KR102365948B1 - Method of manufacturing semiconductor device, substrate processing method, substrate processing apparatus, and program - Google Patents

Abstract

The present invention controls the stress of a film formed on a substrate. (a) at the first temperature, by performing a cycle of a predetermined number of times of non-simultaneously supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate, and supplying a nitriding agent to the substrate , on a substrate, forming a first film containing a cyclic structure and nitrogen; and (c) annealing the second film under the third temperature. By controlling the third temperature in (c), the stress of the second film is controlled.

Description

A semiconductor device manufacturing method, a substrate processing method, a substrate processing apparatus, and a program

The present disclosure relates to a method of manufacturing a semiconductor device, a substrate processing apparatus, and a program.

As one process of the manufacturing process of a semiconductor device (device), the process of forming films, such as a silicon-oxycarbide film (SiOC film), on a board|substrate may be performed (for example, refer patent document 1 and patent document 2).

Japanese Patent Laid-Open No. 2015-165523 International Publication No. 2015/045163 pamphlet

It is an object of the present disclosure to provide a technique capable of controlling the stress of a film formed on a substrate.

According to one aspect of the present disclosure,

(a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;

(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;

(c) annealing the second film under a third temperature

A technique for controlling the stress of the second film by controlling the third temperature in (c) is provided.

According to the present disclosure, it becomes possible to control the stress of a film formed on a substrate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus suitably used by one Embodiment of this indication, and is a figure which shows a processing furnace part in a longitudinal sectional view.
FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a diagram showing a portion of the processing furnace taken along line AA of FIG. 1 .
3 is a schematic configuration diagram of a controller of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a diagram showing a control system of the controller in a block diagram.
4 is a flowchart illustrating a substrate processing sequence according to an embodiment of the present disclosure.
5 is a view showing the chemical structural formula of 1,1,3,3-tetrachloro-1,3-disilacyclobutane used as a raw material.
FIG. 6 is a diagram showing evaluation results of an embodiment of the present disclosure, and is a diagram showing annealing temperature dependence of film stress.

In recent years, the three-dimensionalization of the device structure and the miniaturization of the pattern have progressed, and the destruction and bending of the pattern due to the stress effect of the film formed on the wafer as a substrate has become a major problem. As a result, the demand for stress control of the film formed on the wafer is increasing. The stress (stress) generated in the film formed on the wafer is also referred to as film stress (film stress) in this specification.

In response to the above problem, after forming a film having a predetermined structure to be described later on a wafer, the film is annealed, and the film stress can be significantly changed by controlling the annealing temperature at that time. The present initiator and others found that it is possible to freely control (adjust). That is, when the film has a predetermined structure to be described later, the film stress greatly depends on the annealing temperature, and by controlling the annealing temperature, the film stress can be adjusted to the tensile side or to the compressive side. found out that there is That is, it has been found that the film stress can be made into tensile stress (tensile stress) or compressive stress (compressive stress) by controlling the annealing temperature. This indication is based on the said knowledge discovered by this initiator etc.

<One embodiment of the present disclosure>

Hereinafter, one embodiment of the present disclosure will be described with reference to FIGS. 1 to 5 .

(1) Configuration of substrate processing apparatus

1 , the processing furnace 202 includes a heater 207 as a heating mechanism (temperature adjusting unit). The heater 207 has a cylindrical shape and is vertically mounted by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation part) that activates (excites) the gas with heat.

Inside the heater 207 , a reaction tube 203 is disposed concentrically with the heater 207 . The reaction tube 203 is made of, for example, a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed in a cylindrical shape with an upper end closed and an open lower end open. A processing chamber 201 is formed in the cylindrical hollow portion of the reaction tube 203 . The processing chamber 201 is configured to accommodate the wafer 200 as a substrate.

In the processing chamber 201 , nozzles 249a and 249b are provided so as to penetrate the lower sidewall of the reaction tube 203 . Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively.

The gas supply pipes 232a and 232b are provided with mass flow controllers (MFCs) 241a and 241b serving as flow rate controllers (flow rate controllers) and valves 243a and 243b serving as on-off valves, respectively, in order from the upstream side of the gas flow. A gas supply pipe 232c is connected to the downstream side of the valve 243a of the gas supply pipe 232a. Gas supply pipes 232d and 232e are respectively connected to the downstream side of the valve 243b of the gas supply pipe 232b. MFCs 241c, 241d, and 241e and valves 243c, 243d, and 243e are provided in the gas supply pipes 232c, 232d, and 232e in this order from the upstream side of the gas flow.

As shown in FIG. 2 , the nozzles 249a and 249b are located in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200 , and the lower portion of the inner wall of the reaction tube 203 . They are provided so as to stand upright upwards in the arrangement direction of the wafers 200 along the upper part. That is, the nozzles 249a and 249b are respectively provided along the wafer arrangement area in a region horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged. Gas supply holes 250a and 250b for supplying gas are provided on the side surfaces of the nozzles 249a and 249b, respectively. The gas supply holes 250a and 250b are respectively opened to face the center of the reaction tube 203 , so that gas can be supplied toward the wafer 200 . A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203 .

From the gas supply pipe 232a, as a raw material (raw material gas), for example, a gas containing a halogen and a ring structure composed of silicon (Si) and carbon (C), the MFC 241a, the valve 243a, It is supplied into the processing chamber 201 through the nozzle 249a. The raw material acts as a Si source and a C source. As the raw material, for example, 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C ₂ H ₄ Cl ₄ Si ₂ , abbreviation: TCDSCB) gas can be used. Fig. 5 shows the chemical structural formula of TCDSCB. TCDSCB contains a cyclic structure composed of Si and C, and contains chlorine (Cl) as a halogen. Hereinafter, the cyclic structure composed of Si and C is also referred to simply as a cyclic structure for convenience. The shape of the annular structure included in the TCDSCB is square. This cyclic structure is formed by alternating Si and C bonds, and includes four Si-C bonds, and includes two Si atoms and two C atoms. Cl is couple|bonded with Si in this cyclic structure, and H is couple|bonded with C. That is, TCDSCB contains Si-Cl bonds and CH bonds, respectively, in addition to Si-C bonds.

From the gas supply pipe 232b , a gas containing nitrogen (N) as a reactant (reactive gas) is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b. . As the N-containing gas, for example, a hydrogen nitride-based gas serving as a nitriding agent (nitriding gas) can be used. The hydrogen nitride-based gas can be said to be a substance composed of two elements of N and H, including N and H, and acts as an N source. As the hydrogen nitride-based gas, for example, ammonia (NH ₃ ) gas can be used.

From the gas supply pipes 232c and 232d, nitrogen (N ₂ ) gas as an inert gas is supplied to the MFCs 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b, respectively. is supplied into the processing chamber 201 through The N ₂ gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

From the gas supply pipe 232e , the oxygen (O)-containing gas is supplied into the processing chamber 201 through the MFC 241e , the valve 243e , 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, water vapor (H ₂ O gas) can be used. H ₂ O gas, including O and H, may also be referred to as a substance composed of two elements of O and H, and may also be referred to as a gas containing an OH bond, that is, an OH group.

A raw material supply system is mainly comprised by the gas supply pipe|tube 232a, the MFC 241a, and the valve 243a. The nitriding agent supply system is mainly constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. An oxidizing agent supply system is mainly comprised by the gas supply pipe|tube 232e, the MFC 241e, and the valve 243e. The inert gas supply system is mainly constituted by the gas supply pipes 232c and 232d, the MFCs 241c and 241d, and the valves 243c and 243d.

Any or all of the various supply systems described above may be configured as the integrated supply system 248 in which the valves 243a to 243e, the MFCs 241a to 241e, and the like are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232e, and supplies various gases in the gas supply pipes 232a to 232e, that is, the opening/closing operation of the valves 243a to 243e or the MFC. It is comprised so that the flow rate adjustment operation|movement etc. by 241a to 241e may be controlled by the controller 121 mentioned later. The integrated supply system 248 is configured as an integrated unit or a division type integrated unit, and can be attached and detached to and from the gas supply pipes 232a to 232e in units of the integrated unit, so that the integrated supply system 248 is It is comprised so that it is possible to perform maintenance, replacement|exchange, expansion, etc. in units of an integration unit.

An exhaust pipe 231 for exhausting an atmosphere in the processing chamber 201 is connected below the side wall of the reaction tube 203 . The exhaust pipe 231 is evacuated through a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201 and an Auto Pressure Controller (APC) valve 244 as a pressure control unit (exhaust valve). A vacuum pump 246 as a device is connected. The APC valve 244 can evacuate and stop evacuation of the processing chamber 201 by opening and closing the valve in a state in which the vacuum pump 246 is operated, and in a state in which the vacuum pump 246 is operated, By adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245 , the pressure in the processing chamber 201 can be controlled (adjusted). The exhaust system is mainly constituted by the exhaust pipe 231 , the pressure sensor 245 , and the APC valve 244 . The vacuum pump 246 may be included in the exhaust system.

Below the reaction tube 203 , a seal cap 219 as a furnace-aperture cover capable of hermetically closing the lower end opening of the reaction tube 203 is provided. The seal cap 219 is made of, for example, a metal material such as SUS, and is formed in a disk shape. An O-ring 220 is provided on the upper surface of the seal cap 219 as a sealing member in contact with the lower end of the reaction tube 203 . Below the seal cap 219, a rotation mechanism 267 for rotating a boat 217, which will be described later, is provided. The 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 wafer 200 by rotating the boat 217 . The seal cap 219 is configured to be vertically raised and lowered by the boat elevator 115 as a lifting mechanism provided outside the reaction tube 203 . The boat elevator 115 is configured as a transport device (transport mechanism) for loading and unloading (transporting) wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219 .

The boat 217 serving as the substrate holder is provided with a plurality of boat posts 217a serving as substrate holding posts, and a plurality of, for example, 25 Each of the 200 to 200 wafers 200 is arranged in a vertical direction in a horizontal position and centered on each other to support it in multiple stages, that is, it is configured to be arranged at intervals. The boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. In the lower part of the boat 217, for example, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages in a horizontal position.

A temperature sensor 263 as a temperature detector is provided in the reaction tube 203 . By adjusting the energization state of the heater 207 based on the temperature information detected by the temperature sensor 263 , the temperature in the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203 .

As shown in FIG. 3 , the controller 121 serving as a control unit (control unit) includes a central processing unit (CPU) 121a, a random access memory (RAM) 121b, a storage device 121c, and an I/O port. (121d) is configured as a computer. The RAM 121b, the storage device 121c, and the I/O port 121d are configured such that data can be exchanged with the CPU 121a via the internal bus 121e. An input/output device 122 configured as a touch panel or the like is connected to the controller 121 .

The storage device 121c is configured of, for example, a flash memory, a HDD (Hard Disk Drive), or the like. In the memory device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which a procedure, conditions, and the like of a substrate processing described later are described are stored in a readable manner. The process recipe is combined so that a predetermined result can be obtained by causing the controller 121 to execute each procedure in the substrate processing step to be described later, and functions as a program. Hereinafter, this process recipe, a control program, etc. are generically called, and it is simply called a program. In addition, a process recipe is also simply called a recipe. When the term "program" is used in this specification, only a single recipe is included, only a control program is included, or both are included in some cases. The RAM 121b is configured as a memory area (work area) in which a program, data, etc. read by the CPU 121a are temporarily held.

The I/O port 121d includes the above-described MFCs 241a to 241e, valves 243a to 243e, pressure sensor 245 , APC valve 244 , heater 207 , temperature sensor 263 , and a vacuum pump. 246 , a rotation mechanism 267 , a boat elevator 115 , and the like.

The CPU 121a is configured to read and execute a control program from the storage device 121c and read a recipe from the storage device 121c according to input of an operation command from the input/output device 122 or the like. The CPU 121a performs the flow rate adjustment operation of various gases by the MFCs 241a to 241e, the opening/closing operation of the valves 243a to 243e, the opening/closing operation of the APC valve 244, and The pressure adjustment operation by the APC valve 244 based on the pressure sensor 245 , the starting and stopping of the vacuum pump 246 , the temperature adjustment operation of the heater 207 based on the temperature sensor 263 , the rotation mechanism 267 ) to control the rotation and rotation speed control operation of the boat 217 and the lifting operation of the boat 217 by the boat elevator 115 .

The controller 121 can be configured by installing the above-described program stored in the external storage device 123 in 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. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to as a recording medium. When the term "recording medium" is used in this specification, only the storage device 121c alone, the external storage device 123 alone, or both are included in some cases. In addition, the provision of the program to a computer may be performed using communication means, such as the Internet or a dedicated line, without using the external storage device 123. As shown in FIG.

(2) substrate processing process

An example of a substrate processing sequence for forming and modifying a desired film on the wafer 200 as a substrate as one step of the semiconductor device manufacturing process using the above-described substrate processing apparatus will be mainly described with reference to FIG. 4 . In the following description, the operation of each unit constituting the substrate processing apparatus is controlled by the controller 121 .

In the substrate processing sequence shown in Fig. 4,

(a) a step of supplying a TCDSCB gas as a raw material containing Cl as a halogen and a cyclic structure composed of Si and C to the wafer 200 under a first temperature, and NH ₃ as a nitriding agent to the wafer 200 a step of forming a SiCN film as a first film containing an annular structure and N on the wafer 200 by performing a predetermined number of cycles of asynchronously performing the gas supply step;

(b) converting the SiCN film into a SiOCN film or a SiOC film as a second film containing an annular structure and O by supplying H ₂ O gas as an oxidizing agent to the wafer 200 under a second temperature;

(c) annealing the SiOCN film or SiOC film under a third temperature, and controlling the third temperature in (c) to control the stress of the SiOCN film or SiOC film.

The process of forming a SiCN film as a first film containing an annular structure and N on the wafer 200 under the first temperature in (a) is also referred to as a film formation step. In addition, gases that contribute to substrate processing, such as source gas and reactive gas, are collectively referred to as a processing gas.

The process of converting the SiCN film into a SiOCN film or SiOC film as a second film containing an annular structure and O by supplying H ₂ O gas under the second temperature in (b) is also referred to as an H ₂ O annealing step. .

The step of annealing the SiOCN film or the SiOC film under the third temperature in (c) is also referred to as an N ₂ annealing step.

In this substrate processing sequence, the SiCN film is reformed into a SiOCN film or a SiOC film in an H ₂ O annealing step performed after the film formation step. The SiOCN film or SiOC film is also referred to as a SiOC(N) film for convenience. The SiOC(N) film has a cyclic structure composed of at least Si and C and a film containing O.

In addition, each step of the film-forming step, the H ₂ O annealing step, and the N ₂ annealing step is performed in a non-plasma atmosphere. By carrying out each step in a non-plasma atmosphere, it becomes possible to control the reaction etc. which generate|occur|produce in each step with high precision, and it becomes possible to improve the controllability of the process performed by each step.

In this specification, the substrate processing sequence shown in FIG. 4 may be shown as follows for convenience. Also in the description of the following modified examples, the same notation shall be used.

(TCDSCB→NH ₃ )×n→H ₂ O_ANL→N ₂ _ANL ⇒ SiOC(N)

When the term "wafer" is used in this specification, it may mean a wafer itself or a laminate of a wafer and a predetermined layer or film formed on the surface in some cases. When the term "surface of a wafer" is used in this specification, it may mean the surface of the wafer itself, or the surface of a predetermined layer etc. formed on a wafer. In this specification, when it is described as "forming a predetermined layer on a wafer", it means directly forming a predetermined layer on the surface of the wafer itself, or on a layer formed on the wafer, etc. In some cases, it means forming a predetermined layer. The use of the word "substrate" in this specification is synonymous with the case of using the word "wafer".

(Wafer Charge and Boat Load)

A plurality of wafers 200 are loaded (wafer charged) on the boat 217 . Thereafter, as shown in FIG. 1 , the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 is in a state in which the lower end of the reaction tube 203 is sealed through the O-ring 220 .

(pressure adjustment and temperature adjustment)

The vacuum pump 246 evacuates (depressurizes) so that the inside of the processing chamber 201, ie, the space in which the wafer 200 exists, becomes a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245 , and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, the wafer 200 in the processing chamber 201 is heated by the heater 207 to a desired processing temperature. At this time, the energization state of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 may have a desired temperature distribution. In addition, rotation of the wafer 200 by the rotation mechanism 267 is started. The operation of the vacuum pump 246 and the heating and rotation of the wafer 200 are all continuously performed at least until the processing of the wafer 200 is finished.

(film formation step)

After that, the following steps 1 and 2 are sequentially performed.

[Step 1]

In this step, TCDSCB gas is supplied as a raw material to the wafer 200 accommodated in the processing chamber 201 . Specifically, the valve 243a is opened to flow the TCDSCB gas into the gas supply pipe 232a. The flow rate of the TCDSCB gas is adjusted by the MFC 241a , and is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust pipe 231 . At this time, the TCDSCB gas is supplied to the wafer 200 . At this time, the valves 243c and 243d may be opened to flow the N ₂ gas into the gas supply pipes 232c and 232d.

As processing conditions in this step,

Treatment temperature (first temperature): 200 to 400° C., preferably 250 to 350° C.

Treatment pressure: 133-2666Pa

TCDSCB gas supply flow: 1 to 2000 sccm

N ₂ gas supply flow rate (each gas supply pipe): 0 to 10000 sccm

Each gas supply time: 1 to 120 seconds, preferably 5 to 60 seconds

is exemplified.

In addition, the description of a numerical range, such as "200-400 degreeC" in this specification means that a lower limit and an upper limit are included in the range. For example, "200-400 degreeC" means "200 degreeC or more and 400 degrees C or less". The same is true for other numerical ranges.

The above-described processing conditions, particularly temperature conditions, are conditions in which at least a part of the annular structure composed of Si and C contained in the TCDSCB can be held (maintained) without destruction. That is, the above-described processing conditions are conditions in which at least some of the annular structures contained in the TCDSCB gas (a plurality of TCDSCB molecules) supplied to the wafer 200 are maintained in their intact form without being destroyed. . That is, among the plurality of Si-C bonds constituting the plurality of annular structures included in the TCDSCB gas supplied to the wafer 200 , at least some of the Si-C bonds are maintained as they are. As described above, in this specification, the cyclic structure composed of Si and C is simply referred to as a cyclic structure.

By supplying the TCDSCB gas to the wafer 200 under the above-described conditions, a first layer (initial layer) containing a cyclic structure and Cl as a halogen is formed on the outermost surface of the wafer 200 . That is, as the first layer, a cyclic structure composed of Si and C and a layer containing Cl are formed. In the first layer, among the plurality of annular structures contained in the TCDSCB gas, at least a part of the annular structure is introduced without being destroyed as it is. Moreover, the 1st layer may contain the chain|strand structure produced|generated by breaking some bonds among the some Si-C bond which comprises a cyclic structure. In addition, the 1st layer may contain at least any of a Si-Cl bond and a C-H bond.

After the first layer is formed on the wafer 200 , the valve 243a is closed to stop the supply of the TCDSCB gas into the processing chamber 201 . Then, the inside of the processing chamber 201 is evacuated to remove gas or the like remaining in the processing chamber 201 from the inside of the processing chamber 201 . At this time, the valves 243c and 243d are opened to supply the N ₂ gas into the processing chamber 201 . The N ₂ gas acts as a purge gas.

As the raw material, in addition to TCDSCB gas, 1,1,3,3-tetrachloro-1,3-disilacyclopentane (C ₃ H ₆ Cl ₄ Si ₂ ) gas or the like can be used. That is, the shape of the annular structure composed of Si and C contained in the raw material is not limited to the case of a quadrangle. In addition, this cyclic structure is not limited to the case where Si and C couple|bond alternately. Further, as the raw material, 1,1,3,3-tetrafluoro-1,3-disilacyclobutane (C ₂ H ₄ F ₄ Si ₂ ) gas or the like may be used. That is, the halogen contained in the raw material is not limited to Cl, and may be fluorine (F), bromine (Br), iodine (I), or the like.

As the inert gas, it is possible to use various noble gases such as Ar gas, He gas, Ne gas, and Xe gas other than N ₂ gas. This point is also the same in step 2, a purge step, an H ₂ O annealing step, and an N ₂ annealing step, which will be described later.

[Step 2]

After step 1 is completed, NH ₃ gas serving as a nitriding agent is supplied as a reactant to the wafer 200 in the processing chamber 201 , that is, the first layer formed on the wafer 200 . Specifically, the opening/closing control of the valves 243b to 243d is performed in the same procedure as the opening/closing control of the valves 243a, 243c, and 243d in step 1. The NH ₃ gas is flow-controlled by the MFC 241b, is supplied into the processing chamber 201 through the nozzle 249b, and is exhausted from the exhaust pipe 231 . At this time, NH ₃ gas is supplied to the wafer 200 .

As processing conditions in this step,

Treatment temperature (first temperature): 200 to 400° C., preferably 250 to 350° C.

Treatment pressure: 133 to 3999Pa

NH ₃ gas supply flow rate: 100 to 10000 sccm

Gas supply time: 1 to 120 seconds

is exemplified. Other processing conditions are the same as the processing conditions in step 1.

The above-described processing conditions, particularly temperature conditions, are capable of holding (maintaining) at least a part of the annular structure composed of Si and C included in the first layer formed on the wafer 200 in step 1 without destroying it. is a condition That is, the above-described processing conditions are conditions in which at least some of the annular structures among the plurality of annular structures included in the first layer on the wafer 200 are not destroyed and maintained in their intact form. That is, among the plurality of Si-C bonds constituting the plurality of annular structures included in the first layer on the wafer 200 , at least some of the Si-C bonds are not cut and are maintained in their intact form. The Si-C bond constituting this cyclic structure is strong, and C is in a state in which it is difficult to detach from Si.

By supplying NH ₃ gas to the wafer 200 under the above-described conditions, at least a portion of the first layer may be modified (nitrided). This makes it possible to desorb Cl, H, and the like from the first layer, and to introduce N contained in the NH ₃ gas into the first layer in a state in which H is bonded to N. That is, it becomes possible to couple|bond N contained in NH3 gas to Si which comprises the cyclic structure contained in the 1st layer, _and H couple|bonded with N. The Si-N bond bonded to Si in this NH state is weak, and N is easily released from Si. By nitriding the first layer in this way, the first layer, which is a layer containing a cyclic structure and Cl, can be converted into a second layer which is a layer containing a cyclic structure and N.

That is, by supplying the NH ₃ gas to the wafer 200 under the above-described conditions, at least a part of the annular structure included in the first layer is introduced (remained) into the second layer while maintaining it without destroying it. thing becomes possible That is, the nitridation of the first layer can be made unsaturated (unsaturated nitridation) so that at least a part of the cyclic structures among the plurality of cyclic structures contained in the first layer remain intact. As the first layer is nitrided, a silicon carbonitride layer (SiCN layer), which is a layer containing N and an annular structure composed of Si and C, is formed as a second layer on the wafer 200 . This SiCN layer contains Si, C and N and becomes an O-free layer. In addition, C contained in the second layer is introduced into the second layer while maintaining the cyclic structure composed of Si and C, and N contained in the second layer is in a state where N is bonded to H; It will be introduced in the second layer. That is, C contained in the second layer is in a state where it is difficult to detach due to a strong Si-C bond, and N contained in the second layer is in a state where it is easy to detach due to a weak Si-N bond. do.

After the second layer is formed on the wafer 200 , the valve 243b is closed to stop the supply of the NH ₃ gas into the processing chamber 201 . Then, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201 by the same processing procedure as in Step 1.

As the nitriding agent (N-containing gas), in addition to NH ₃ gas, diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas, a gas containing these compounds, or the like may be used. possible.

[Perform a certain number of times]

Si and C as a first film on the wafer 200 by performing a predetermined number of cycles (n times, n is an integer greater than or equal to 1) in which steps 1 and 2 are alternately performed asynchronously, that is, without synchronization A SiCN film, which is a film containing the constituted annular structure and N, is formed. The cycle described above is preferably repeated a plurality of times. This first film (SiCN film) contains Si, C, and N and becomes an O-free film, but since Cl and N having a weak bond remain, it becomes a film in which absorption and adsorption of moisture easily occur.

(Purge step)

After the film forming step is completed, the N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d and exhausted from the exhaust pipe 231 . As a result, the inside of the processing chamber 201 is purged, and gases, reaction byproducts, and the like remaining in the processing chamber 201 are removed from the interior of the processing chamber 201 .

(H ₂ O annealing step)

After the purge step is completed, in a state in which the wafer 200 having the first film formed thereon is accommodated in the processing chamber 201 , the wafer 200 in the processing chamber 201 , that is, the first film formed on the wafer 200 . As an oxidizing agent, H ₂ O gas is supplied to the SiCN film. Specifically, the opening/closing control of the valves 243e, 243c, and 243d is performed in the same procedure as the opening/closing control of the valves 243a, 243c, 243d in step 1. The H ₂ O gas is flow-controlled by the MFC 241e, supplied into the processing chamber 201 through the nozzle 249b, and exhausted from the exhaust pipe 231 . At this time, H ₂ O gas is supplied to the wafer 200 .

As processing conditions in this step,

Treatment temperature (second temperature): 200 to 600°C, preferably 250 to 500°C

Treatment pressure: 1333 to 101325 Pa, preferably 53329 to 101325 Pa

H ₂ O gas supply flow rate: 50 to 10000 sccm

H ₂ O gas supply time: 10 to 360 minutes, preferably 60 to 360 minutes

This is exemplified. Other processing conditions are the same as the processing conditions in step 1.

The above-described processing conditions, particularly temperature conditions and pressure conditions, hold (maintain) without destroying at least a part of the annular structure composed of Si and C included in the first film formed on the wafer 200 in the film forming step. It is a condition in which N contained in the first film can be substituted with O while doing so. Here, when the treatment temperature and the treatment pressure are too high, the oxidizing power by the H ₂ O gas becomes too strong, the annular structure contained in the first film collapses, and C in the film is easily detached. On the other hand, when the treatment temperature and the treatment pressure are too low, the oxidizing power by the H ₂ O gas becomes too weak, and the reaction for replacing N with O in the first film may become insufficient. If it is the above-mentioned processing conditions, it becomes possible to fully generate|occur|produce the above-mentioned substitution reaction, suppressing destruction of the cyclic structure contained in the 1st film|membrane.

That is, under the above-described processing conditions, among the plurality of annular structures included in the first film on the wafer 200 , at least some of the annular structures are not destroyed and remain intact, while N contained in the first film is O The condition is replaced by That is, among the plurality of Si-C bonds constituting the plurality of annular structures included in the first film on the wafer 200 , at least a portion of the Si-C bonds are not broken and are maintained as they are, while in the first film It is a condition that included N is substituted with O.

That is, under the above-mentioned conditions, it becomes possible to substitute O for N contained in the first film, while maintaining at least a part of the cyclic structure contained in the first film without destroying it. That is, it becomes possible to substitute O for N contained in the first film while at least a part of the cyclic structures among the plurality of cyclic structures contained in the first film remain in the film as they are.

In addition, as described above, in the first film before the H ₂ O annealing treatment, N is bonded to Si constituting the cyclic structure in the film in the state of NH. The Si-N bond in which N is bonded to Si in the state of NH is weak, and N is in a state in which it is easy to detach. In addition, the Si-C bond constituting the cyclic structure in the first film is strong, and C is in a state in which it is difficult to detach.

By subjecting the first film to an H ₂ O annealing treatment under the conditions described above, the first film is oxidized while maintaining at least a part of the annular structure (Si-C bond) composed of Si and C contained in the first film. , a substitution reaction in which N contained in the first film is replaced with O contained in H ₂ O gas may be generated. At this time, N or Cl contained in the first film is desorbed from the film together with H. As described above, by oxidizing the first film by the H ₂ O gas, the first film including the cyclic structure and N may be modified into the second film including the cyclic structure and O. In addition, when all of the N contained in the first film is substituted with O, the first film is modified into a SiOC film. In addition, if all of N contained in the first film is not substituted with O and N remains, the first film is reformed into a SiOCN film. That is, the second film becomes a SiOC film or a SiOCN film, that is, a SiOC(N) film. In addition, by oxidizing the first film with H ₂ O gas, Cl or N having a weak bond can be desorbed from the film, whereby moisture absorption sites in the film can be annihilated, and the second film after H ₂ O annealing treatment When the second film is exposed to the atmosphere, it becomes possible to suppress absorption and adsorption of moisture contained in the air into the second film. On the other hand, during the H ₂ O annealing treatment, moisture is absorbed into the second film, and the second film contains moisture.

(Purge step)

After the H ₂ O annealing step is completed, the N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d and exhausted from the exhaust pipe 231 . As a result, the inside of the processing chamber 201 is purged, and gases, reaction byproducts, and the like remaining in the processing chamber 201 are removed from the interior of the processing chamber 201 .

(N ₂ annealing step)

After the purge step is completed, the wafer 200 in the processing chamber 201, that is, formed on the wafer 200, is continuously accommodated in the processing chamber 201 with the second film formed thereon. As the thermal annealing treatment for the second film, an N ₂ annealing treatment is performed. Thereby, the water|moisture content contained in the 2nd film|membrane can be desorbed. At this time, the N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d and exhausted from the exhaust pipe 231 . The N ₂ gas is flow rate adjusted by the MFCs 241c and 241d, is supplied into the processing chamber 201 through the nozzles 249a and 249b, respectively, and is exhausted from the exhaust pipe 231 . At this time, N ₂ gas is supplied to the wafer 200 .

As processing conditions in this step,

Treatment temperature (third temperature): 400 to 1200°C

Treatment pressure: 67 to 101325Pa

N ₂ gas supply flow rate: 1000 to 5000 sccm

N ₂ gas supply time: 10 to 120 minutes

This is exemplified.

By controlling the processing temperature (third temperature), which is the annealing temperature in this step, the film stress of the second film can be controlled. Specifically, by setting the treatment temperature to 400°C or higher and 600°C or lower, the film stress of the second film can be made into tensile stress, and when the treatment temperature is set to 700°C or higher and 1200°C or lower, the film stress of the second film is compressed. stress can do it.

Under the temperature condition of the treatment temperature of 400 to 600° C. described above, the annular structure composed of Si and C contained in the second film formed in the H ₂ O annealing step is retained (maintained) without destruction, while in the second film The contained moisture and impurities such as H and Cl can be removed. That is, at a treatment temperature of 400 to 600° C., moisture and impurities contained in the second film are maintained while all, or most, of the plurality of annular structures included in the second film are not destroyed. is the temperature at which In other words, it is the temperature at which all or most of the Si-C bonds among the plurality of Si-C bonds constituting the plurality of annular structures included in the second film are maintained in their intact form without being cut. Therefore, by setting the annealing temperature to 400 to 600°C, all or most of the cyclic structures among the plurality of cyclic structures included in the second film are maintained, and all of the plurality of Si-C bonds constituting the cyclic structure are maintained. , or, most of the Si-C bonds are not cleaved and remain intact. As a result, the film stress of the second film can be taken as the tensyl stress. In addition, by controlling the amount of impurities removed from the second film, it is possible to fine-tune the film stress of the second film on the stencil side. In addition, most means 70 % or more, Preferably it is 80 % or more, More preferably, it means 90 % or more.

In addition, under the above-described processing temperature of 700 to 1200 ° C., while destroying the annular structure composed of Si and C contained in the second film, moisture and impurities such as H and Cl contained in the second film are desorbed. can In addition, at this time, at least a part of C which has comprised the cyclic structure may detach|desorb. That is, at a processing temperature of 700 to 1200° C., all or most of the cyclic structures among the plurality of cyclic structures included in the second film are destroyed, while moisture and impurities such as H and Cl are desorbed from the second film. is the temperature In other words, it is the temperature at which all or most of the Si-C bonds among the plurality of Si-C bonds constituting the plurality of cyclic structures included in the second film are cleaved. Accordingly, by setting the annealing temperature to 700 to 1200°C, all or most of the cyclic structures among the plurality of cyclic structures included in the second film are destroyed, and all of the plurality of Si-C bonds constituting the cyclic structure , or, most of the Si-C bonds are cleaved. As a result, the film stress of the second film can be taken as the compressive stress. In addition, by controlling the amount of impurities removed from the second film, the film stress of the second film can be finely adjusted on the compressive side.

In addition, under the temperature condition in which the above-described processing temperature is more than 600°C and less than 700°C, at least a part of the annular structure composed of Si and C contained in the second film is maintained, and Si and C contained in the second film are maintained. At least a part of the constituted annular structure is destroyed. That is, the film stress of the second film changes into a tensile stress or a compressive stress according to the rate at which the annular structure included in the second film is maintained and the rate at which it is destroyed.

That is, in this step, by controlling the annealing temperature, the maintenance and destruction of the annular structure composed of Si and C contained in the second film can be controlled. Specifically, each ratio of maintenance and destruction of the annular structure contained in the second film can be controlled. And thereby, the film stress of the second film can be freely controlled. Specifically, by increasing the rate at which the annular structure contained in the second film is maintained, the film stress of the second film can be controlled on the tensile side, and by increasing the rate at which the annular structure contained in the second film is destroyed, The film stress of the second film can be controlled to the compressive side.

In other words, by controlling the annealing temperature, it is possible to control the maintenance and cleavage of the Si-C bond constituting the cyclic structure included in the second film. Specifically, it is possible to control the respective ratios of retention and cleavage of Si-C bonds constituting the cyclic structure included in the second film. And thereby, the film stress of the second film can be freely controlled. Specifically, by increasing the ratio at which the Si-C bonds constituting the annular structure contained in the second film are maintained, the film stress of the second film can be controlled on the tensile side, and the annular structure contained in the second film is reduced. By increasing the rate at which the constituting Si-C bond is broken, the film stress of the second film can be controlled to the compressive side.

That is, in this step, by controlling the annealing temperature, it is possible to control the stress of the second film to be either a tensyl stress or a compressive stress.

In addition, in the present embodiment, the film forming step, the H ₂ O annealing step, and the N ₂ annealing step are performed in this order in a state in which the wafer 200 is accommodated in the same processing chamber 201 , in-situ. to be done continuously. In this case, it becomes possible to continuously perform these series of processes without exposing the film formed on the wafer 200 to the atmosphere. As a result, it becomes possible to suppress fluctuations in the composition of the film formed on the wafer, thereby enhancing the controllability of the processing performed in each step, and it is also possible to improve the throughput, that is, the productivity.

(After purge and return to atmospheric pressure)

After the N ₂ annealing step is completed, the N ₂ gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d and exhausted from the exhaust pipe 231 . As a result, the inside of the processing chamber 201 is purged, and gases, reaction by-products, and the like remaining in the processing chamber 201 are removed from the interior of the processing chamber 201 (after-purge). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

(Boat unload and wafer discharge)

Thereafter, the seal cap 219 is lowered by the boat elevator 115 , the lower end of the reaction tube 203 is opened, and the processed wafer 200 is supported by the boat 217 . It is carried out (boat unloading) from the lower end of the tube 203 to the outside of the reaction tube 203 . The processed wafer 200 is taken out of the reaction tube 203 and then taken out from the boat 217 (wafer discharge).

(3) Effects of the present embodiment

According to this embodiment, one or a plurality of effects shown below are obtained.

(a) By controlling the annealing temperature in the N ₂ annealing step, it becomes possible to control the film stress of the SiOC(N) film. For example, the film stress may be adjusted to the tensil side or to the compressive side. That is, the film stress may be a tensile stress or a compressive stress.

(b) By controlling the annealing temperature in the N ₂ annealing step, it becomes possible to control the maintenance and destruction of the annular structure composed of Si and C contained in the SiOC (N) film. Specifically, it becomes possible to control the respective ratios of maintenance and destruction of the annular structure contained in the SiOC(N) film, thereby controlling the film stress of the SiOC(N) film both on the tensile side and on the compressive side. it becomes possible to do More specifically, by making the ratio in which the annular structure is maintained in the SiOC(N) film greater than the ratio in which the annular structure is destroyed, it is possible to make the film stress of the SiOC(N) film the tensyl stress. In addition, by making the rate at which the annular structure in the SiOC(N) film is broken is higher than the rate at which the annular structure is maintained, it is possible to make the film stress of the SiOC(N) film as the compressive stress.

(c) By controlling the annealing temperature in the N ₂ annealing step, it becomes possible to control the maintenance and cleavage of the Si-C bond constituting the cyclic structure included in the SiOC(N) film. Specifically, it becomes possible to control the respective ratios of retention and cleavage of Si-C bonds constituting the annular structure included in the SiOC(N) film, thereby shifting the film stress of the SiOC(N) film to the tensile side. It also becomes possible to control to the compressive side. More specifically, the SiOC(N) film film of the SiOC(N) film by making the ratio in which the Si-C bonds constituting the annular structure is maintained in the SiOC(N) film greater than the ratio in which the Si-C bonds constituting the annular structure are severed. It becomes possible to make stress into tensile stress. In addition, the film stress of the SiOC(N) film can be reduced by making the ratio of the Si-C bonds constituting the annular structure cleaved in the SiOC(N) film higher than the rate at which the Si-C bonds constituting the annular structure are maintained. It becomes possible to do it with a press stress.

(d) The film formation step, the H ₂ O annealing step, and the N ₂ annealing step are successively performed on the spot in this order, so that the film formed on the wafer 200 is not exposed to the atmosphere, and these series of processes are performed. It becomes possible to do it continuously. As a result, it becomes possible to suppress fluctuations in the composition of the film formed on the wafer, thereby enhancing the controllability of the processing performed in each step, and it is also possible to improve the throughput, that is, the productivity.

(e) By a series of processes from H ₂ O annealing to N ₂ annealing, the moisture absorption sites of the film finally formed on the wafer 200 can be annihilated, and when the film is exposed to the atmosphere, it is contained in the atmosphere. It becomes possible to suppress absorption and adsorption of moisture into the film.

(f) The above-described effect is achieved when a source gas other than TCDSCB gas is used, when a reactive gas other than NH ₃ gas is used, when an oxidizing gas other than H ₂ O gas is used, or N ₂ gas It can be obtained similarly also when using other inert gases.

<Other embodiment>

As mentioned above, embodiment of this indication was demonstrated concretely. However, this indication is not limited to the above-mentioned embodiment, It can change variously in the range which does not deviate from the summary.

For example, like the process sequence shown below, you may add the step _of supplying O2 gas as an oxidizing agent to the above-mentioned film-forming step. That is, the cycle in the above-mentioned film-forming step may further include the step of supplying O ₂ gas. In this processing sequence, an example in which the step of supplying the O ₂ gas is performed asynchronously with the process of supplying the TCDSCB gas and the process of supplying the NH ₃ gas is shown. Also in this case, the same effect as that of the process sequence shown in FIG. 4 is acquired. Further, in this case, it becomes possible to further control the composition ratio of the SiOC(N) film finally formed on the wafer 200 in the O-rich direction, for example.

(TCDSCB→NH ₃ →O ₂ )×n→H ₂ O_ANL→N ₂ _ANL ⇒ SiOC(N)

As the oxidizing agent, nitrous oxide (N ₂ O) gas, nitrogen monoxide (NO) gas, H ₂ O gas, or H ₂ gas+O ₂ gas may be used instead of the O ₂ gas, for example.

It is preferable that the recipe used for substrate processing is individually prepared according to the processing content, and stored in the memory|storage device 121c via a telecommunication line or the external memory|storage device 123. Then, when starting the substrate processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from among a plurality of recipes stored in the storage device 121c according to the contents of the substrate processing. Thereby, it becomes possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility with one substrate processing apparatus. Moreover, the burden on the operator can be reduced, and processing can be started quickly, avoiding an operation error.

The above-mentioned recipe is not limited to the case of newly created, For example, you may prepare by changing the existing recipe already installed in the substrate processing apparatus. When changing a recipe, you may install the recipe after a change in the substrate processing apparatus via a telecommunication line or the recording medium in which the said recipe was recorded. Moreover, you may make it change directly the existing recipe already installed in the substrate processing apparatus by operating the input/output device 122 with which the existing substrate processing apparatus is equipped.

In the above-described embodiment, an example in which a film is formed using a batch type substrate processing apparatus that processes a plurality of substrates at once 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 substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, the example which forms a film|membrane using the substrate processing apparatus which has a hot wall type processing furnace was demonstrated. The present disclosure is not limited to the above-described embodiment, and can be suitably applied even when a film is formed using a substrate processing apparatus having a cold wall type processing furnace.

Even in the case of using these substrate processing apparatuses, the substrate processing can be performed under the same processing procedures and processing conditions as those of the above-described embodiments and modifications, and effects similar to these can be obtained.

In addition, the above-mentioned embodiment and modified example can be used combining suitably. The processing procedure and processing conditions at this time can be made similarly to the processing procedure and processing conditions of the above-mentioned embodiment, for example.

[Example 1]

Samples 1 to 6 were produced by forming a SiOC (N) film on the wafer mainly by the substrate processing sequence shown in FIG. 4 using the substrate processing apparatus shown in FIGS. 1 and 2 . When preparing each sample, the treatment temperature (third temperature) in the N ₂ annealing step was set to a different temperature, respectively. Other processing conditions were set as predetermined conditions within the processing conditions range in the above-described embodiment.

When the sample 1 was produced, the film-forming step and the H ₂ O annealing step were performed in this order, and the N ₂ annealing step was not performed. When producing Samples 2, 3, 4, 5, and 6, the film formation step, H ₂ O annealing step, and N ₂ annealing step were performed in this order, and the processing temperature (annealing temperature) at the time of performing the N ₂ annealing step was determined. They were set to 400°C, 500°C, 600°C, 700°C, and 800°C, respectively. After samples 1 to 6 were prepared, the film stress of the SiOC(N) film in each sample was measured.

6 is a diagram showing the measurement results of the film stress of the SiOC(N) film in each of Samples 1 to 6; That is, Fig. 6 is a diagram showing the annealing temperature dependence of the film stress of the SiOC(N) film formed in this embodiment. The horizontal axis in FIG. 6 represents each sample. The vertical axis of FIG. 6 represents the film stress. When the value of the film stress is positive, the film stress of the formed film is the tensile stress. When the value of the film stress is negative, the film stress of the formed film is compressive. indicates stress.

As shown in FIG. 6 , in Sample 1 in which the N ₂ annealing step was not performed, it was confirmed that the film stress of the formed SiOC(N) film was the tensyl stress. In addition, it was confirmed that the film stress of the formed SiOC(N) film was the tensyl stress also in Samples 2, 3, and 4 in which the treatment temperature in the N ₂ annealing step was set to 400 to 600°C. In addition, in Samples 5 and 6 in which the processing temperature in the N ₂ annealing step was set to 700°C and 800°C, it was confirmed that the film stress of the formed SiOC(N) film was the compressive stress. In addition, it was confirmed that the annular structure contained in the SiOC(N) film in Samples 1, 2, 3, and 4 was maintained, and the annular structure contained in the SiOC(N) film in Samples 5 and 6 was destroyed. That is, by controlling the processing temperature in the N ₂ annealing step, the maintenance and destruction of the annular structure included in the formed SiOC (N) film can be controlled, and the film stress can be freely applied to both the tensile side and the compressive side. It was confirmed that it was controllable.

Claims (21)

(a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
By controlling the third temperature in (c), each ratio of maintenance and destruction of the annular structure contained in the second film is controlled, and the stress of the second film is controlled. method. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
to control the stress of the second film by controlling the third temperature in (c),
The annular structure includes a Si-C bond, and in (c), the holding and cleavage of the Si-C bond included in the second film are controlled. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
to control the stress of the second film by controlling the third temperature in (c),
The annular structure includes a Si-C bond, and in (c), each ratio of maintenance and cleavage of the Si-C bond included in the second film is controlled. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein in (c), the stress of the second film is controlled to be either a tensile stress or a compressive stress. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the third temperature in (c) is a temperature at which the annular structure included in the second film is maintained. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
to control the stress of the second film by controlling the third temperature in (c),
The cyclic structure includes a Si-C bond, and the third temperature in (c) is a temperature at which the Si-C bond contained in the second film is maintained. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the third temperature in (c) is set to 400°C or higher and 600°C or lower. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the stress of the second film is made into a tensile stress by maintaining the annular structure contained in the second film according to (c). . The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the third temperature in (c) is a temperature at which the annular structure included in the second film is destroyed. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
to control the stress of the second film by controlling the third temperature in (c),
The cyclic structure includes a Si-C bond, and the third temperature in (c) is a temperature at which the Si-C bond included in the second film is cleaved. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the third temperature in (c) is set to 700°C or higher and 1200°C or lower. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
to control the stress of the second film by controlling the third temperature in (c),
The third temperature in (c) is set to 700°C or higher and 1200°C or lower,
The method for manufacturing a semiconductor device according to (c), wherein the stress of the second film is made a compressive stress by destroying the annular structure included in the second film. The method according to any one of claims 1 to 3, 6, 10, and 12, wherein (a), (b) and (c) are performed in a state in which the substrate is accommodated in the same processing chamber. , a method of manufacturing a semiconductor device. 13. The method according to any one of claims 1 to 3, 6, 10, 12, wherein the second film in (b) comprises water,
The method of manufacturing a semiconductor device according to (c), wherein moisture contained in the second film is desorbed. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature at which the annular structure included in the second film is destroyed
have,
In (c), the second film is annealed under the third temperature to destroy the annular structure included in the second film, and the stress of the second film is used as a compressive stress. . (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature
and, by controlling the third temperature in (c), each ratio of maintenance and destruction of the annular structure contained in the second film is controlled, and the stress of the second film is controlled. (a) at a first temperature, a cycle of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to the substrate and supplying a nitriding agent to the substrate a predetermined number of times asynchronously thereby forming a first film containing the annular structure and nitrogen on the substrate;
(b) converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) annealing the second film under a third temperature at which the annular structure included in the second film is destroyed
have,
In (c), the second film is annealed under the third temperature to destroy the annular structure included in the second film, and the stress of the second film is made a compressive stress. a processing chamber in which the substrate is processed;
a raw material supply system for supplying a raw material containing a cyclic structure composed of silicon and carbon and a halogen to the substrate in the processing chamber;
a nitriding agent supply system for supplying a nitriding agent to the substrate in the processing chamber;
an oxidizing agent supply system for supplying an oxidizing agent to the substrate in the processing chamber;
a heater for heating the substrate in the processing chamber;
In the processing chamber, (a) at a first temperature, a cycle of non-simultaneously performing a process of supplying the raw material to the substrate and a process of supplying the nitriding agent to the substrate is performed a predetermined number of times, whereby the , a process for forming a first film containing the cyclic structure and nitrogen, and (b) supplying the oxidizing agent to the substrate under a second temperature, thereby converting the first film to a second film containing the cyclic structure and oxygen a process for converting the film into a film, (c) performing a process for annealing the second film under a third temperature, and controlling the third temperature in (c), thereby forming the annular structure contained in the second film. a control unit configured to be able to control the raw material supply system, the nitriding agent supply system, the oxidizer supply system, and the heater so as to control the respective ratios of holding and breaking, and to control the stress of the second film
A substrate processing apparatus having a. a processing chamber in which the substrate is processed;
a raw material supply system for supplying a raw material containing a cyclic structure composed of silicon and carbon and a halogen to the substrate in the processing chamber;
a nitriding agent supply system for supplying a nitriding agent to the substrate in the processing chamber;
an oxidizing agent supply system for supplying an oxidizing agent to the substrate in the processing chamber;
a heater for heating the substrate in the processing chamber;
In the processing chamber, (a) at a first temperature, a cycle of non-simultaneously performing a process of supplying the raw material to a substrate and a process of supplying the nitriding agent to the substrate a predetermined number of times is performed, thereby , a process for forming a first film containing the cyclic structure and nitrogen, and (b) supplying the oxidizing agent to the substrate under a second temperature, whereby the first film is formed into a second film containing the cyclic structure and oxygen a process for converting the film into a film, and (c) a process for annealing the second film under a third temperature at which the annular structure included in the second film is destroyed;
In (c), the raw material supply system is annealed to the second film under the third temperature to destroy the annular structure included in the second film, and to make the stress of the second film a compressive stress; A control unit configured to be able to control the nitriding agent supply system, the oxidizer supply system, and the heater
having, a substrate processing apparatus. In the processing chamber of the substrate processing apparatus,
(a) A cycle in which a process of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to a substrate and a procedure of supplying a nitriding agent to the substrate are asynchronously performed a predetermined number of times under the first temperature By doing so, the procedure of forming a first film containing the cyclic structure and nitrogen on the substrate;
(b) a procedure of converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) a procedure for performing thermal annealing on the second film under a third temperature;
A procedure for controlling the respective ratios of maintenance and destruction of the annular structure included in the second film by controlling the third temperature in (c), and controlling the stress of the second film
A program recorded on a computer-readable recording medium that causes the substrate processing apparatus to execute by a computer. In the processing chamber of the substrate processing apparatus,
(a) A cycle in which a process of supplying a raw material containing a halogen and a cyclic structure composed of silicon and carbon to a substrate and a procedure of supplying a nitriding agent to the substrate are asynchronously performed a predetermined number of times under the first temperature By doing so, the procedure of forming a first film containing the cyclic structure and nitrogen on the substrate;
(b) a procedure of converting the first film into a second film containing the annular structure and oxygen by supplying an oxidizing agent to the substrate under a second temperature;
(c) a procedure of annealing the second film under a third temperature at which the annular structure included in the second film is destroyed;
In (c), a procedure in which the annular structure included in the second film is destroyed by annealing the second film under the third temperature, and the stress of the second film is converted to a compressive stress.
A program recorded on a computer-readable recording medium that causes the substrate processing apparatus to execute by a computer.

Images