Method for manufacturing semiconductor device, substrate processing method, substrate processing apparatus, and recording medium

Abstract

The present invention includes a step of forming a film by repeating a cycle including the following (a) to (d) a predetermined number of times to fill a recess formed on the surface of a substrate. (a) A step of supplying a dummy catalyst to the substrate in a processing chamber; (b) A step of discharging the dummy catalyst remaining in the processing chamber; (c) A step of supplying a raw material to the substrate in the processing chamber; and (d) A step of discharging the raw material remaining in the processing chamber. In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate is unsaturated.

Description

Technical Field

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

[0002] As one of the manufacturing processes of a semiconductor device, a substrate processing step of forming a film in such a manner as to fill a recess formed in the surface of a substrate may be performed (for example, see Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Pamphlet of International Publication No. 2015 / 045099 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] An object of the present disclosure is to provide a technique capable of improving the filling characteristics of a film formed in a recess formed in the surface of a substrate.

[0008] Means for Solving the Problems

[0009] According to one aspect of the present disclosure, there is provided the following technique, which includes a step of forming a film in such a manner as to fill a recess formed in the surface of the substrate by performing a cycle including the following (a) to (d) a predetermined number of times,

[0010] (a) A step of supplying a dummy catalyst to the substrate in the processing chamber;

[0011] (b) A step of discharging the dummy catalyst remaining in the processing chamber;

[0012] (c) A step of supplying a raw material to the substrate in the processing chamber; and

[0013] (d) A step of discharging the raw material remaining in the processing chamber,

[0014] In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate is unsaturated.

[0015] Effects of the Invention

[0016] According to the present disclosure, it is possible to improve the filling characteristics of a film formed in a recess formed in the surface of a substrate. Brief Description of the Drawings

[0017] Figure 1A schematic configuration diagram of a vertical processing furnace in a substrate processing apparatus preferably used in one aspect of the present disclosure, and a diagram showing the processing furnace portion in a longitudinal cross-sectional view.

[0018] Figure 2 A schematic configuration diagram of a vertical processing furnace in a substrate processing apparatus preferably used in one aspect of the present disclosure, and Figure 1 a diagram showing the processing furnace portion in a cross-sectional view taken along line A-A

[0019] Figure 3 A schematic configuration diagram of a controller of a substrate processing apparatus preferably used in one aspect of the present disclosure, and a diagram showing the control system of the controller in a block diagram.

[0020] Figure 4 A diagram showing the gas supply sequence in a substrate processing step of one aspect of the present disclosure.

[0021] Figure 5 (a) of is a diagram showing the chemical structural formula of trimethylsilylamine, Figure 5 (b) of is a diagram showing the chemical structural formula of monochlorotrimethylsilylamine.

[0022] Figure 6 (a) of is a diagram showing the chemical structural formula of 1,3-disilapropane, Figure 6 (b) of is a diagram showing the chemical structural formula of 1,4-disilabutane, Figure 6 (c) of is a diagram showing the chemical structural formula of 1,3-disilabutane, Figure 6 (d) of is a diagram showing the chemical structural formula of 1,3,5-trisilapentane, Figure 6 (e) of is a diagram showing the chemical structural formula of 1,3,5-trisilacyclohexane, Figure 6 (f) of is a diagram showing the chemical structural formula of 1,3-disilacyclobutane.

[0023] Figure 7 (a) of is an enlarged cross-sectional view of a wafer surface after supplying a dummy catalyst into the processing chamber, Figure 7 (b) of is an enlarged cross-sectional view of the surface of a wafer after discharging the dummy catalyst remaining in the processing chamber, Figure 7 (c) of is an enlarged cross-sectional view of the surface of a wafer after supplying a raw material into the processing chamber. Detailed Description of the Invention

[0024] <One Aspect of the Present Disclosure>

[0025] Hereinafter, one aspect of the present disclosure will be mainly described using Figures 1 to 4 as an example.

[0026] (1) Configuration of the substrate processing apparatus

[0027] As Figure 1 shown in the figure, the processing furnace 202 has a heater 207 as a heating mechanism (temperature control unit). The heater 207 has a cylindrical shape and is vertically assembled by being supported on a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) a gas using heat.

[0028] Inside the heater 207, a reaction tube 203 is disposed concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. A processing chamber 201 is formed in the hollow portion of the reaction tube 203. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed inside the processing chamber 201.

[0029] Inside the processing chamber 201, nozzles 249a and 249b are respectively provided so as to penetrate the lower side wall of the reaction tube 203. Gas supply tubes 232a and 232b are respectively connected to the nozzles 249a and 249b.

[0030] On the gas supply tubes 232a and 232b, mass flow controllers (MFCs) 241a and 241b as flow controllers (flow control units) and valves 243a and 243b as on-off valves are respectively provided in order from the upstream side. Gas supply tubes 232c to 232f are respectively connected to the gas supply tubes 232a and 232b on the downstream side of the valves 243a and 243b. On the gas supply tubes 232c to 232f, MFCs 241c to 241f and valves 243c to 243f are respectively provided in order from the upstream side. The gas supply tubes 232a to 232f are made of a metal material such as SUS (stainless steel).

[0031] As Figure 2As shown, the nozzles 249a and 249b are respectively disposed in an annular space when viewed from above between the inner wall of the reaction tube 203 and the wafer 200 in such a manner that they stand upright from the lower part of the inner wall of the reaction tube 203 along the upper part and upward in the arrangement direction of the wafer 200. That is, in a region on the side of the wafer arrangement region where the wafers 200 are arranged and horizontally surrounding the wafer arrangement region, the nozzles 249a and 249b are respectively disposed along the wafer arrangement region. On the side surfaces of the nozzles 249a and 249b, gas supply holes 250a and 250b for supplying gas are respectively provided. The gas supply holes 250a and 250b are respectively opened in a manner facing the center of the reaction tube 203 and can supply gas to the wafer 200. A plurality of the gas supply holes 250a and 250b are provided in the range from the lower part to the upper part of the reaction tube 203. The nozzles 249a and 249b are made of a heat-resistant material such as quartz or SiC, for example.

[0032] From the gas supply pipe 232a, a first raw material (first raw material gas) containing silicon (Si) (which is the main element constituting the film formed on the wafer 200) is supplied into the processing chamber 201 via the MFC241a, the valve 243a, and the nozzle 249a. The raw material gas refers to a raw material in a gaseous state. For example, it is a gas obtained by vaporizing a raw material that is in a liquid state at normal temperature and pressure, a raw material that is in a gaseous state at normal temperature and pressure, and the like. As the first raw material gas, for example, trimethylsilylamine (N(SiH3)3, abbreviated as: TSA) gas, which is a gas containing a chemical bond between Si and nitrogen (N) (Si-N bond) and does not contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl, can be used. As shown in Figure 5 the chemical structural formula shown in (a) of, TSA is a substance containing an Si-N bond and a chemical bond between Si and hydrogen (H) (Si-H bond), and contains 3 Si-N bonds and 9 Si-H bonds in one molecule. TSA is also a raw material that does not contain halogens such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). Three Si atoms are bonded to one N (central element) in TSA. TSA also functions as an Si source and an N source.

[0033] A dummy catalyst (dummy catalyst gas) is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b. As the dummy catalyst gas, for example, a gas of boron trichloride (BCl3), which is a kind of haloborane containing boron (B) and chlorine (Cl) as a halogen, can be used. The BCl3 gas plays a catalytic role in promoting film formation on the wafer 200 in the substrate processing step described later. Here, a "catalyst" refers to a substance that does not change itself before and after a chemical reaction but changes the reaction rate. The BCl3 gas in the reaction system of this embodiment has a catalytic effect of changing the reaction rate and the like, but sometimes it changes itself before and after the chemical reaction. For example, in the case of the BCl3 gas, when reacting with the TSA gas, sometimes a part of the molecular structure decomposes and it changes itself before and after the chemical reaction. That is, the BCl3 gas in the reaction system of this embodiment has a catalytic effect and is not strictly a "catalyst". Thus, in this specification, a substance that acts like a "catalyst" but changes itself before and after a chemical reaction is called a "dummy catalyst".

[0034] A second raw material (second raw material gas) containing Si (which is the main element constituting the film formed on the wafer 200) is supplied into the processing chamber 201 from the gas supply pipe 232c via the MFC 241c, the valve 243c, the gas supply pipe 232a, and the nozzle 249a. As the second raw material gas, for example, 1,4-disilabutane (SiH3CH2CH2SiH3, abbreviated as: 1,4-DSB) gas, which is a gas containing a chemical bond between Si and carbon (Si-C bond) and no halogen, can be used. As shown in the chemical structural formula of (b) in Figure 6 , 1,4-DSB is a substance containing Si-C bonds, Si-H bonds, and chemical bonds between C and H (C-H bonds), etc., and contains 2 Si-C bonds, 6 Si-H bonds, and 4 C-H bonds in one molecule. 1,4-DSB contains ethylene (C2H4) as an alkylene group and is also a raw material without an alkyl group described later. Among the 4 connecting bonds of C in 1,4-DSB, 1 is configured as an Si-C bond and 2 are configured as C-H bonds. In this specification, 1,4-DSB is also abbreviated as DSB. DSB acts as an Si source and a C source.

[0035] A reaction body (reaction gas), for example, an oxygen (O)-containing gas, is supplied into the processing chamber 201 from the gas supply pipe 232d via the MFC 241d, the valve 243d, the gas supply pipe 232b, and the nozzle 249b. The O-containing gas acts as an oxidizing agent (oxidizing gas), that is, an O source. As the O-containing gas, for example, oxygen (O2) gas can be used.

[0036] Nitrogen (N2) gas, which is an inert gas, is supplied into the processing chamber 201 from the gas supply pipes 232e and 232f via the MFCs 241e and 241f, the valves 243e and 243f, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b. The N2 gas functions as a purge gas, a carrier gas, a dilution gas, etc.

[0037] The raw material supply system is mainly composed of the gas supply pipes 232a and 232c, the MFCs 241a and 241c, and the valves 243a and 243c. The dummy catalyst supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The reaction body supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The inert gas supply system is mainly composed of the gas supply pipes 232e and 232f, the MFCs 241e and 241f, and the valves 243e and 243f.

[0038] Any or all of the above various supply systems can be configured as an integrated supply system 248 obtained by integrating the valves 243a to 243f, the MFCs 241a to 241f, etc. The integrated supply system 248 is configured as follows: It is connected to each of the gas supply pipes 232a to 232f, and the controller 121 described later is used to control the supply operation of various gases into the gas supply pipes 232a to 232f, that is, the opening and closing operations of the valves 243a to 243f, the flow rate adjustment operations using the MFCs 241a to 241f, etc. The integrated supply system 248 is configured as an integrated unit of an integral type or a separable type, so that it can be disassembled and assembled in units of the integrated unit with respect to the gas supply pipes 232a to 232f, etc., and the integrated supply system 248 can be maintained, replaced, added, etc. in units of the integrated unit.

[0039] Below the side wall of the reaction tube 203, an exhaust pipe 231 for exhausting (venting) the atmosphere in the processing chamber 201 is connected. On the exhaust pipe 231, a vacuum pump 246 as a vacuum exhaust device is connected via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulation unit). The APC valve 244 is configured such that by opening and closing the valve in a state where the vacuum pump 246 is operating, vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 can be performed, and further, by regulating the valve opening based on the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is operating, the pressure in the processing chamber 201 can be regulated. The exhaust system (venting system) is mainly composed of the exhaust pipe 231, the pressure sensor 245, and the APC valve 244. It is also possible to consider including the vacuum pump 246 in the exhaust system.

[0040] Below the reaction tube 203, a seal cover 219 as a furnace mouth cover body capable of hermetically closing the lower end opening of the reaction tube 203 is provided. The seal cover 219 is made of a metal material such as SUS, for example, and is formed in a disc shape. On the upper surface of the seal cover 219, an O-ring 220 as a sealing member that abuts against the lower end of the reaction tube 203 is provided. Below the seal cover 219, a rotation mechanism 267 for rotating a susceptor 217 described later is provided. The rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS, for example, and penetrates the seal cover 219 and is connected to the susceptor 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The seal cover 219 is configured to be lifted and lowered in the vertical direction by a susceptor elevator 115 as a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is configured as a transfer device (transfer mechanism) for transferring the wafer 200 into and out of the processing chamber 201 by lifting and lowering the seal cover 219.

[0041] The susceptor 217 as a substrate support member is configured such that a plurality of (for example, 25 to 200) wafers 200 are arranged in a horizontal posture and centered with respect to each other in the vertical direction and supported in multiple layers, that is, the plurality of wafers 200 are arranged at intervals. The susceptor 217 is made of a heat-resistant material such as quartz or SiC, for example. Below the susceptor 217, a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in a horizontal posture and in multiple layers.

[0042] Inside the reaction tube 203, a temperature sensor 263 serving as a temperature detector is provided. 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.

[0043] As Figure 3 shown, the controller 121 as a control unit (control means) is configured in the form of a computer having 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 perform data exchange with the CPU 121a via an internal bus 121e. An input / output device 122 configured in the form of a touch panel or the like is connected to the controller 121.

[0044] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), or the like. Inside the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe including steps, conditions, etc. of a film formation process described later, etc. are stored in a readable manner. The process recipe is combined in such a way that the controller 121 can execute each step in the film formation process described later and obtain a specified result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are also collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. When the term "program" is used in this specification, there are cases where it includes only the recipe alone, only the control program alone, or both. The RAM 121b is configured as a storage area (working area) that temporarily holds programs, data, etc. read by the CPU 121a.

[0045] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, susceptor elevator 115, etc.

[0046] The CPU 121a is configured as follows: It can read and execute a control program from the storage device 121c, and read a process from the storage device 121c according to the input of an operation command from the input / output device 122 or the like. The CPU 121a is configured as follows: It can control various gas flow adjustment operations performed by the MFCs 241a to 241f, the opening and closing operations of the valves 243a to 243f, the opening and closing operations of the APC valve 244, and the pressure adjustment operation performed 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 susceptor 217 using the rotation mechanism 267, the lifting operation of the susceptor 217 using the susceptor elevator 115, etc. according to the content of the read process.

[0047] The controller 121 can be configured by installing the above program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, semiconductor memories such as USB memories, etc. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, they will also be collectively and simply referred to as recording media. When using the term recording medium in this specification, there are cases where only the storage device 121c is included alone, cases where only the external storage device 123 is included alone, or cases where both are included. It should be noted that providing a program to a computer can also be performed without using the external storage device 123, but using communication means such as the Internet or dedicated lines.

[0048] (2) Substrate processing step

[0049] An example of the substrate processing sequence, i.e., the film formation sequence, for forming a silicon nitride film (SiN film) on a wafer 200 as a substrate using the above substrate processing apparatus as one step of the semiconductor device manufacturing process will be described using Figure 4 as an example. It should be noted that in this mode, an example in which a substrate having recesses such as grooves and holes formed on its surface is used as the wafer 200 will be described. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0050] In Figure 4 the substrate processing sequence shown, it includes repeating the cycle including the following steps A to D a specified number of times (n times, n is an integer of 1 or more) to form a SiN film in a manner of filling the recesses formed on the surface of the wafer 200 as a film,

[0051] Step A: Supply BCl3 gas as a dummy catalyst to the wafer 200 in the processing chamber 201;

[0052] Step B, discharging the BCl3 gas remaining in the processing chamber 201;

[0053] Step C, supplying the TSA gas as a raw material to the wafer 200 in the processing chamber 201; and,

[0054] Step D, discharging the TSA gas remaining in the processing chamber 201,

[0055] In Step A, the BCl3 is adsorbed onto the surface of the wafer 200 under the condition that the chemisorption of BCl3 onto the surface of the wafer 200 is unsaturated.

[0056] In this specification, for convenience, sometimes Figure 4 the gas supply sequence shown is presented as follows. The same expression is also used in the following modification examples and descriptions of other modes.

[0057]

[0058] When the term "wafer" is used in this specification, there are cases where it represents the wafer itself and cases where it represents a laminate of the wafer and a specified layer or film formed on its surface. When the term "surface of the wafer" is used in this specification, there are cases where it represents the surface of the wafer itself and cases where it represents the surface of a specified layer or the like formed on the wafer. When it is described in this specification that "a specified layer is formed on the wafer", there are cases where it represents directly forming a specified layer on the surface of the wafer itself and cases where it represents forming a specified layer on top of a layer or the like formed on the wafer. The case of using the term "substrate" in this specification has the same meaning as the case of using the term "wafer".

[0059] (Wafer filling and susceptor loading)

[0060] A plurality of wafers 200 are loaded (wafer filling) into the susceptor 217. Then, as Figure 1 shown, the susceptor 217 supporting a plurality of wafers 200 is lifted by the susceptor elevator 115 and carried into the processing chamber 201 (susceptor loading). In this state, the seal cover 219 is in a state of sealing the lower end of the reaction tube 203 by means of the O-ring 220.

[0061] (Pressure adjustment and temperature adjustment)

[0062] Vacuum exhaust (pressure reduction exhaust) is performed using a vacuum pump 246 so that the inside of the processing chamber 201 (i.e., the space where the wafer 200 exists) becomes a desired pressure (degree of vacuum). At this time, the pressure inside the processing chamber 201 is measured using a pressure sensor 245, and feedback control (pressure adjustment) is performed on the APC valve 244 based on the measured pressure information. In addition, heating is performed using a heater 207 so that the wafer 200 inside the processing chamber 201 becomes a desired temperature. At this time, feedback control (temperature adjustment) is performed on the energization of the heater 207 based on the temperature information detected by the temperature sensor 263 so that a desired temperature distribution is achieved inside the processing chamber 201. In addition, rotation of the wafer 200 using the rotation mechanism 267 is started. The operation of the vacuum pump 246, the heating, and the rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0063] (Film formation step)

[0064] Then, the following steps A to D are sequentially performed.

[0065] [Step A]

[0066] In this step, BCl3 gas is supplied to the wafer 200 inside the processing chamber 201. Specifically, the valve 243b is opened, and BCl3 gas flows into the gas supply pipe 232b. The BCl3 gas is flow-regulated by the MFC241b, supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust pipe 231. At this time, BCl3 gas is supplied to the wafer 200. At this time, the valves 243e and 243f can be opened, and N2 gas flows into the gas supply pipes 232e and 232f.

[0067] In this step, BCl3 gas is supplied to the wafer 200 in such a manner that the chemisorption of BCl3 on the surface of the wafer 200 is unsaturated. By supplying BCl3 gas to the wafer 200 under such conditions, BCl3 can be adsorbed on the outermost surface of the wafer 200 without saturating the chemisorption of BCl3 on the outermost surface of the wafer 200. As a result, as shown in (a) of Figure 7 , a layer containing an adsorbed component of BCl3, that is, a layer containing B and Cl, can be formed as the first layer (initial layer) on the wafer 200, that is, inside the recess formed on the wafer 200. It should be noted that at this time, it is further preferable to supply BCl3 gas under conditions that can suppress the decomposition (gas-phase decomposition), that is, thermal decomposition, of BCl3 gas in the gas phase inside the processing chamber 201. Thereby, it is easy to achieve the following various conditions and adsorption states.

[0068] In Figure 7In (a) of [description], the ○ mark represents the physically adsorbed component of BCl3, and the ● mark represents the chemically adsorbed component of BCl3. The physically adsorbed component of BCl3 refers to BCl3 physically adsorbed on the wafer 200. The chemically adsorbed component of BCl3 refers to the substance formed when B contained in BCl3 is chemically adsorbed on the wafer 200. When B contained in BCl3 is chemically adsorbed on the surface of the wafer 200, most of the Cl bonded to B contained in BCl3 is maintained, but a part of Cl detaches. Compared with the adsorption state of the physically adsorbed component of BCl3, the adsorption state of the chemically adsorbed component of BCl3 is stable, and when performing step B described later, it becomes an adsorption state that is more difficult to detach from the surface of the wafer 200 than the physically adsorbed component of BCl3.

[0069] These substances (physically adsorbed component and chemically adsorbed component of BCl3) adsorbed on the surface of the wafer 200 function as a pseudo-catalyst for causing a film-forming reaction (formation reaction of the second layer described later) on the surface of the wafer 200 in step C described later. Hereinafter, for convenience, these substances that function as a pseudo-catalyst are also referred to as BCl x (x is 1 to 3). In addition, the first layer that functions as a pseudo-catalyst is also referred to as a pseudo-catalyst layer.

[0070] As described above, in this step, BCl3 is adsorbed on the surface of the wafer 200 under the condition that the chemical adsorption of BCl3 on the surface of the wafer 200 becomes unsaturated. As Figure 7 shown in (a) of [description], the adsorption component of BCl3 on the surface of the wafer 200 in this step includes at least the physically adsorbed component. It should be noted that, as shown in this figure, the adsorption component of BCl3 on the surface of the wafer 200 in this step may include both the physically adsorbed component and the chemically adsorbed component. In addition, depending on the conditions, the adsorption component of BCl3 on the surface of the wafer 200 in this step may not include the chemically adsorbed component but include the physically adsorbed component.

[0071] It should be noted that this step can be performed under the condition that the physically adsorbed component of BCl3 exists in both the upper and lower parts of the recess formed on the surface of the wafer 200. In this case, in each of the upper and lower parts of the recess formed on the surface of the wafer 200, the adsorption component of BCl3 on the surface of the wafer 200 in this step includes at least the physically adsorbed component.

[0072] In addition, this step can be performed under the condition that both the physically adsorbed component and the chemically adsorbed component of BCl3 exist in both the upper and lower parts of the recess formed on the surface of the wafer 200. In this case, in each of the upper and lower parts of the recess formed on the surface of the wafer 200, the adsorption component of BCl3 on the surface of the wafer 200 in this step includes both the physically adsorbed component and the chemically adsorbed component.

[0073] Alternatively, this step can be carried out under the condition that the physically adsorbed component of BCl3 exists in both the upper and lower parts of the recess formed on the surface of the wafer 200, while the chemically adsorbed component of BCl3 does not exist in both. In this case, in each of the upper and lower parts of the recess formed on the surface of the wafer 200, the adsorbed component of BCl3 on the surface of the wafer 200 in this step includes the physically adsorbed component and does not include the chemically adsorbed component.

[0074] Alternatively, in this step, BCl3 gas can be supplied to the wafer 200 under the condition that the adsorption reaction of BCl3 on the surface of the wafer 200 becomes the rate-determining step of the reaction. Alternatively, in this step, BCl3 gas can be supplied to the wafer 200 under the condition that film formation does not occur when BCl3 gas exists alone in the processing chamber 201. In these cases, for example, excessive consumption of BCl3 gas at the upper part of the recess formed on the surface of the wafer 200 can be suppressed, and BCl3 gas can be reliably supplied to the lower part of the recess. As a result, the first layer can be completely formed over the entire range from the upper part to the lower part of the recess formed on the surface of the wafer 200.

[0075] As the processing conditions in this step, the following can be exemplified:

[0076] BCl3 gas supply flow rate: 1 - 5000 sccm, preferably 5 - 500 sccm

[0077] N2 gas supply flow rate (each gas supply pipe): 0 - 10000 sccm

[0078] Each gas supply time: 1 - 60 seconds, preferably 1 - 30 seconds

[0079] Processing temperature: 200 - 500 °C, preferably 300 - 450 °C

[0080] Processing pressure: 20 - 1000 Pa, preferably 30 - 500 Pa.

[0081] It should be noted that the expression of the numerical range such as "200 - 500 °C" in this specification means that the lower limit value and the upper limit value are included in this range. Therefore, for example, "200 - 500 °C" means "200 °C or higher and 500 °C or lower". The same applies to other numerical ranges.

[0082] By appropriately adjusting each processing condition within such a range of processing conditions, the above-mentioned various conditions can be achieved, and the above-mentioned various adsorption states of BCl3 in the recess can be achieved.

[0083] It should be noted that if the treatment temperature is less than 200 °C, BCl3 is sometimes difficult to adsorb on the surface of the wafer 200, and there is a case where the film formation rate decreases. By setting the treatment temperature to 200 °C or higher, this can be eliminated. By setting the treatment temperature to 300 °C or higher, this can be reliably eliminated.

[0084] If the treatment temperature exceeds 500 °C, the following situation occurs: at the upper part of the concave portion formed on the surface of the wafer 200, etc., the BCl3 gas is excessively consumed, and it is difficult to supply the BCl3 gas to the lower part of the concave portion. In this case, it is sometimes difficult to achieve the above-described various adsorption states of BCl3 into the concave portion. By setting the treatment temperature to 500 °C or lower, this can be eliminated. By setting the treatment temperature to 450 °C or lower, this can be reliably eliminated.

[0085] If the treatment pressure is less than 20 Pa, there is a case where it is difficult to efficiently supply (reach) the BCl3 gas to the lower part of the concave portion formed on the surface of the wafer 200. By setting the treatment pressure to 20 Pa or higher, this can be eliminated. By setting the treatment pressure to 30 Pa or higher, this can be reliably eliminated.

[0086] If the treatment pressure exceeds 1000 Pa, there is a case where the chemisorption of BCl3 on the surface of the wafer 200 is likely to saturate. By setting the treatment pressure to 1000 Pa or lower, this can be eliminated. By setting the treatment pressure to 500 Pa or lower, this can be reliably eliminated.

[0087] As the dummy catalyst gas, in addition to the BCl3 gas, boron trifluoride (BF3) gas, boron tribromide (BBr3) gas, boron triiodide (BI3) gas, trimethylborane (B(CH3)3) gas, triethylborane (B(C2H5)3) gas, etc. can also be used.

[0088] As the inert gas, in addition to the N2 gas, noble gases such as Ar gas, He gas, Ne gas, Xe gas, etc. can also be used. This is the same in the subsequent steps B to D, etc.

[0089] [Step B]

[0090] After forming the first layer on the wafer 200, the valve 243b is closed to stop supplying BCl3 gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to discharge the residual BCl3 gas and the like in the processing chamber 201. At this time, the valves 243e and 243f are opened to supply N2 gas into the processing chamber 201. The N2 gas acts as a purge gas. Thereby, the floating BCl3 gas in the processing chamber 201 can be removed. Moreover, thereby, the subsequent step C can be performed in a state where the BCl3 gas does not float in the processing chamber 201 (non-floating state).

[0091] In this embodiment, as described later, this step can be performed under the condition that at least a part of the physically adsorbed component of BCl3 on the surface of the wafer 200 remains. For example, this step can be performed under the condition that at least a part of the physically adsorbed component of BCl3 on the upper part of the recess formed on the surface of the wafer 200 is detached, and at least a part of the physically adsorbed component of BCl3 on the lower part of the recess remains. Additionally, for example, this step can be performed under the condition that the amount of detachment of the physically adsorbed component of BCl3 on the upper part of the recess formed on the surface of the wafer 200 is more than the amount of detachment of the physically adsorbed component of BCl3 on the lower part of the recess.

[0092] By performing this step under such conditions, as shown in (b) of Figure 7 , at least a part of the physically adsorbed component of BCl3 on the surface of the wafer 200 can remain. Additionally, the amount of the physically adsorbed component of BCl3 remaining on the lower part of the recess formed on the surface of the wafer 200 can be made more than the amount of the physically adsorbed component of BCl3 remaining on the upper part of the recess.

[0093] As the processing conditions in this step, the following can be exemplified:

[0094] N2 gas supply flow rate: 1 - 10000 sccm

[0095] N2 gas supply time: 1 - 60 seconds, preferably 5 - 30 seconds

[0096] Processing pressure: 1 - 1000 Pa, preferably 30 - 500 Pa, more preferably 100 - 500 Pa.

[0097] Other processing conditions are the same as those in step A.

[0098] By appropriately adjusting each processing condition within such a processing condition range, the above-mentioned various conditions can be achieved, and the state where the physically adsorbed component of BCl3 remains in the recess can be achieved.

[0099] If the processing pressure is less than 10 Pa, it may be difficult to leave the physically adsorbed component of BCl3 on the surface of the wafer 200. For example, there may be a situation where it is difficult to achieve the detachment of at least a part of the physically adsorbed component of BCl3 from the upper part of the recess formed on the surface of the wafer 200 and the retention of at least a part of the physically adsorbed component of BCl3 in the lower part of the recess. By setting the processing pressure to 10 Pa or more, this can be eliminated. By setting the processing pressure to 30 Pa or more, more preferably 100 Pa or more, this can be reliably eliminated.

[0100] If the processing pressure exceeds 1000 Pa, there may be a situation where it is difficult to discharge BCl3 gas or the like from the processing chamber 201, and in the subsequent step C, impurities are generated in the processing chamber 201 due to the gas-phase reaction between the BCl3 gas floating in the processing chamber 201 and the TSA gas. By setting the processing pressure to 1000 Pa or less, this can be eliminated. By setting the processing pressure to 500 Pa or less, this can be reliably eliminated.

[0101] [Step C]

[0102] In this step, in a state where BCl3 gas does not float in the processing chamber 201, TSA gas is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200. Specifically, the opening and closing control of valves 243a, 243e, and 243f is performed in the same manner as the opening and closing control of valves 243b, 243e, and 243f in step A. The flow rate of the TSA gas is controlled by the MFC241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the TSA gas is supplied to the wafer 200.

[0103] As the processing conditions in this step, the following can be exemplified:

[0104] TSA gas supply flow rate: 1 - 2000 sccm

[0105] TSA gas supply time: 1 - 300 seconds

[0106] Processing pressure: 1 - 2000 Pa.

[0107] Other processing conditions are the same as those in step A.

[0108] By supplying the TSA gas to the wafer 200 under the above conditions, using the BCl included in the first layer xA pseudo-catalytic reaction occurs due to the pseudo-catalysis, and thereby, a part of the molecular structure of TSA can be decomposed. Moreover, substances generated due to the decomposition of a part of the molecular structure of TSA, such as intermediates containing Si-N bonds, can be adsorbed (chemisorbed) onto the surface of the wafer 200. Thus, as shown in (c) of Figure 7 a silicon nitride layer (SiN layer) as a layer containing Si and N can be formed in the recess formed on the wafer 200, i.e., inside the recess formed on the surface of the wafer 200, as the second layer. In Figure 7 (c) of

[0109] As shown in (a) of Figure 5 , the TSA gas has the property of being difficult to adsorb onto the surface of the wafer 200 because it is capped with Si-H bonds. However, by utilizing the pseudo-catalysis of the above-mentioned BCl x , a part of its molecular structure is decomposed (for example, a part of the Si-H bond is cut), and it becomes adsorbed onto the surface of the wafer 200 efficiently. That is, the formation of the second layer is carried out by the pseudo-catalysis of BCl x contained in the first layer, and the surface reaction (rather than the gas-phase reaction) becomes the main body and proceeds. It should be noted that at this time, since there is no BCl3 gas floating in the processing chamber 201, the formation of the second layer can be reliably achieved by the surface reaction rather than the gas-phase reaction.

[0110] Here, as described above, in step B, at least a part of the physical adsorption component of BCl3 on the surface of the wafer 200 is left, and the remaining amount of the physical adsorption component of BCl3 in the lower part of the recess formed on the surface of the wafer 200 is more than the remaining amount of the physical adsorption component of BCl3 in the upper part of the recess. Thus, the pseudo-catalysis of BCl x generated in the lower part of the recess formed on the surface of the wafer 200 can be stronger than the pseudo-catalysis of BCl x generated in the upper part of the recess. Moreover, thereby, the formation reaction of the second layer occurring in the lower part of the recess formed on the wafer 200 can be more easily carried out than the formation reaction of the second layer occurring in the upper part of the recess. As a result, as shown in (c) of Figure 7 , the thickness of the second layer formed in the lower part of the recess formed on the surface of the wafer 200 can be thicker than the thickness of the second layer formed in the upper part of the recess.

[0111] Note that, in this step, the TSA gas can be supplied to the wafer 200 under the condition that film formation is not performed when the TSA gas alone exists in the processing chamber 201. By performing this step under such conditions, the formation of the second layer by surface reaction rather than gas-phase reaction can be more reliably achieved. As a result, the formation rate of the second layer in the lower part of the recess formed on the wafer 200 can be more reliably greater than the formation rate of the second layer in the upper part of the recess.

[0112] Note that, under the above conditions, at least a part of the Si-N bond of the TSA gas is maintained without being broken. Therefore, the second layer becomes a layer containing Si and N in the form of Si-N bonds. In addition, under the above conditions, most of the BCl contained in the first layer x is consumed when reacting with the TSA gas. As a result, the amount of BCl contained in the second layer x is reduced to the impurity level. Since the second layer contains B at the impurity level, the second layer can also be referred to as a B-containing SiN layer. In addition to B, the second layer may also contain Cl, H, etc. as impurities.

[0113] As the first raw material, in addition to the TSA gas, monochlorosilylamine (N(SiH3)2SiH2Cl) gas, etc. can also be used. Figure 5 The chemical structural formula of monochlorosilylamine is shown in (b) of. Monochlorosilylamine contains 3 Si-N bonds in one molecule and is a substance without an alkyl group. As Figure 5 shown in (a) of Figure 5 (b) of, these substances contain Si-H bonds and Si-N bonds. In addition, these substances do not contain at all the following bonds that can cause a reduction in the dry-etch resistance, wet-etch resistance, ashing resistance, etc. (hereinafter, these will also be collectively referred to as processing resistance) of the SiN film formed on the wafer 200, for example, a bond between Cs in which 2 or more, 3 or more, or all (4) of the connecting bonds are bonded to C (hereinafter, this bond will be abbreviated as C-C bond), a chemical bond between C and O (C-O bond), a chemical bond between Si and an alkyl group (R) (Si-R bond), a chemical bond between N and H (N-H bond), a chemical bond between N and O (N-O bond).

[0114] [Step D]

[0115] After the second layer is formed on the wafer 200, the valve 243a is closed to stop the supply of the TSA gas into the processing chamber 201. Then, through the same processing steps as in Step B, the gas remaining in the processing chamber 201 is exhausted from the processing chamber 201. Thereby, the TSA gas floating in the processing chamber 201 can be removed. Moreover, thereby, the next cycle of Step A can be performed in a state where the TSA gas does not float in the processing chamber 201 (non-floating state).

[0116] As the processing conditions in this step, the following can be exemplified:

[0117] N2 gas supply flow rate: 10 to 10000 sccm

[0118] N2 gas supply time: 1 to 300 seconds

[0119] Processing pressure: 0.1 to 100 Pa.

[0120] Other processing conditions are the same as those in step A.

[0121] [Execute specified number of times]

[0122] By performing the cycles of the above steps A to D non-simultaneously, i.e., asynchronously, for a specified number of times (n times, where n is an integer of 1 or more), a SiN film with a specified composition and a specified film thickness can be formed in a manner that fills the recesses formed on the surface of the wafer 200. This film contains Si and N in the form of Si-N bonds, and in addition, does not contain bonds that can cause a reduction in processability, so it becomes a film with excellent processability.

[0123] The above cycles are preferably repeated multiple times. That is, preferably, the thickness of the SiN layer formed by performing one cycle of the above is less than the desired film thickness, and the above cycles are repeated multiple times until the film thickness of the SiN film formed by laminating the SiN layers becomes the desired film thickness. For the above reasons, in the film formation step, the formation rate of the SiN layer in the lower part of the recess formed on the wafer 200 is greater than the formation rate of the SiN layer in the upper part of the recess. Therefore, by repeating the above cycles multiple times, a SiN film can be formed from the lower part to the upper part from the inside of the recess formed on the surface of the wafer 200 in a bottom-up manner. As a result, the SiN film filling the recess becomes a film with excellent filling characteristics without internal voids and seams.

[0124] (Post-purge and atmospheric pressure recovery)

[0125] After the film formation step is completed, N2 gas is supplied into the processing chamber 201 from each of the gas supply pipes 232e and 232f, and discharged from the exhaust pipe 231. Thereby, the inside of the processing chamber 201 is purged, and gases, by-products, etc. remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (post-purge). Then, the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure recovery).

[0126] (Cassette unloading and wafer removal)

[0127] Then, the seal cover 219 is lowered by the susceptor elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafer 200 is carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 (susceptor unloading) while being supported by the susceptor 217. The wafer 200 after the film formation step is taken out from the susceptor 217 (wafer takeout).

[0128] (3) Effects brought by this method

[0129] According to this method, one or more of the following effects can be obtained.

[0130] (a) According to this method, it is possible to make the formation rate of the SiN layer in the lower part of the recess formed on the wafer 200 greater than the formation rate of the SiN layer in the upper part of the recess. As a result, it is possible to form the SiN film from the bottom up in the recess, and as a result, the SiN film formed in the recess can be a film with excellent filling characteristics that does not contain voids and seams.

[0131] The reason is that in step A, BCl3 is adsorbed on the surface of the wafer 200 under the condition that the chemisorption of BCl3 on the surface of the wafer 200 becomes unsaturated. Assuming that in step A, BCl3 is adsorbed on the surface of the wafer 200 under the condition that the chemisorption of BCl3 on the surface of the wafer 200 is saturated, BCl3 is chemisorbed on most of the adsorption sites in the recess formed on the surface of the wafer 200, and a chemisorbed layer of BCl3 is uniformly formed on the entire surface including the upper and lower parts of the recess. The chemisorbed component of BCl3 is difficult to be detached under the action of the purge gas. Therefore, in this case, even if step B is carried out, the chemisorbed component of BCl3 remains uniformly in the upper and lower parts of the recess. As a result, in step C, it is difficult to make the false catalytic action of BCl x produced in the lower part of the recess stronger than the false catalytic action of BCl x produced in the upper part of the recess. As a result, it is difficult to obtain the above effects.

[0132] In contrast, according to this method, in step A, since the chemisorption of BCl3 in the recess formed on the surface of the wafer 200 is unsaturated, a chemisorbed layer of BCl3 is not uniformly formed on the entire surface including the upper and lower parts of the recess, and the adsorption sites that are not chemisorbed with BCl3 are maintained. In step B, the amount of detachment, that is, the remaining amount, of the adsorbed component of BCl3 can be changed as described above in the upper and lower parts of the recess. As a result, in step C, it is possible to make the false catalytic action of BCl x produced in the lower part of the recess stronger than the false catalytic action of BCl x produced in the upper part of the recess, and the above effects can be appropriately obtained.

[0133] (b) According to this method, it is possible to fill the recess formed on the surface of the wafer 200 with the SiN film without additionally performing an etching step outside the film formation step. That is, it is possible to avoid a reduction in the productivity of the substrate processing including the filling process of the film into the recess.

[0134] (c) According to this method, it is possible to form a SiN film formed on the wafer 200 into a film excellent in processability, which contains Si and N in the form of Si-N bonds and does not contain bonds that can be factors for reducing processability.

[0135] (d) The above effects can be similarly obtained in the case of using the above-described pseudo-catalyst gas other than BCl3 gas, the case of using the above-described first raw material gas other than TSA gas, and the case of using the above-described inert gas other than N2 gas.

[0136] (4) Modification example

[0137] The substrate processing sequence in this method is not limited to Figure 4 the method shown, and can be changed as in the following modification examples. In addition, these modification examples can be arbitrarily combined. It should be noted that, unless otherwise specified, the processing steps and processing conditions in each step of each modification example are the same as those in each step of the above substrate processing sequence.

[0138] (Modification example 1)

[0139] As in the following film formation sequence, a cycle having the following steps E and F in addition to steps A to D can be specified a predetermined number of times (n times, n is an integer of 1 or more) to form a silicon carbonitride film (SiCN film) as a film in such a manner as to fill the recess formed on the surface of the wafer 200. Step E is a step of supplying DSB gas as a second raw material to the wafer 200 in the processing chamber 201, and step F is a step of discharging the remaining DSB gas in the processing chamber 201.

[0140]

[0141] In step E, a DSB gas is supplied to the wafer 200 in the processing chamber 201, that is, to the second layer formed on the wafer 200. Specifically, the opening and closing control of valves 243c, 243e, and 243f is performed in the same steps as the opening and closing control of valves 243b, 243e, and 243f in step A. The flow rate of the DSB gas is controlled by the MFC241c, supplied into the processing chamber 201 via the gas supply pipe 232a and the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the DSB gas is supplied to the wafer 200. The processing conditions in step E can be the same as those in step C, for example. By supplying the DSB gas to the wafer 200 under such processing conditions, a pseudo-catalytic reaction occurs under the pseudo-catalysis of BCl x contained in the second layer. As a result, substances generated by the decomposition of a part of the molecular structure of DSB, such as intermediates containing Si-C bonds, can be adsorbed (chemisorbed) on the second layer. Thus, a silicon carbonitride layer (SiCN layer) as a layer containing Si, C, and N can be formed in the recesses formed on the wafer 200 or the like as the third layer.

[0142] As the second raw material, in addition to the DSB gas, 1,3-disilapropane (SiH3CH2SiH3, abbreviated as: 1,3-DSP) gas, 1,3-disilabutane (SiH3CH2SiH2CH3, abbreviated as: 1,3-DSB) gas, 1,3,5-trisilapentane (SiH3CH2SiH2CH2SiH3, abbreviated as: 1,3,5-TSP) gas, 1,3,5-trisilacyclohexane (SiH2CH2SiH2CH2SiH2CH2, abbreviated as: 1,3,5-TSCH) gas, 1,3-disilacyclobutane (SiH2CH2SiH2CH2, abbreviated as: 1,3-DSCB) gas, trimethylsilylmethane ((SiH3)3CH) gas, etc. can also be used. Figure 6 The chemical structural formula of 1,3-DSP is shown in (a) of Figure 6 The chemical structural formula of 1,3-DSB is shown in (c) of Figure 6 The chemical structural formula of 1,3,5-TSP is shown in (d) of Figure 6 The chemical structural formula of 1,3,5-TSCH is shown in (e) of Figure 6 The chemical structural formula of 1,3-DSCB is shown in (f) of. These substances contain Si-H bonds and Si-C bonds and are completely halogen-free. In addition, these substances are substantially or completely free of C-C bonds, C-O bonds, Si-R bonds, N-H bonds, and N-O bonds that can be factors reducing the processability of the SiCN film formed on the wafer 200.

[0143] The processing steps and conditions in step F can be the same as those in step D. By step F, the DSB gas floating in the processing chamber 201 can be removed.

[0144] In this modification example, the same effect as that Figure 4 shown in the film formation sequence can also be obtained. In addition, according to this modification example, the SiCN film formed on the wafer 200 can be made into a film with excellent processability, which contains Si and N in the form of Si-N bonds, contains Si and C in the form of Si-C bonds, and does not contain bonds that can be factors reducing the processability.

[0145] (Modification example 2)

[0146] As shown in the following film formation sequence, in addition to steps A to D, the cycles including the following step G and step H can be performed a specified number of times (n times, n is an integer of 1 or more) to fill the recesses formed on the surface of the wafer 200, and a silicon oxynitride film (SiON film) is formed as the film. Step G is a step of supplying O2 gas as a reaction body to the wafer 200 in the processing chamber 201, and step H is a step of discharging the remaining O2 gas in the processing chamber 201.

[0147]

[0148] In step G, O2 gas is supplied to the wafer 200 in the processing chamber 201, that is, the second layer formed on the wafer 200. Specifically, the opening and closing control of valves 243d, 243e, and 243f is performed by the same steps as the opening and closing control of valves 243b, 243e, and 243f in step A. The flow rate of the O2 gas is controlled by MFC241d, supplied into the processing chamber 201 via the gas supply pipe 232b and the nozzle 249b, and exhausted from the exhaust pipe 231. At this time, O2 gas is supplied to the wafer 200. The processing conditions in step G can be the same as those in step C, for example. By supplying O2 gas to the wafer 200 under such processing conditions, at least a part of the second layer can be oxidized (modified). Thus, a silicon oxynitride layer (SiON layer) containing Si, O, and N can be formed as the third layer in the recesses formed on the wafer 200, etc.

[0149] As the reaction body (O-containing gas), in addition to O2 gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, ozone (O3) gas, hydrogen peroxide (H2O2) gas, water vapor (H2O gas), O2 gas + hydrogen (H2) gas, etc. can also be used.

[0150] The processing steps and conditions in step H can be the same as those in step D. Through step H, the O2 gas floating in the processing chamber 201 can be removed.

[0151] In this modification example, the same effect as that Figure 4 shown in the film formation sequence can also be obtained.

[0152] (Modification Example 3)

[0153] After the film formation step, the temperature of the heater 207 can be appropriately adjusted. As a post-treatment, the formed film is heat-treated (annealed) to fill the recesses on the surface of the wafer 200.

[0154] As the processing conditions in this step, the following can be exemplified:

[0155] N2 gas supply flow rate (each gas supply pipe): 0 - 20000 sccm

[0156] Processing temperature: 600 - 1000 °C

[0157] Processing pressure: 0.1 - 100000 Pa

[0158] Processing time: 1 - 300 minutes.

[0159] In this modification example, the same effect as that Figure 4 shown in the film formation sequence can also be obtained. In addition, through the annealing treatment, impurities such as H contained in the film formed on the wafer 200 can be removed from the film. In addition, the film formed on the wafer 200 can be densified, further improving the processability of the film. In addition, it is also possible to prevent the dielectric constant of the film from increasing when the film formed on the wafer 200 is exposed to the atmosphere or the like.

[0160] <Other aspects of the present disclosure>

[0161] The above has specifically described the aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and various modifications can be made without departing from its gist.

[0162] For example, a silicon carbide film (SiC film), SiCN film, silicon oxycarbide film (SiOC film), or silicon oxycarbonitride film (SiOCN film) can also be formed in a manner that fills the recesses formed on the surface of the wafer 200 through the film formation sequence shown below. In these cases, the same effect as that of the above-described aspects and the above modification examples can also be obtained. Figure 4 described above can also be obtained.

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] Preferably, the processes used in substrate processing are prepared separately according to the processing content and pre-stored in the storage device 121c via the telecommunication line and the external storage device 123. Further, when starting the substrate processing, preferably, the CPU 121a appropriately selects a suitable process from among the plurality of processes stored in the storage device 121c according to the processing content. Thereby, it will be possible to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses in one substrate processing apparatus. In addition, the burden on the operator can be reduced, and the substrate processing can be quickly started while avoiding operation errors.

[0169] The above-described processes are not limited to newly made cases. For example, they can also be prepared by changing the existing processes already installed in the substrate processing apparatus. In the case of changing the process, the changed process can also be installed in the substrate processing apparatus via the telecommunication line and the recording medium on which the process is recorded. In addition, the input / output device 122 provided in the existing substrate processing apparatus can also be operated to directly change the existing processes installed in the substrate processing apparatus.

[0170] In the above-described manner, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time has been described. The present disclosure is not limited to the above-described manner. For example, it can also be suitably applied to a case of forming a film using a single-wafer substrate processing apparatus that processes one or more substrates at a time. In addition, in the above-described manner, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-described manner and can also be suitably applied to a case of forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0171] When using these substrate processing apparatuses, the film formation processing can also be performed according to the same processing steps and processing conditions as in the above-described manner and modified examples, and the same effects as in the above-described manner and modified examples can be obtained.

[0172] In addition, the above-described manner, modified examples, etc. can be used in appropriate combinations. The processing steps and processing conditions at this time can be, for example, the same as the processing steps and processing conditions of the above-described manner, modified examples, etc.

[0173] Description of Reference Numerals

[0174] 200 Wafer (substrate)

Claims

1. A method of manufacturing a semiconductor device, comprising a step of forming a film in a manner of filling a recess formed on a surface of a substrate by performing a cycle including the following (a) to (d) a predetermined number of times, (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate becomes unsaturated, Among them, (a) is performed under the condition that the physical adsorption component of the dummy catalyst exists in both the upper part and the lower part of the recess, (b) is performed under the condition that at least a part of the physical adsorption component of the dummy catalyst on the upper part of the recess is detached and at least a part of the physical adsorption component of the dummy catalyst on the lower part of the recess remains.

2. A method of manufacturing a semiconductor device, comprising a step of forming a film in a manner of filling a recess formed on a surface of a substrate by performing a cycle including the following (a) to (d) a predetermined number of times, (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate becomes unsaturated, Among them, (a) is performed under the condition that the physical adsorption component of the dummy catalyst exists in both the upper part and the lower part of the recess, (b) is performed under the condition that the amount of the physical adsorption component of the dummy catalyst detached from the upper part of the recess is larger than the amount of the physical adsorption component of the dummy catalyst detached from the lower part of the recess.

3. A method of manufacturing a semiconductor device, comprising a step of forming a film in a manner of filling a recess formed on a surface of a substrate by performing a cycle including the following (a) to (d) a predetermined number of times, (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate becomes unsaturated, Among them, (a) is performed under the condition that the physical adsorption component of the dummy catalyst exists in both the upper part and the lower part of the recess, (b) is performed under the condition that the amount of the physical adsorption component of the dummy catalyst remaining in the lower part of the recess is larger than the amount of the physical adsorption component of the dummy catalyst remaining in the upper part of the recess.

4. The manufacturing method of the semiconductor device according to any one of claims 1 to 3, wherein, Perform (a) under the condition that both the physical adsorption component and the chemical adsorption component of the dummy catalyst are present in both the upper and lower parts of the concave portion.

5. The manufacturing method of the semiconductor device according to any one of claims 1 to 3, wherein, In (a), supply the dummy catalyst under the condition that the adsorption reaction of the dummy catalyst to the surface of the substrate becomes the rate-determining step of the reaction.

6. The manufacturing method of a semiconductor device according to any one of claims 1 to 3, wherein, In (a), supply the dummy catalyst under the condition that film formation does not occur when the dummy catalyst exists alone.

7. The method of manufacturing a semiconductor device according to any one of claims 1 to 3, wherein, In (c), supply the raw material under the condition that film formation does not occur when the raw material exists alone.

8. The manufacturing method of the semiconductor device according to any one of claims 1 to 3, wherein, The dummy catalyst contains boron and a halogen.

9. The manufacturing method of a semiconductor device according to any one of claims 1 to 3, wherein, The dummy catalyst contains at least any one of BCl3, BF3, BBr3, and BI3.

10. The method of manufacturing a semiconductor device according to claim 8, wherein, The raw material contains an Si-H bond.

11. The method of manufacturing a semiconductor device according to claim 10, wherein, The raw material further contains at least any one of an Si-N bond and an Si-C bond.

12. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, further comprising: (e) A step of supplying a second raw material to the substrate in the processing chamber; and (f) A step of discharging the second raw material remaining in the processing chamber.

13. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, further comprising: (g) A step of supplying a reactant to the substrate in the processing chamber; and (h) A step of discharging the reactant remaining in the processing chamber.

14. A substrate processing method, comprising a step of forming a film in a manner of filling a concave portion formed on the surface of a substrate by performing a cycle including the following (a) to (d) a specified number of times, (a) A step of supplying a dummy catalyst to the substrate in the processing chamber; (b) A step of discharging the dummy catalyst remaining in the processing chamber; (c) A step of supplying a raw material to the substrate in the processing chamber; and (d) A step of discharging the raw material remaining in the processing chamber, In (a), adsorb the dummy catalyst to the surface of the substrate under the condition that the chemical adsorption of the dummy catalyst to the surface of the substrate becomes unsaturated. Among them, Perform (a) under the condition that the physical adsorption component of the dummy catalyst is present in both the upper and lower parts of the concave portion. Perform (b) under the condition that at least a part of the physical adsorption component of the dummy catalyst on the upper part of the concave portion is detached and at least a part of the physical adsorption component of the dummy catalyst on the lower part of the concave portion remains.

15. A substrate processing method, comprising a step of forming a film in a manner of filling a concave portion formed on the surface of a substrate by performing a cycle including the following (a) to (d) a specified number of times, (a) A step of supplying a dummy catalyst to the substrate in the processing chamber; (b) A step of discharging the dummy catalyst remaining in the processing chamber; (c) A step of supplying a raw material to the substrate in the processing chamber; and (d) A step of discharging the raw material remaining in the processing chamber, In (a), adsorb the dummy catalyst to the surface of the substrate under the condition that the chemical adsorption of the dummy catalyst to the surface of the substrate becomes unsaturated. Among them, Perform (a) under the condition that the physical adsorption components of the dummy catalyst are present in both the upper and lower portions of the recess. Perform (b) under the condition that the amount of desorbed physical adsorption components of the dummy catalyst on the upper portion of the recess is greater than the amount of desorbed physical adsorption components of the dummy catalyst on the lower portion of the recess.

16. A substrate processing method, comprising a step of forming a film in such a manner as to fill a recess formed on the surface of a substrate by repeating the cycle of the following (a) to (d) a predetermined number of times. (a) A step of supplying a dummy catalyst to the substrate in the processing chamber. (b) A step of discharging the dummy catalyst remaining in the processing chamber. (c) A step of supplying a raw material to the substrate in the processing chamber. (d) A step of discharging the raw material remaining in the processing chamber. In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate becomes unsaturated. Among them, Perform (a) under the condition that the physical adsorption components of the dummy catalyst are present in both the upper and lower portions of the recess. Perform (b) under the condition that the amount of remaining physical adsorption components of the dummy catalyst on the lower portion of the recess is greater than the amount of remaining physical adsorption components of the dummy catalyst on the upper portion of the recess.

17. A substrate processing apparatus, comprising: A processing chamber for processing a substrate. A dummy catalyst supply system that supplies a dummy catalyst to the substrate in the processing chamber. A raw material supply system that supplies a raw material to the substrate in the processing chamber. A discharge system that discharges substances remaining in the processing chamber. A heater that heats the substrate in the processing chamber. A control unit configured to control the dummy catalyst supply system, the raw material supply system, the discharge system, and the heater to perform a process of forming a film in such a manner as to fill a recess formed on the surface of the substrate by repeating the cycle of the following (a) to (d) a predetermined number of times. (a) A process of supplying the dummy catalyst to the substrate in the processing chamber. (b) A process of discharging the dummy catalyst remaining in the processing chamber. (c) A process of supplying the raw material to the substrate in the processing chamber. And (d) A process of discharging the raw material remaining in the processing chamber. In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate becomes unsaturated. Among them, perform (a) under the condition that the physical adsorption components of the dummy catalyst are present in both the upper and lower portions of the recess. Perform (b) under the condition that at least a part of the physical adsorption components of the dummy catalyst on the upper portion of the recess is desorbed and at least a part of the physical adsorption components of the dummy catalyst on the lower portion of the recess remains.

18. A substrate processing apparatus, comprising: A processing chamber for processing a substrate. A dummy catalyst supply system that supplies a dummy catalyst to the substrate in the processing chamber. A raw material supply system that supplies a raw material to the substrate in the processing chamber. An exhaust system that discharges substances remaining in the processing chamber; A heater that heats a substrate in the processing chamber; and, A control unit configured to control the dummy catalyst supply system, the raw material supply system, the exhaust system, and the heater to perform a process of forming a film by repeating a cycle including the following (a) to (d) a specified number of times to fill recesses formed on the surface of the substrate, (a) A process of supplying the dummy catalyst to the substrate in the processing chamber; (b) A process of discharging the dummy catalyst remaining in the processing chamber; (c) A process of supplying the raw material to the substrate in the processing chamber; and (d) A process of discharging the raw material remaining in the processing chamber, In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate is unsaturated, wherein (a) is performed under the condition that the physical adsorption component of the dummy catalyst exists in both the upper and lower parts of the recess, (b) is performed under the condition that the amount of the physical adsorption component of the dummy catalyst detached from the upper part of the recess is greater than the amount of the physical adsorption component of the dummy catalyst detached from the lower part of the recess.

19. A substrate processing apparatus having: A processing chamber for processing a substrate; A dummy catalyst supply system that supplies a dummy catalyst to the substrate in the processing chamber; A raw material supply system that supplies a raw material to the substrate in the processing chamber; An exhaust system that discharges substances remaining in the processing chamber; A heater that heats a substrate in the processing chamber; and, A control unit configured to control the dummy catalyst supply system, the raw material supply system, the exhaust system, and the heater to perform a process of forming a film by repeating a cycle including the following (a) to (d) a specified number of times to fill recesses formed on the surface of the substrate, (a) A process of supplying the dummy catalyst to the substrate in the processing chamber; (b) A process of discharging the dummy catalyst remaining in the processing chamber; (c) A process of supplying the raw material to the substrate in the processing chamber; and (d) A process of discharging the raw material remaining in the processing chamber, In (a), the dummy catalyst is adsorbed on the surface of the substrate under the condition that the chemisorption of the dummy catalyst on the surface of the substrate is unsaturated, wherein (a) is performed under the condition that the physical adsorption component of the dummy catalyst exists in both the upper and lower parts of the recess, (b) is performed under the condition that the amount of the physical adsorption component of the dummy catalyst remaining in the lower part of the recess is greater than the amount of the physical adsorption component of the dummy catalyst remaining in the upper part of the recess.

20. A computer-readable recording medium that records a program for causing a computer to execute the following steps on a substrate processing apparatus: A step of forming a film by repeating a cycle including the following steps (a) to (d) a predetermined number of times to fill a recess formed on the surface of a substrate: (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), a step of adsorbing the dummy catalyst onto the surface of the substrate under the condition that the chemisorption of the dummy catalyst onto the surface of the substrate is unsaturated, The step (a) is carried out under the condition that the physically adsorbed component of the dummy catalyst exists in both the upper part and the lower part of the recess, and The step (b) is carried out under the condition that at least a part of the physically adsorbed component of the dummy catalyst on the upper part of the recess is detached and at least a part of the physically adsorbed component of the dummy catalyst on the lower part of the recess remains.

21. A computer-readable recording medium that records a program for causing a substrate processing apparatus to execute the following steps by a computer: A step of forming a film by repeating a cycle including the following steps (a) to (d) a predetermined number of times to fill a recess formed on the surface of a substrate: (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), a step of adsorbing the dummy catalyst onto the surface of the substrate under the condition that the chemisorption of the dummy catalyst onto the surface of the substrate is unsaturated, The step (a) is carried out under the condition that the physically adsorbed component of the dummy catalyst exists in both the upper part and the lower part of the recess, and The step (b) is carried out under the condition that the amount of the physically adsorbed component of the dummy catalyst detached from the upper part of the recess is larger than the amount of the physically adsorbed component of the dummy catalyst detached from the lower part of the recess.

22. A computer-readable recording medium that records a program for causing a substrate processing apparatus to execute the following steps by a computer: A step of forming a film by repeating a cycle including the following steps (a) to (d) a predetermined number of times to fill a recess formed on the surface of a substrate: (a) a step of supplying a dummy catalyst to the substrate in a processing chamber; (b) a step of discharging the dummy catalyst remaining in the processing chamber; (c) a step of supplying a raw material to the substrate in the processing chamber; and (d) a step of discharging the raw material remaining in the processing chamber, In (a), a step of adsorbing the dummy catalyst onto the surface of the substrate under the condition that the chemisorption of the dummy catalyst onto the surface of the substrate is unsaturated, The step (a) is carried out under the condition that the physically adsorbed component of the dummy catalyst exists in both the upper part and the lower part of the recess, and Step (b) is carried out under the condition that the residual amount of the physically adsorbed component of the dummy catalyst on the lower part of the concave portion is larger than the residual amount of the physically adsorbed component of the dummy catalyst on the upper part of the concave portion.

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