0019] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243e, MFCs 241a to 241e, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232e, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a to 232e, i.e., the opening and closing operation of the valves 243a to 243e and the flow rate adjustment operation by the MFCs 241a to 241e, etc., are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a to 232e, etc., so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0020] An exhaust port 231a for exhausting the atmosphere inside the process chamber 201 is provided at the bottom of the sidewall of the reaction tube 203. As shown in FIG. 2 , the exhaust port 231a is provided at a position facing the nozzles 249a and 249b (gas supply holes 250a and 250b) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the sidewall of the reaction tube 203 from the bottom to the top, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure inside the process chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0021] A seal cap 219 serving as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209 is provided below the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220b serving as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cap 219. A rotation mechanism 267 for rotating the boat 217 (described later) is provided below the seal cap 219. A rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the boat 217, thereby rotating the wafers 200. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 serving as an elevating mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a device for preparing wafers 200 in the processing chamber 201, i.e., a transport device (transport mechanism) that transports wafers 200 in and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0022] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is unloaded from the process chamber 201. The shutter 219s is made of a metal material such as SUS and has a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that abuts against the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0023] The boat 217 serving as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in multiple stages, in a horizontal position, with their centers aligned and aligned vertically, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages.

[0024] A temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution inside the processing chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0025] As shown in FIG. 3 , the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able 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. An external storage device 123 can also be connected to the controller 121. Note that the processing device may be configured to include one or more control units. That is, the control for performing the processing sequence described below may be performed using one control unit or multiple control units. Furthermore, the multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and the control for carrying out the processing sequence described below may be performed by the entire control system. When the term "control unit" is used in this specification, it may include not only one control unit but also multiple control units or a control system configured by multiple control units.

[0026] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. Control programs for controlling the operation of the processing device, process recipes describing procedures and conditions for substrate processing (described later), etc., are readably recorded and stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (film formation processing) (described later) that are executed by the controller 121 in the processing device to obtain a predetermined result, and functions as a program. Hereinafter, the process recipes, control programs, etc. are collectively referred to simply as programs. The process recipes are also simply referred to as recipes. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0027] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241e, valves 243a to 243e, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0028] 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 an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241e, the opening and closing operation of the valves 243a to 243e, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting 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, and the like.

[0029] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to as recording media. When the term recording medium is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0030] (2) Processing Step An example of a method of processing a substrate (processing method) as one step in a semiconductor device manufacturing process (manufacturing method) using the processing apparatus described above, i.e., a processing sequence for forming a film on the surface of a wafer 200 as a substrate, will be described mainly with reference to FIG. 4( a). In this embodiment, an example will be described in which a silicon substrate (silicon wafer) having recesses such as trenches and holes formed in its surface is used as the wafer 200. In the following description, the operation of each component constituting the processing apparatus is controlled by a controller 121. The processing apparatus will also be referred to as a substrate processing apparatus, a film formation processing apparatus, or a film formation apparatus. The processing method will also be referred to as a substrate processing method, a film formation processing method, or a film formation method.

[0031] The processing sequence in this embodiment includes: Step A of preparing a wafer 200 having a recess on its surface; and Step B of forming a film on the surface of wafer 200 and in the recess by supplying to wafer 200 a raw material that contains a halogeno group and an alkyl group and that contains a silicon-silicon bond (a chemical bond between silicon and silicon), and a reactant that contains oxygen and hydrogen, under conditions in which, when the raw material exists alone, physical adsorption of the raw material predominates among thermal decomposition of the raw material, chemical adsorption of the raw material, and physical adsorption of the raw material.

[0032] In the processing sequence of this embodiment, after step B, step C is further performed in which the wafer 200, on which a film has been formed on the surface and inside the recesses, is subjected to a heat treatment at a processing temperature higher than the processing temperature in step B. The treatment performed in step C is also called a modification treatment or a post-treatment (PT).

[0033] In addition, in the processing sequence of this embodiment, steps B and C are performed consecutively (in-situ) in the same processing chamber 201 of the same processing apparatus. That is, after supplying raw materials and reactants (raw materials + reactants) to the wafers 200 in the processing chamber 201, the processing chamber 201 is purged and evacuated (PRG / VAC), and further, post-treatment (PT) is performed on the wafers 200 in the processing chamber 201. Note that, since the wafers 200 are prepared in the processing chamber 201 in step A, steps A, B, and C in this embodiment can also be considered to be performed in-situ.

[0034] In this specification, the above-described processing sequence may be expressed as follows for convenience: Note that similar notations may be used in the following explanations of modified examples, etc.

[0035] (raw material + reactant) → PRG / VAC → PT

[0036] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0037] As used herein, the terms "raw material," "reactant," "modifier," and "substance" include at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist-like substance. That is, each of the raw material, reactant, and modifier may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0038] (Step A: Wafer Charging and Boat Loading) When a plurality of 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). Thereafter, as shown in FIG. 1 , the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this manner, the wafers 200 are prepared in the processing chamber 201.

[0039] (Pressure Adjustment and Temperature Adjustment) After the boat loading is completed, the inside of the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the desired pressure (vacuum level) is reached. 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. Furthermore, the wafers 200 inside the processing chamber 201 are heated by the heater 207 so that the desired processing temperature is reached. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the desired temperature distribution is achieved inside the processing chamber 201. Furthermore, the rotation mechanism 267 starts to rotate the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0040] (Step B: Film Formation) After that, raw materials and reactants are supplied to the wafer 200 having a recess on its surface.

[0041] Specifically, valves 243a and 243b are opened to allow the raw materials and reactants to flow into gas supply pipes 232a and 232b, respectively. The raw materials and reactants are supplied into the processing chamber 201 via nozzles 249a and 249b with their flow rates adjusted by MFCs 241a and 241b, and are then exhausted from the exhaust port 231a. At this time, the raw materials and reactants are supplied to the wafer 200 from the side of the wafer 200 (raw materials + reactant supply). At this time, valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a and 249b, respectively.

[0042] The raw material may be a silicon (Si)-containing substance that contains a halogeno group and an alkyl group and a silicon-silicon bond (Si-Si bond). Examples of halogeno groups include chloro, fluoro, bromo, and iodo groups. Specifically, halogeno groups include halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). Examples of alkyl groups include methyl (-Me), ethyl (-Et), propyl (-Pr), and butyl (-Bu). The alkyl group may be a linear alkyl group or a branched alkyl group such as an isopropyl group, an isobutyl group, a secondary butyl group, or a tertiary butyl group. The raw material may be a substance containing four or more halogeno groups per molecule. Alternatively, the raw material may be a substance containing two or more alkyl groups per molecule. Alternatively, the raw material may be a substance containing four or more halogeno groups and silicon chemical bonds per molecule. Alternatively, the raw material may be a substance containing two or more alkyl groups and silicon chemical bonds per molecule.

[0043] The raw material is, for example, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH ３ ) ２ Si ２ Cl ４ ), 1,1,2,2-tetrachloro-1,2-diethyldisilane ((C ２ H ５ ) ２ Si ２ Cl ４), 1,2-diisopropyl-1,1,2,2-tetrachlorodisilane ((C ３ H ７ ) ２ Si ２ Cl ４ ), 1,1,3,3-tetrachloro-1,3-dimethyldisiloxane ((CH ３ ) ２ Si ２ OCl ４ ), 1,1,3,3-tetrachloro-1,3-diethyldisiloxane ((C ２ H ５ ) ２ Si ２ OCl ４ ), 1,1,3,3-tetrachloro-1,3-dimethyldisilazane ((CH ３ ) ２ Si ２ NHCl ４ ), bis(dichloromethylsilyl)methane ((CH ３ ) ２ Si ２ CH ２ Cl ４ ), 1,2-bis(dichloromethylsilyl)ethane ((CH ３ ) ２ Si ２ C ２ H ４ Cl ４ As the raw material, one or more of these can be used.

[0044] The reactant can be a substance containing oxygen (O) and hydrogen (H). The reactant can be a substance containing two or more hydroxyl groups (-OH) in one molecule. The reactant can also be a substance containing two or more oxygen-hydrogen bonds (O-H bonds) in one molecule.

[0045] The reactant may be, for example, lactic acid (CH ３ -C(OH)H-COOH), propylene glycol (H ３ C-C(OH)H-CH ２ OH), diethanolamine (HN(C ２ H ４ OH) ２), 2-[(hydroxymethyl)amino]ethanol ((HOCH ２ ) HN-C ２ H ４ OH), ethylene glycol (HO-CH ２ -CH ２ —OH), 1,2-propanediol (HO—CH(CH ３ )-CH ２ —OH), 1,3-propanediol (HO—C ３ H ６ —OH), methanediol (HO-CH ２ The reactants may be hydrogen peroxide (HO-OH), hydrogen peroxide (HO-OH), or water (H-O-H). One or more of these may be used as the reactant. Preferably, the reactant is H ２ At least one of ethylene glycol and propylene glycol can be used.

[0046] The inert gas is nitrogen (N ２ Inert gases that can be used include rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, krypton (Kr) gas, and xenon (Xe) gas. One or more of these gases can be used as the inert gas. This also applies to the steps described below.

[0047] The processing conditions for supplying the raw material and reactants in step B are conditions under which, when the raw material is present alone, the physical adsorption of the raw material predominates among the thermal decomposition, chemical adsorption, and physical adsorption of the raw material. These conditions are non-plasma conditions, which can also be considered as conditions under which no plasma chemical reaction occurs. These conditions can also be considered as conditions under which a thermochemical reaction occurs, which can also be considered as conditions under which a thermochemical reaction predominates.

[0048] In step B, the catalyst is not supplied to the wafer 200, for example, triethylamine ((C ２ H ５ ) ３ N) and pyridine (C ５ H ５ It is preferable not to supply an amine-based catalyst such as amine-based catalyst (N).

[0049] In addition, it is preferable to set the supply flow rate of the reactants higher than the supply flow rate of the raw materials in step B. For example, in step B, the supply flow rate of the reactants is preferably set to at least twice the supply flow rate of the raw materials, more preferably at least three times, and even more preferably at least four times.

[0050] Examples of treatment conditions for supplying the raw materials and reactants in step B include: treatment temperature (first temperature): 0 to 80°C, preferably room temperature (25°C) to 60°C treatment pressure: 1 to 30,000 Pa, preferably 133 to 10,000 Pa treatment time: 1 to 180 minutes, preferably 5 to 60 minutes raw material supply flow rate: 0.02 to 2 slm, preferably 0.05 to 0.5 slm reactant supply flow rate: 0.05 to 50 slm, preferably 0.1 to 10 slm inert gas supply flow rate (per gas supply pipe): 0 to 20 slm

[0051] In this specification, when a numerical range such as "0 to 80°C" is expressed, it means that the lower limit and the upper limit are included in the range. Therefore, for example, "0 to 80°C" means "0°C or higher and 80°C or lower." The same applies to other numerical ranges. In this specification, the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure means the pressure inside the processing chamber 201. The processing time means the time the processing continues. In addition, when the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied. These also apply to the following explanations.

[0052] By supplying raw materials and reactants to wafer 200 under the above-described processing conditions, it is possible to generate and flow at least one of clusters and oligomers containing elements contained in at least one of the raw materials and reactants on the surface and within the recesses of wafer 200, thereby forming a film on the surface and within the recesses of wafer 200.

[0053] Here, a cluster refers to an aggregate that is bound together by relatively weak forces such as van der Waals forces or hydrogen bonds. The cluster includes at least one of a cluster of reactants and a cluster of a substance (intermediate) in which at least a portion of the halogeno groups contained in the raw material have been replaced with hydroxyl groups. An oligomer refers to a polymer with a relatively low molecular weight (e.g., a molecular weight of 10,000 or less) in which a relatively small number (e.g., 10 to 100) of monomers (smallest unit molecules) are bonded. The oligomer includes an oligomer of a substance (intermediate) in which at least a portion of the halogeno groups contained in the raw material have been replaced with hydroxyl groups.

[0054] When the above-mentioned materials are used as the source material and the reactant, the film formed on the surface of the wafer 200 and in the recessed portion contains either silicon and oxygen or silicon, oxygen, and carbon, i.e., the film becomes a silicon oxide film (SiO film) or a silicon oxycarbonide film (SiOC film).

[0055] The above-described film formed on the surface of the wafer 200 and in the recesses often serves as an insulating film. This film may be used as a retaining film (non-sacrificial film), i.e., a film that remains on the wafer 200 without being removed, rather than a sacrificial film that is removed from the wafer 200 after this step (film formation process). This film may be affected by metal contamination during the film formation process. In particular, when the raw material contains a halogen group, i.e., a halogen element, the corrosiveness of the raw material may make the film more susceptible to metal contamination. When the film formation process is performed under higher temperature conditions than the above-described process conditions, it may be possible to remove contaminants (metal elements) incorporated into the film during the film formation process. However, as described above, this step is performed under relatively low temperature conditions. Therefore, the metal elements incorporated into the film during the film formation process may not be removed during the film formation process and may remain in the film even after the film formation process is completed. Metal elements remaining in the film, such as sodium (Na), potassium (K), iron (Fe), chromium (Cr), nickel (Ni), and copper (Cu), can degrade the physical properties (insulating and dielectric properties) of the film. For this reason, it is preferable that the raw materials used in this step be highly pure. For example, the concentrations of metal elements in the raw materials, such as Na, K, Fe, Cr, Ni, and Cu, are each preferably less than 10 ppb. Unless the raw material manufacturing process is properly managed and the raw materials are properly manufactured, it is impossible to refine (highly purify) a substance with such high purity, and it may be difficult to apply the obtained substance to the manufacturing process of a semiconductor device. For example, if the concentration of metal elements contained in the raw materials is 10 ppb or more, the impact of metal contamination becomes significant, which may deteriorate the insulating and dielectric properties of the formed film. By properly managing the manufacturing process of the raw materials and keeping the concentration of metal elements contained in the raw materials below 10 ppb, the effects of metal contamination can be significantly reduced, and the insulating and dielectric properties of the formed film can be significantly improved, resulting in significantly improved electrical properties.The same can be said for other metal elements not exemplified here, as long as they affect the physical properties of the film.The same can be said for reactants as well as raw materials.

[0056] In view of these facts and the above-mentioned explanation of the raw material, in this embodiment, a high-purity raw material composition containing a raw material containing a silicon-silicon bond, X (X is an integer of 1 or more) halogeno groups, and Y (Y is an integer of 1 or more) alkyl groups per molecule, and containing a metal element at a concentration of less than 10 ppb, is preferably used as a raw material (precursor) for forming a flowable film. That is, in this embodiment, a high-purity raw material composition containing a raw material containing a silicon-silicon bond, X (X is an integer of 1 or more) halogeno groups, and Y (Y is an integer of 1 or more) alkyl groups per molecule, and containing a metal element at a concentration of less than 10 ppb, is preferably used, the raw material being capable of forming a flowable film on the surface of the wafer 200 and in the recesses by supplying the raw material and a reactant containing oxygen and hydrogen to the wafer 200 having a recess on its surface. Note that X and Y are preferably integers that satisfy the relationship X + Y = 6. Furthermore, X and Y are preferably integers that satisfy X+Y=6 and 5≧X / Y≧1. Furthermore, X and Y are preferably integers that satisfy X+Y=6 and X≧Y, and more preferably integers that satisfy X+Y=6 and X>Y. Furthermore, X and Y are preferably integers that satisfy X+Y=6 and X≧4, and more preferably integers that satisfy X+Y=6 and Y≧2.

[0057] After a predetermined time has elapsed, the valves 243a and 243b are closed to stop the supply of raw materials and reactants into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gases remaining in the processing chamber 201. At this time, the valves 243d and 243e are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b. The inert gas supplied from the nozzles 249a and 249b acts as a purge gas, thereby purging the processing chamber 201 (PRG / VAC).

[0058] Examples of processing conditions when PRG / VAC is performed in step B include: processing pressure: 1 to 30 Pa processing time: 1 to 120 seconds, preferably 1 to 60 seconds inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm It is noted that the processing temperature when PRG / VAC is performed in this step is preferably the same as the processing temperature when the raw materials and reactants are supplied.

[0059] By performing PRG / VAC under the above-described processing conditions, it is possible to exhaust excess components contained in the film formed on the surface of the wafer 200 and in the recess, such as excess gas and by-products containing Cl.

[0060] (Step C: PT) After a film is formed on the surface of the wafer 200 and in the recess, the output of the heater 207 is adjusted to change the temperature of the wafer 200 to a processing temperature (second temperature) higher than the processing temperature (first temperature) in step B.

[0061] At this time, a modifying agent is supplied to the wafers 200 in the processing chamber 201. Specifically, the valve 243c is opened to allow the modifying agent to flow into the gas supply pipe 232c. The flow rate of the modifying agent is adjusted by the MFC 241c, and the modifying agent is supplied into the processing chamber 201 via the gas supply pipe 232a and the nozzle 249a, and is exhausted from the exhaust port 231a. At this time, the modifying agent is supplied to the wafers 200.

[0062] Examples of treatment conditions when supplying the modifier in step C include: treatment temperature (second temperature): 100 to 1000°C, preferably 200 to 600°C; treatment pressure: 10 to 80000 Pa, preferably 200 to 6000 Pa; treatment time: 300 to 10800 seconds; and modifier supply flow rate: 0.01 to 20 slm.

[0063] By performing step C under the above-described conditions, a dehydration condensation reaction or the like occurs in the film formed on the surface of the wafer 200 and in the recessed portion, and unreacted bonding groups (Si—OH) contained in the film are converted into siloxane bonds (Si—O—Si bonds), thereby strengthening the bonds. This makes it possible to modify the film formed on the surface of the wafer 200 and in the recessed portion into a film containing strong bonds. Furthermore, by performing step C under the above-described conditions, it is possible to expel excess components (impurities) contained in the film formed on the surface of the wafer 200 and in the recessed portion, repair defects present in the film, and densify and harden the film.

[0064] The modifiers include oxygen (O ２ ) gas, ozone (O ３ ) Gas, O ２ Gas + Hydrogen (H ２ ) Gas, O ２ Gas + Deuterium (D ２ ) Gas, O ３ Gas + H ２ Gas, O ３ Gas + D ２ Gas, hydrogen peroxide (H ２ O ２ ) gas, water vapor (H ２ O gas), nitrous oxide (N ２ O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO ２ ) gas, carbon dioxide (CO ２ Oxygen-containing gases such as carbon monoxide (CO) gas and the like can be used. ２ Gas + H ２ In the case of a description of two gases, such as "O gas", ２ Gas and H ２ When supplying a mixed gas, the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be supplied separately into the processing chamber 201 through different supply pipes and then mixed (postmixed) in the processing chamber 201.

[0065] In addition, the modifier is H ２ hydrogen-containing gases such as D ２A deuterium-containing gas such as a gas can be used.

[0066] The modifying agent may be the inert gas described above. In this case, the modifying agent may be supplied from at least one of the gas supply pipes 232d and 232e, rather than the gas supply pipe 232c.

[0067] As the modifier, one or more of these can be used.

[0068] (After-Purge and Atmospheric Pressure Return) After step C is completed, an inert gas serving as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249 a and 249 b and exhausted from the exhaust port 231 a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0069] (Boat Unloading and Wafer Discharge) Thereafter, 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 from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After the boat unloading, the shutter 219s is moved, and the opening at the lower end of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being unloaded to the outside of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer discharge).

[0070] It is preferable to perform steps B and C in the same processing chamber (in-situ). If a series of processes is performed in-situ, the wafer 200 is not exposed to the atmosphere during the process, and the wafer 200 can be processed consistently while being kept under vacuum, making it possible to perform stable processing.

[0071] (3) Effects of this Aspect According to this aspect, one or more of the following effects can be obtained.

[0072] (a) By supplying a raw material containing a halogeno group and an alkyl group and a silicon-silicon bond, and a reactant containing oxygen and hydrogen under conditions in which the physical adsorption of the raw material predominates among the thermal decomposition, chemical adsorption, and physical adsorption of the raw material when the raw material is present alone, it is possible to improve the properties of the film formed on the substrate. That is, it is possible to increase the fluidity of the film formed on the surface of the substrate and within the recessed portion, thereby improving the filling properties of the film formed within the recessed portion. As a result, void-free and seamless filling is possible. Furthermore, it is possible to suppress the generation of by-products such as ammonium halides such as ammonium chloride during the film formation process, thereby suppressing the generation of particles resulting from such by-products.

[0073] (b) By setting the conditions in step B to non-plasma conditions, i.e., conditions under which no plasma chemical reaction occurs, it is possible to effectively increase the fluidity of the film formed on the surface of the substrate and in the recesses while avoiding plasma damage, and it is possible to effectively improve the filling characteristics of the film formed in the recesses. As a result, it is possible to effectively perform void-free and seamless filling.

[0074] Furthermore, by setting the conditions in step B to conditions under which a thermochemical reaction occurs, that is, conditions under which a thermochemical reaction occurs predominantly, it becomes possible to obtain the same effects as those described above.

[0075] (c) By using a substance containing four or more halogeno groups per molecule as a raw material, the fluidity of the film formed on the surface of the substrate and in the recesses can be effectively increased, and the filling characteristics of the film formed in the recesses can be effectively improved. As a result, void-free and seamless filling can be effectively achieved.

[0076] Furthermore, by using a substance containing two or more alkyl groups in one molecule as a raw material, the same effect as that described above can be obtained.

[0077] Furthermore, by using a substance containing four or more chemical bonds between halogeno groups and silicon in one molecule as a raw material, the same effect as described above can be obtained.

[0078] Furthermore, by using a substance containing two or more alkyl groups and silicon chemical bonds in one molecule as a raw material, the same effect as described above can be obtained.

[0079] Furthermore, by using high-purity materials as raw materials in which the concentrations of metal elements, for example, Na, K, Fe, Cr, Ni, Cu, etc., are each less than 10 ppb, the effects of metal contamination on the film formed on the substrate can be significantly reduced, and the insulating properties, dielectric properties, etc. of the film can be significantly improved. Note that by using a high-purity raw material composition containing a raw material containing a silicon-silicon bond, X (X is an integer of 1 or more) halogeno groups, and Y (Y is an integer of 1 or more) alkyl groups in one molecule, and containing metal elements at a concentration of less than 10 ppb, as a raw material (precursor) for forming a flowable film, it is possible to effectively obtain the above-mentioned effects while significantly reducing the effects of metal contamination.

[0080] (d) By using a substance containing two or more hydroxyl groups in one molecule, i.e., a substance containing two or more oxygen-hydrogen bonds (chemical bonds between oxygen and hydrogen) in one molecule as a reactant, the fluidity of the film formed on the surface of the substrate and in the recesses can be effectively increased, and the same effects as those described above can be obtained.

[0081] Also, the reactant is H ２ By including at least one of O and ethylene glycol, the same effects as those described above can be more appropriately obtained.

[0082] (e) In step B, by not supplying a catalyst to the substrate, the fluidity of the film formed on the surface of the substrate and in the recesses can be effectively increased, thereby achieving the same effect as described above.

[0083] (f) When the film formed on the surface of the substrate and in the recess contains silicon and oxygen, or silicon, oxygen, and carbon, the fluidity of the film can be effectively increased, and the same effect as that described above can be obtained.

[0084] (g) In step B, if the supply flow rate of the reactants is smaller than the supply flow rate of the precursor, the fluidity of the film formed on the surface of the substrate and in the recesses may decrease. By making the supply flow rate of the reactants larger than the supply flow rate of the precursor, the fluidity of the film can be increased, and the same effect as that described above can be obtained.

[0085] In addition, by setting the supply flow rate of the reactants at least twice the supply flow rate of the raw materials, it is possible to effectively increase the fluidity of the film. By setting the supply flow rate of the reactants at least three times the supply flow rate of the raw materials, it is possible to more effectively increase the fluidity of the film. By setting the supply flow rate of the reactants at least four times the supply flow rate of the raw materials, it is possible to even more effectively increase the fluidity of the film.

[0086] However, if the supply flow rate of the reactants is set to a flow rate that exceeds 500 times the supply flow rate of the raw materials, it may become difficult to stably supply the reactants. Therefore, the supply flow rate of the reactants is preferably set to 500 times or less, more preferably 200 times or less, and even more preferably 100 times or less, the supply flow rate of the raw materials.

[0087] (h) In step B, at least one of clusters and oligomers containing elements contained in at least one of the raw materials and reactants is generated on the surface of the substrate and in the recesses and allowed to flow, thereby more effectively increasing the fluidity of the film formed on the surface of the substrate and in the recesses and more effectively improving the filling characteristics of the film formed in the recesses. As a result, void-free and seamless filling can be more effectively performed.

[0088] By including in the clusters at least one of clusters of reactants and clusters of substances in which at least some of the halogeno groups contained in the raw materials have been replaced with hydroxyl groups, the fluidity of the film formed on the surface of the substrate and within the recesses can be more effectively increased, and effects similar to those described above can be more appropriately obtained.

[0089] By including an oligomer of a substance in which at least some of the halogeno groups contained in the raw material have been replaced with hydroxyl groups, the fluidity of the film formed on the surface of the substrate and within the recesses can be more effectively increased, and the same effects as those described above can be more appropriately obtained.

[0090] (i) By carrying out step B and then step C, i.e., by subjecting the substrate having a film formed on the surface of the substrate and in the recesses to a heat treatment at a treatment temperature (second temperature) higher than the treatment temperature (first temperature) in step B, it is possible to remove excess components contained in the film formed on the surface of the substrate and in the recesses, such as halogeno groups, alkyl groups, or impurities and by-products containing elements that constitute these, and further to densify and harden the film.

[0091] (j) The above-mentioned effects can be similarly obtained when a predetermined substance is arbitrarily selected from the various raw materials, reactants, modifiers, and inert gases mentioned above.

[0092] Other Aspects of the Present Disclosure The above describes specific aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0093] For example, as shown in FIG. 4B and the processing sequence shown below, in step B, a cycle including a step of supplying a source material and a reactant to a substrate and a step of performing PRG / VAC may be performed a predetermined number of times (n times, where n is an integer of 1 or 2 or more). The processing procedures and processing conditions in each step of this embodiment may be the same as those in the above-described embodiment. In this embodiment, the same effects as those in the above-described embodiment can be obtained.

[0094] [(raw material + reactant) → PRG / VAC] × n → PT

[0095] 4(c) and the processing sequence shown below, in step B, a cycle of continuously supplying a raw material to a substrate and a reactant to a substrate may be performed a predetermined number of times (n times, where n is an integer of 1 or 2 or more), followed by PRG / VAC. The processing procedures and processing conditions in each step of this embodiment may be the same as those in the above-described embodiment. In this embodiment, the same effects as those in the above-described embodiment can be obtained.

[0096] (raw material → reactant) × n → PRG / VAC → PT

[0097] It is preferable that the recipes used for each process are individually prepared according to the process content and recorded and stored in the storage device 121c via an electric communication line or the external storage device 123. When starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from among the multiple recipes recorded and stored in the storage device 121c. This enables the processing device to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses. It also reduces the burden on the operator, avoids operational errors, and enables each process to be started quickly.

[0098] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe already installed in the processing device. When modifying a recipe, the modified recipe may be installed in the processing device via an electric communication line or a recording medium on which the recipe is recorded. Furthermore, an existing recipe already installed in the processing device may be directly modified by operating the input / output device 122 provided in the existing processing device.

[0099] In the above-described embodiment, an example of forming a film using a batch-type processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied, for example, to a case where a film is formed using a single-wafer processing apparatus that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of forming a film using a processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied to a case where a film is formed using a processing apparatus having a cold-wall processing furnace.

[0100] In the above-described embodiment, the processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiment, and for example, one step and another step of the processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus.

[0101] When using these processing devices, each process can be performed using the same processing procedures and conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0102] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example.

[0103] A film was formed on a wafer by the process sequence of the above-described embodiment, and evaluation sample 1 of Example 1 was produced. The process conditions in each step when producing evaluation sample 1 were set to predetermined conditions within the range of the process conditions in each step of the above-described embodiment. When producing evaluation sample 1, a Si wafer having a recess on its surface and the outermost surface of which was made of a SiN film was used as the wafer, the raw materials exemplified in the above-described embodiment were used as the raw materials, and H ２ O was used to form a SiOC film.

[0104] Furthermore, a film was formed on a wafer using the process sequence of the above-described embodiment, to produce evaluation sample 2 of Example 2. The process conditions for each step in producing evaluation sample 2 were set to predetermined conditions within the range of the process conditions for each step of the above-described embodiment. When producing evaluation sample 2, a Si wafer having a recess on its surface and the outermost surface of which was formed of a SiN film was used as the wafer, the raw materials exemplified in the above-described embodiment were used as the raw materials, ethylene glycol was used as the reactant, and a SiOC film was formed as the film.

[0105] Thereafter, the surface portion of the wafer of each evaluation sample was observed with a transmission electron microscope (TEM) to obtain images (TEM images). Fig. 5(a) is a TEM image showing the surface portion of the wafer of evaluation sample 1, and Fig. 5(b) is a TEM image showing the surface portion of the wafer of evaluation sample 2.

[0106] From the TEM images of FIGS. 5( a ) and 5 ( b ), it was confirmed that void-free and seamless filling was possible in all of the evaluation samples, and high filling properties were obtained.

[0107] 200 wafers (substrates)

Claims

1. A processing method comprising the steps of: (a) preparing a substrate having a recess on its surface; and (b) supplying to the substrate a raw material that contains a halogeno group and an alkyl group and that contains a silicon-silicon bond, and a reactant that contains oxygen and hydrogen, under conditions in which, when the raw material exists alone, physical adsorption of the raw material predominates among thermal decomposition of the raw material, chemisorption of the raw material, and physical adsorption of the raw material, thereby forming a film on the surface of the substrate and in the recess.

2. The processing method according to claim 1, wherein the conditions in (b) are non-plasma conditions.

3. The processing method according to claim 1, wherein the conditions in (b) are conditions under which no plasma chemical reaction occurs.

4. The processing method according to claim 1, wherein the conditions in (b) are conditions under which a thermochemical reaction occurs.

5. The processing method according to claim 1, wherein the conditions in (b) are conditions under which a thermochemical reaction occurs predominantly.

6. The processing method according to claim 1, wherein the raw material contains four or more halogeno groups in one molecule.

7. The processing method according to claim 1, wherein the raw material contains two or more alkyl groups in one molecule.

8. The processing method according to claim 1, wherein the raw material contains four or more chemical bonds between halogen groups and silicon in one molecule.

9. The processing method according to claim 1, wherein the raw material contains chemical bonds between two or more alkyl groups and silicon in one molecule.

10. The treatment method according to claim 1, wherein the concentration of metal elements contained in the raw material is less than 10 ppb.

11. The method according to claim 1, wherein the reactant contains two or more hydroxyl groups in one molecule.

12. The method of claim 1, wherein the reactant contains two or more oxygen-hydrogen bonds in one molecule.

13. The reactant is H ２ 2. The method according to claim 1, wherein the solvent contains at least one of O and ethylene glycol.

14. The processing method according to claim 1, wherein in (b), no catalyst is supplied to the substrate.

15. The process of claim 1, wherein the film comprises silicon and oxygen, or silicon, oxygen, and carbon.

16. The method according to any one of claims 1 to 15, wherein the flow rate of the reactants fed is greater than the flow rate of the raw material fed.

17. The method according to any one of claims 1 to 15, wherein the flow rate of the reactants fed is at least twice the flow rate of the raw material fed.

18. A processing method according to any one of claims 1 to 15, wherein in (b), at least one of clusters and oligomers containing elements contained in at least one of the raw material and the reactant is generated and flowed on the surface of the substrate and within the recess, thereby forming the film on the surface of the substrate and within the recess.

19. The processing method according to claim 18, wherein the clusters include at least one of clusters of the reactants and clusters of a substance in which at least a portion of the halogeno groups contained in the raw material have been replaced with hydroxyl groups.

20. The processing method according to claim 18, wherein the oligomer comprises an oligomer of a substance in which at least a portion of the halogeno groups contained in the raw material have been replaced with hydroxyl groups.

21. A processing method according to any one of claims 1 to 15, further comprising the step of (c) subjecting the substrate, on which the film has been formed on the surface of the substrate and in the recess, to a heat treatment at a processing temperature higher than the processing temperature in (b).

22. A processing apparatus comprising: a processing chamber in which a substrate is processed; an apparatus for preparing a substrate within the processing chamber; a raw material supply system for supplying a raw material containing a halogeno group and an alkyl group and a silicon-silicon bond to the substrate within the processing chamber; a reactant supply system for supplying a reactant containing oxygen and hydrogen to the substrate within the processing chamber; and a control unit configured to be capable of controlling the apparatus, the raw material supply system, and the reactant supply system so as to perform, within the processing chamber: (a) a process for preparing a substrate having a recess on its surface; and (b) a process for forming a film on the surface of the substrate and in the recess by supplying the raw material and the reactant to the substrate under conditions in which, when the raw material is present alone, physical adsorption of the raw material is predominant among thermal decomposition of the raw material, chemisorption of the raw material, and physical adsorption of the raw material.

23. A program that causes a processing device to execute, by a computer, the following steps: (a) a procedure for preparing a substrate having a recess on its surface; and (b) a procedure for forming a film on the surface of the substrate and in the recess by supplying to the substrate a raw material that contains a halogeno group and an alkyl group and a silicon-silicon bond, and a reactant that contains oxygen and hydrogen, when the raw material exists alone, under conditions in which physical adsorption of the raw material predominates among thermal decomposition of the raw material, chemisorption of the raw material, and physical adsorption of the raw material.

24. A high-purity raw material composition comprising a raw material containing, in one molecule, a silicon-silicon bond, X (X is an integer of 1 or more) halogeno groups, and Y (Y is an integer of 1 or more) alkyl groups, and containing a metal element at a concentration of less than 10 ppb, said raw material being capable of forming a flowable film on the surface of a substrate having recesses on its surface and within the recesses by supplying said raw material and a reactant containing oxygen and hydrogen to said substrate.

Images