阅读说明：本技术 清洗方法、半导体器件的制造方法、衬底处理装置及存储介质 (cleaning method, method for manufacturing semiconductor device, substrate processing apparatus, and storage medium ) 是由 栗林幸永 花岛建夫 宫岸宏幸 山岸裕人 于 2019-06-03 设计创作，主要内容包括：本发明公开了一种清洗方法、半导体器件的制造方法、衬底处理装置、及存储介质。其技术问题在于,提高对衬底供给处理气体的供给部内的清洗处理的品质。为此,提供一种清洗方法,通过将包含(a)工序和(b)工序的循环进行规定次数来对供给部内进行清洗,上述(a)工序是在从供给部对衬底供给处理气体而对衬底进行了处理后,从供给部向处理完衬底后的处理容器内供给清洗气体及与清洗气体反应的添加气体中的某一方气体的工序；上述(b)工序是在停止一方气体的供给后,在一方气体的一部分残留在供给部内的状态下,从供给部向处理容器内供给清洗气体及添加气体中的与一方气体不同的另一方气体的工序。(The invention discloses a cleaning method, a method for manufacturing a semiconductor device, a substrate processing apparatus, and a storage medium. The technical problem is to improve the quality of the cleaning treatment in a supply part for supplying the treatment gas to the substrate. To achieve this, there is provided a cleaning method for cleaning the inside of a supply part by performing a cycle including a step (a) of supplying a process gas to a substrate from the supply part to process the substrate, and then supplying one of the process gas and an additive gas that reacts with the process gas from the supply part to a process container after the substrate has been processed; the step (b) is a step of supplying the other of the purge gas and the additive gas, which is different from the one gas, from the supply unit into the process chamber in a state where a part of the one gas remains in the supply unit after the supply of the one gas is stopped.)

1. A cleaning method is characterized in that the cleaning method comprises the following steps,

comprises a step of cleaning the inside of the supply part by performing a cycle comprising the step (a) and the step (b) a predetermined number of times,

The step (a) is a step of supplying a process gas from the supply unit to the substrate to process the substrate, and then supplying one of a purge gas and an additive gas that reacts with the purge gas from the supply unit into the process container after the substrate has been processed;

the step (b) is a step of supplying the other gas different from the one gas of the purge gas and the additive gas from the supply unit into the processing chamber in a state where a part of the one gas remains in the supply unit after the supply of the one gas is stopped.

2. The cleaning method according to claim 1,

The step (b) is performed in a state where the inside of the processing container is exhausted.

3. The cleaning method according to claim 1,

and (b) moving a part of the one gas remaining in the supply portion into the processing container.

4. The cleaning method according to claim 1,

In the step (b), the remaining amount of the one gas in the supply portion is reduced with time.

5. The cleaning method according to claim 1,

In the step (b), the concentration of the one gas in the supply portion is decreased with time.

6. The cleaning method according to claim 1,

In the step (b), the volume ratio of the other gas to the one gas in the supply unit is increased with time.

7. The cleaning method according to claim 1,

In the step (b), a peak point of a reaction between the one gas and the other gas in the supply unit is moved.

8. The cleaning method according to claim 1,

In the step (b), a peak point of a heat generation amount of reaction heat generated by a reaction between the one gas and the other gas in the supply unit is shifted.

9. The cleaning method according to claim 1,

the cycle further comprises (c) a step,

(c) The step of removing the gas remaining in the supply portion after stopping the supply of the other gas.

10. The cleaning method according to claim 9,

in the step (c), the gas remaining in the supply portion and the processing container is removed.

11. the cleaning method according to claim 1,

in the step (a), the pressure in the processing container is adjusted using the one gas, and the processing container is filled with the one gas.

12. The cleaning method according to claim 1,

The one gas is the purge gas and the other gas is the additive gas.

13. the cleaning method according to claim 1,

The one gas is the additive gas, and the other gas is the purge gas.

14. The cleaning method according to claim 1,

In the step (a), the other gas is supplied into the processing container from a supply unit different from the supply unit,

In the step (b), after the supply of the other gas is stopped, the one gas is supplied from the other supply unit into the process container in a state where a part of the other gas remains in the other supply unit.

15. The cleaning method according to claim 14,

The other supply unit is a supply unit that supplies the process gas when the substrate is processed.

16. The cleaning method according to claim 1,

In the step (a), the one gas is supplied into the processing container from a supply unit different from the supply unit,

In the step (b), after the supply of the one gas is stopped, the other gas is supplied from the other supply unit into the processing chamber in a state where a part of the one gas remains in the other supply unit.

17. the cleaning method according to claim 16,

The other supply unit is a supply unit that supplies the process gas when the substrate is processed.

18. The cleaning method according to claim 1,

The cleaning gas comprises fluorine gas, hydrogen fluoride gas, chlorine fluoride gas, nitrogen fluoride gas or a mixed gas of the gases, and the additive gas comprises nitric oxide gas, hydrogen gas, oxygen gas, nitrous oxide gas, isopropanol gas, methanol gas, water vapor, hydrogen fluoride gas or a mixed gas of the gases.

19. A method for manufacturing a semiconductor device, comprising:

Supplying a process gas from a supply unit to a substrate in a process container to process the substrate; and

a step of cleaning the inside of the supply part after the substrate is processed,

Cleaning the inside of the supply part by performing a cycle including the step (a) and the step (b) a predetermined number of times in the step of cleaning the inside of the supply part,

The step (a) is a step of supplying one of a purge gas and an additive gas that reacts with the purge gas from the supply unit into the processing chamber,

The step (b) is a step of supplying the other gas different from the one gas of the purge gas and the additive gas from the supply unit into the processing chamber in a state where a part of the one gas remains in the supply unit after the supply of the one gas is stopped.

20. a substrate processing apparatus, comprising:

A processing container in which processing of a substrate is performed;

a supply unit configured to supply a process gas into the process container;

A cleaning gas supply system configured to supply a cleaning gas into the processing chamber;

An additive gas supply system configured to supply an additive gas that reacts with the purge gas into the processing chamber; and

A control unit configured to control the purge gas supply system and the additive gas supply system so that the inside of the supply unit is purged by performing a cycle including the process (a) and the process (b) a predetermined number of times,

The (a) process is a process in which, after a substrate is processed by supplying the process gas from the supply unit to the substrate, one of the purge gas and the additive gas is supplied from the supply unit into the process container after the substrate has been processed;

the step (b) is a step of supplying the other gas different from the one gas of the purge gas and the additive gas from the supply unit into the process container in a state where a part of the one gas remains in the supply unit after the supply of the one gas is stopped.

21. a storage medium characterized in that,

Which is readable by a computer and stores a program for causing a computer to execute a step of cleaning the inside of the supply section by performing a cycle including the step (a) and the step (b) a predetermined number of times,

The step (a) is a step of supplying a cleaning gas or an additive gas that reacts with the cleaning gas from a supply unit into a processing chamber of the substrate processing apparatus after a substrate is processed by supplying the processing gas from the supply unit to the substrate;

The step (b) is a step of supplying the other gas different from the one gas of the purge gas and the additive gas from the supply unit into the processing chamber in a state where a part of the one gas remains in the supply unit after the supply of the one gas is stopped.

Technical Field

The invention relates to a cleaning method, a method for manufacturing a semiconductor device, a substrate processing apparatus, and a storage medium.

Background

As one of the steps of the manufacturing process of the semiconductor device, there is a case where the following steps are performed: a process gas is supplied from a supply unit to the substrate in the process container to process the substrate. When a predetermined amount of deposit adheres to the inside of the supply unit by performing this step, the inside of the supply unit may be cleaned at a predetermined timing (see, for example, patent document 1).

Disclosure of Invention

The invention aims to provide a technology capable of improving the quality of cleaning treatment in a supply part for supplying a treatment gas to a substrate.

According to one embodiment of the present invention, there is provided a technique for cleaning the inside of a supply portion by performing a cycle including the step (a) and the step (b) a predetermined number of times.

(a) A step of supplying a process gas from the supply unit to the substrate to process the substrate, and then supplying one of a purge gas and an additive gas that reacts with the purge gas from the supply unit into the process container after the substrate has been processed;

(b) The step of supplying the other of the purge gas and the additive gas, which is different from the one of the purge gas and the additive gas, from the supply unit into the processing chamber in a state where a part of the one of the purge gas and the additive gas remains in the supply unit after the supply of the one of the purge gas and the additive gas is stopped.

Effects of the invention

According to the present invention, the quality of the cleaning process in the supply unit for supplying the process gas to the substrate can be improved.

Drawings

fig. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in the embodiment of the present invention, and is a diagram showing a part of the processing furnace in a longitudinal sectional view.

fig. 2 is a schematic configuration diagram of a part of a vertical processing furnace of a substrate processing apparatus preferably used in the embodiment of the present invention, and is a diagram showing a part of the processing furnace in a sectional view along line a-a of fig. 1.

Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in the embodiment of the present invention, and is a diagram showing a control system of the controller in a block diagram.

Fig. 4 (a) is a diagram showing a gas supply procedure of the 1 st cleaning process according to the embodiment of the present invention, and (b) is a diagram showing a modification of the gas supply procedure of the 1 st cleaning process according to the embodiment of the present invention.

Fig. 5 (a) and (b) are views showing modifications of the gas supply sequence in the 1 st cleaning process according to the embodiment of the present invention.

Fig. 6 is a diagram showing a modification of the gas supply procedure in the 1 st cleaning process according to the embodiment of the present invention.

fig. 7 is a diagram showing a modification of the gas supply procedure in the 1 st cleaning process according to the embodiment of the present invention.

Fig. 8 (a) and (b) are cross-sectional views showing modifications of the vertical processing furnace, respectively, and are views showing a reaction tube, a buffer chamber, a nozzle, and the like, which are partially extracted.

Detailed Description

< one embodiment of the present invention >

An embodiment of the present invention will be described below with reference to fig. 1 to 3 and (a) of fig. 4.

(1) Constitution of substrate processing apparatus

as shown in fig. 1, the processing furnace 202 has a heater 207 as a heating means (temperature adjustment 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 portion) that activates (excites) the gas by heat.

A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207, the reaction tube 203 is made of a heat-resistant material such as quartz (SiO ₂) or silicon carbide (SiC), and is formed into a cylindrical shape having a closed upper end and an open lower end, a manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203, the manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape having an open upper end and a open lower end, the upper end of the manifold 209 is engaged with the lower end of the reaction tube 203 to support the reaction tube 203, an O-ring 220a serving as a sealing member is provided between the manifold 209 and the reaction tube 203, the reaction tube 203 is vertically mounted in the same manner as the heater 207, a process container (reaction container) is mainly made of the reaction tube 203 and the manifold 209, a process chamber 201 is formed in a cylindrical hollow portion of the process container, a wafer 200 serving as a substrate is housed in the process chamber 201.

In the processing chamber 201, nozzles 249a to 249c as the 1 st to 3 rd supply units are provided so as to penetrate through the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as nozzles 1 to 3. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. The nozzles 249a to 249c are connected to the gas supply pipes 232a to 232c, respectively. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are provided adjacent to the nozzle 249b, respectively, and are arranged so as to sandwich the nozzle 249b from both sides.

The gas supply pipes 232a to 232c are provided with Mass Flow Controllers (MFCs) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as opening and closing valves, respectively, in this order from the upstream side of the gas flow. Gas supply pipes 232d and 232e are connected to the gas supply pipe 232b on the downstream side of the valve 243 b. The gas supply pipes 232d and 232e are provided with MFCs 241d and 241e and valves 243d and 243e, respectively, in this order from the upstream side of the gas flow. Gas supply pipes 232f to 232h are connected to the gas supply pipes 232a to 232c on the downstream side of the valves 243a to 243c, respectively. The gas supply pipes 232f to 232h are provided with MFCs 241f to 241h and valves 243f to 243h, respectively, in this order from the upstream side of the gas flow. The gas supply pipes 232a to 232h are made of a metal material such as stainless steel (SUS), for example.

As shown in fig. 2, the nozzles 249a to 249c are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafers 200, and stand upright along the lower portion to the upper portion of the inner wall of the reaction tube 203 in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided along the wafer arrangement region, in regions horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged. The nozzle 249b is disposed so as to face the exhaust port 231a described later on a straight line across the center of the wafer 200 carried into the processing chamber 201 in a plan view. The nozzles 249a and 249c are arranged along the inner wall of the reaction tube 203 (the outer peripheral portion of the wafer 200) so as to sandwich a straight line L passing through the centers of the nozzle 249b and the exhaust port 231a from both sides. The line L is also a line passing through the nozzle 249b and the center of the wafer 200. The nozzle 249c may be provided on the opposite side of the nozzle 249a with the straight line L therebetween. The nozzles 249a and 249c are arranged symmetrically about the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided in side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are opened so as to face (face) the exhaust port 231a in a plan view, and can supply gas to the wafer 200. The gas supply holes 250a to 250c are provided in plural numbers from the lower portion to the upper portion of the reaction tube 203.

A hydrogen nitride-based gas, which is, for example, a nitrogen (N) -containing gas, is supplied as a process gas, i.e., a reactant (reactant) having a chemical structure (molecular structure) different from that of a raw material described later, into the process chamber 201 from the gas supply pipes 232a and 232c through the MFCs 241a and 241c, the valves 243a and 243c, and the nozzles 249a and 249c, and the hydrogen nitride-based gas functions as a nitrogen source (N source), i.e., a nitrogen source, and, for example, ammonia (NH ₃) gas can be used as the hydrogen nitride-based gas.

_{2 6}A halosilane-based gas containing, for example, Si and halogen as a predetermined element (main element) constituting a film is supplied as a process gas, that is, a raw material (raw material gas), into the process chamber 201 from the gas supply pipe 232b via the MFC241b, the valve 243b, and the nozzle 249b, the raw material gas refers to a gaseous raw material, for example, a gas obtained by vaporizing a raw material which is liquid at normal temperature and normal pressure, a raw material which is gaseous at normal temperature and normal pressure, and the like.

A fluorine-based gas is supplied as a purge gas into the processing chamber 201 from the gas supply pipe 232d through the MFC241d, the valve 243d, the gas supply pipe 232b, and the nozzle 249b, and a fluorine (F ₂) gas, for example, can be used as the fluorine-based gas.

The nitrogen oxide-based gas is supplied as an additive gas having a chemical structure (molecular structure) different from that of the cleaning gas from the gas supply pipe 232e through the MFC241e, the valve 243e, the gas supply pipe 232b, and the nozzle 249b into the processing chamber 201. The nitrogen oxide-based gas does not have a cleaning effect, but reacts with the fluorine-based gas to generate active species such as fluorine radicals and/or nitrosofluorine compounds, thereby improving the cleaning effect of the fluorine-based gas. As the nitrogen oxide-based gas, for example, nitrogen monoxide (NO) gas can be used.

For example, nitrogen (N ₂) gas is supplied as an inert gas into the processing chamber 201 from the gas supply pipes 232f to 232h through the MFCs 241f to 241h, the valves 243f to 243h, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c, respectively, and the N ₂ gas functions as a purge gas, a carrier gas, a diluent gas, and the like.

the 2 nd process gas supply system (reactant supply system) is mainly constituted by the gas supply pipe 232a, the MFC241a, the valve 243a, and/or the gas supply pipe 232c, the MFC241c, and the valve 243 c. The gas supply pipe 232b, the MFC241b, and the valve 243b mainly constitute a 1 st process gas supply system (source material supply system). The purge gas supply system is mainly constituted by the gas supply pipe 232d, the MFC241d, and the valve 243 d. The additive gas supply system is mainly constituted by the gas supply pipe 232e, the MFC241e, and the valve 243 e. The inert gas supply system is mainly constituted by gas supply pipes 232f to 232h, MFCs 241f to 241h, and valves 243f to 243 h.

Any or all of the various supply systems described above may be configured as an integrated supply system 248 that is integrated with the valves 243a to 243h and/or the MFCs 241a to 241 h. The integrated supply system 248 is connected to the gas supply pipes 232a to 232h, and configured to control supply operations of various gases into the gas supply pipes 232a to 232h, that is, opening and closing operations of the valves 243a to 243h, flow rate adjustment operations by the MFCs 241a to 241h, and the like, by the controller 121 described below. The integrated supply system 248 is configured as an integrated unit or a divided integrated unit, and is configured such that the gas supply pipes 232a to 232h and the like can be attached and detached in units of integrated units, and maintenance, replacement, addition and the like of the integrated supply system 248 can be performed in units of integrated units.

An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. As shown in fig. 2, the exhaust port 231a is provided at a position facing (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in a plan view. The exhaust port 231a may be disposed along the lower portion to the upper portion of the sidewall of the reaction tube 203, i.e., along the wafer arrangement region. The exhaust port 231a is connected to the exhaust pipe 231. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a Pressure sensor 245 as a Pressure detector (Pressure detector) for detecting the Pressure in the processing chamber 201 and an apc (auto Pressure controller) valve 244 as a Pressure regulator (Pressure adjuster). The APC valve 244 is a valve constructed in the following manner: the vacuum pump 246 is operated to open and close the valve, whereby the inside of the processing chamber 201 can be evacuated and the evacuation can be stopped, and the vacuum pump 246 is operated to adjust the opening of the valve based on the pressure information detected by the pressure sensor 245, thereby adjusting the pressure inside the processing chamber 201. The exhaust system is mainly constituted by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is contemplated that a vacuum pump 246 may be included in the exhaust system.

Exhaust pipe 231 is made of an alloy having excellent heat resistance and/or corrosion resistance. As the alloy, for example, Hastelloy (registered trademark) in which heat resistance and corrosion resistance are improved by adding iron (Fe), molybdenum (Mo), chromium (Cr), or the like to nickel (Ni), inconel (registered trademark) in which heat resistance and corrosion resistance are improved by adding Fe, Cr, niobium (Nb), Mo, or the like to Ni, or the like can be preferably used in addition to SUS.

A seal cap 219 serving as a furnace opening cover capable of hermetically sealing the lower end opening of the collecting pipe 209 is provided below the collecting pipe 209. The seal cap 219 is made of a metal material such as SUS, and is formed in a disk shape. An O-ring 220b as a sealing member is provided on the upper surface of the seal cap 219 to be in contact with the lower end of the manifold 209. A rotation mechanism 267 for rotating the vessel 217 described later is provided below the seal cap 219. The rotary shaft 255 of the rotary mechanism 267 penetrates the seal cap 219 and is connected to the vessel 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the vessel 217. The sealing cap 219 is configured to be vertically moved up and down by a dish lifter 115 as an elevating mechanism provided outside the reaction tube 203. The dish elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafer 200 into and out of the processing chamber 201 (transfers the wafer inside and outside the processing chamber 201) by moving the sealing cap 219 up and down. Below the header pipe 209 are provided: in a state where the sealing cap 219 is lowered to carry out the peripheral plate 217 from the processing chamber 201, a shutter (shutter)219s as a furnace opening lid body which is a lower end opening of the manifold 209 can be hermetically closed. The shutter 219s is formed of a metal material such as SUS, and is formed in a disk shape. An O-ring 220c as a sealing member is provided on the upper surface of the shutter 219s and abuts against the lower end of the manifold 209. The opening and closing operation (the lifting operation, the turning operation, and the like) of the shutter 219s is controlled by the shutter opening and closing mechanism 115 s.

The peripheral dish 217 serving as a substrate holder is configured in such a manner that: a plurality of (e.g., 25 to 200) wafers 200 are arranged in a horizontal posture and aligned with each other in the center in the vertical direction, and the wafers 200 are supported in a multi-stage manner, that is, the wafers 200 are arranged at intervals. The vessel 217 is made of a heat-resistant material such as quartz and/or SiC. A heat shield plate 218 made of a heat-resistant material such as quartz and/or SiC is supported in a plurality of stages on the lower portion of the vessel 217.

A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. By adjusting the energization 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 disposed along the inner wall of the reaction tube 203.

As shown in fig. 3, the controller 121 as a control Unit (control means) is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121 d. The RAM121b, the storage device 121c, and the I/O port 121d are configured to be able to exchange data with the CPU121a via the internal bus 121 e. The controller 121 is connected to an input/output device 122 configured as a touch panel or the like, for example.

The storage device 121c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, there are stored in a readable manner: a control program for controlling the operation of the substrate processing apparatus, a process recipe (process recipe) in which steps and/or conditions of the substrate processing described later are described, a cleaning recipe in which steps and/or conditions of the cleaning processing described later are described, and the like. The process recipe is a recipe obtained by combining the steps of the substrate processing described later and the controller 121 so that a predetermined result can be obtained, and functions as a program. The cleaning recipe is a recipe obtained by combining the steps of the cleaning process described later and the controller 121 so that a predetermined result can be obtained, and functions as a program. Hereinafter, the process recipe, the cleaning recipe, the control program, and the like are also collectively referred to as simply "programs". Furthermore, the process recipe and/or cleaning recipe is also referred to as recipe for short. In the present specification, when the term "program" is used, there are cases where only a recipe is contained, only a control program is contained, or both of them are contained. The RAM121b is configured as a storage area (work area) that temporarily holds programs and data read by the CPU121 a.

The I/O port 121d is connected to the MFCs 241a to 241h, the valves 243a to 243h, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the temperature sensor 263, the heater 207, the rotating mechanism 267, the dish elevator 115, the shutter opening/closing mechanism 115s, and the like.

The CPU121a is configured to read and execute a control program from the storage device 121c, and read a recipe from the storage device 121c in response to input of an operation command from the input/output device 122, and the like. The CPU121a is configured to control the following operations according to the contents of the read recipe: flow rate adjustment operation of various gases by MFCs 241a to 241h, opening and closing operation of valves 243a to 243h, opening and closing operation of APC valve 244, pressure adjustment operation by APC valve 244 based on pressure sensor 245, start and stop of vacuum pump 246, temperature adjustment operation of heater 207 based on temperature sensor 263, rotation and rotation speed adjustment operation of week dish 217 by rotation mechanism 267, lifting and lowering operation of week dish 217 by week dish lifter 115, opening and closing operation of shutter 219s by shutter opening and closing mechanism 115s, and the like.

The controller 121 can be configured by installing the above-described program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory, and the like. The storage device 121c and/or the external storage device 123 are configured as computer-readable storage media. Hereinafter, they are also collectively referred to simply as storage media. In the present specification, when the term storage medium is used, there are cases where only the storage device 121c is included, where only the external storage device 123 is included, or where both of them are included. Further, the computer may be provided with a program using a communication means such as the internet and/or a dedicated line without using the external storage device 123.

(2) substrate processing procedure

as one step of a manufacturing process of a semiconductor device using the substrate processing apparatus, a substrate processing sequence example, i.e., a film processing sequence example, in which a film is formed on a wafer 200 as a substrate will be described. In the following description, the operations of the respective parts constituting the substrate processing apparatus are controlled by the controller 121.

In the film formation sequence of the present embodiment, a silicon nitride film (SiN film) as a film containing Si and N is formed on the wafer 200 by performing a cycle of performing the following steps 1 and 2 not simultaneously for a predetermined number of times.

Step 1: HCDS gas is supplied as a raw material to the wafer 200 in the processing container.

Step 2, NH ₃ gas is supplied as a reactant to the wafer 200 in the processing chamber.

In the present specification, the above-described film formation sequence is sometimes shown as follows for convenience. The same expressions are used in the following description of modifications and the like.

In the present specification, the term "wafer" is used to include: this refers to the case of the wafer itself, and/or the case of a laminate of the wafer and a predetermined layer and/or film formed on the surface thereof. In the present specification, the case where the expression "the surface of the wafer" is used includes: the term "wafer" refers to a wafer itself and/or a predetermined layer formed on a wafer. In the present specification, the case where "a predetermined layer is formed on a wafer" includes: the term "forming a predetermined layer" refers to a case where a predetermined layer is directly formed on the surface of the wafer itself and/or a case where a predetermined layer is formed on a layer formed on the wafer or the like. In this specification, the term "substrate" is used in the same manner as the term "wafer".

(wafer Loading and Zhou dish Loading)

When the peripheral dish 217 is loaded with a plurality of wafers 200 (wafer loading), the shutter 219s is moved by the shutter opening/closing mechanism 115s, and the lower end opening of the manifold 209 is opened (the shutter is opened). Then, as shown in fig. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220 b.

(pressure adjustment and temperature adjustment)

Vacuum evacuation (reduced pressure evacuation) is performed by the vacuum pump 246 so that the pressure (degree of vacuum) in the processing chamber 201, that is, the space in which the wafer 200 is present is a desired pressure. 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. The wafer 200 in the processing chamber 201 is heated by the heater 207 so that the temperature thereof becomes a desired temperature. At this time, feedback control is performed on the condition that the heater 207 is energized based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes a desired temperature distribution. Further, the rotation of the wafer 200 by the rotation mechanism 267 is started. The evacuation of the process chamber 201, the heating of the wafer 200, and the rotation are continued at least until the processing of the wafer 200 is completed.

(film Forming step)

Then, the following steps 1 and 2 are sequentially performed.

[ step 1]

in this step, HCDS gas is supplied to the wafer 200 in the processing container (HCDS gas supply step), specifically, the valve 243b is opened to flow the HCDS gas into the gas supply pipe 232b, the flow rate of the HCDS gas is adjusted by the MFC241b, the HCDS gas is supplied into the processing chamber 201 through the nozzle 249b and is discharged from the exhaust port 231a, at this time, HCDS gas is supplied to the wafer 200, at this time, the valves 243f and 243h are opened to supply N ₂ gas into the processing chamber 201 through the nozzles 249a and 249c, at this time, the valve 243g may be opened to supply N ₂ gas into the processing chamber 201 through the nozzle 249 b.

As the processing conditions in this step, the following conditions are exemplified:

HCDS gas supply flow rate: 0.01 to 2slm, preferably 0.1 to 1 slm;

The N ₂ gas supply flow rate (per gas supply pipe) is 0-10 slm;

Supply time of each gas: 1-120 seconds, preferably 1-60 seconds;

treatment temperature: 250-800 ℃, preferably 400-700 ℃;

Treatment pressure: 1 to 2666Pa, preferably 67 to 1333 Pa.

In the present specification, the expression of a numerical range of "250 to 800 ℃ means that the lower limit value and the upper limit value are included in the range. Thus, for example, "250 to 800 ℃ means" 250 ℃ to 800 ℃. Other numerical ranges are also the same.

The Si-containing layer containing Cl is formed as the 1 st layer by physically adsorbing HCDS, or a substance obtained by chemically adsorbing a part of HCDS (hereinafter, Si _x Cl _y), or depositing Si by thermally decomposing HCDS on the outermost surface of the wafer 200. the Si-containing layer containing Cl may be an adsorption layer (a physically adsorption layer and/or a chemically adsorption layer) of HCDS and/or Si _x Cl _y, or may be an Si-containing layer containing Cl (a Si deposition layer).

After the layer 1 is formed, the valve 243b is closed to stop the supply of the HCDS gas into the process chamber 201, and the process chamber 201 is evacuated to remove the gas and the like remaining in the process chamber 201 from the process chamber 201 (purge step). at this time, the valves 243f to 243h are opened to supply the N ₂ gas into the process chamber 201, and the N ₂ gas functions as a purge gas.

as the raw material, chlorosilane-based gases such as monochlorosilane (SiH ₃ Cl, abbreviated as MCS) gas, dichlorosilane (SiH ₂ Cl ₂, abbreviated as DCS) gas, trichlorosilane (SiHCl ₃, abbreviated as TCS) gas, tetrachlorosilane (SiCl ₄, abbreviated as STC) gas, octachlorotris silane (Si ₃ Cl ₈, abbreviated as OCTS) gas, which are gases capable of depositing a film alone under the above-mentioned process conditions, can be used in addition to HCDS gas.

As the inert gas, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to the N ₂ gas, and this point is also the same in step 2 and the cleaning process step described later.

[ step 2]

After step 1 is completed, NH ₃ gas is supplied to the wafer 200 in the processing chamber, that is, the 1 st layer formed on the wafer 200 (NH ₃ gas supply step). specifically, NH ₃ gas is flowed into the gas supply pipe 232a by opening the valve 243 a. NH ₃ gas is supplied into the processing chamber 201 through the nozzle 249a by adjusting the flow rate of MFC241a gas, and is discharged from the exhaust port 231 a. at this time, NH ₃ gas is supplied to the wafer 200. at this time, N ₂ gas is supplied into the processing chamber 201 through the nozzles 249b and 249c by opening the valves 243g and 243h, and at this time, N ₂ gas may be supplied into the processing chamber 201 through the nozzle 249a by opening the valve 243 f.

As the processing conditions in this step, the following conditions are exemplified:

The NH ₃ gas supply flow rate is 0.1-10 slm;

The N ₂ gas supply flow rate (per gas supply pipe) is 0-2 slm;

NH ₃ gas is supplied for 1 to 120 seconds, preferably 1 to 60 seconds;

Treatment pressure: 1 to 4000Pa, preferably 1 to 3000 Pa.

The other treatment conditions were the same as those in step 1.

in the above-described conditions, NH ₃ gas is supplied to the wafer 200, whereby at least a part of the 1 st layer formed on the wafer 200 is nitrided (modified), the 1 st layer is modified, whereby the 2 nd layer containing Si and N, that is, an SiN layer is formed on the wafer 200, in the formation of the 2 nd layer, impurities such as Cl contained in the 1 st layer constitute gaseous substances containing at least Cl in the process of the modification reaction of the 1 st layer by NH ₃ gas, and are discharged from the inside of the processing chamber 201, whereby the 2 nd layer becomes a layer containing less impurities such as Cl than the 1 st layer.

After the layer 2 is formed, the valve 243a is closed to stop the supply of the NH ₃ gas into the process chamber 201, and the gas and the like remaining in the process chamber 201 are removed from the process chamber 201 by the same process step as the purge step of step 1 (purge step).

As the reactant, besides NH ₃ gas, for example, a hydrogen nitride-based gas such as diazene (N ₂ H ₂) gas, hydrazine (N ₂ H ₄) gas, or N ₃ H ₈ gas can be used.

[ predetermined number of executions ]

By executing the cycle of steps 1 and 2a predetermined number of times (m times, m being an integer of 1 or more) non-simultaneously, i.e., asynchronously, SiN films having a predetermined composition and a predetermined film thickness can be formed on the wafer 200. The above cycle is preferably repeated a plurality of times. That is, the thickness of the 2 nd layer formed when the above-described cycle is performed 1 time is preferably made thinner than a desired film thickness, and the above-described cycle is repeated a plurality of times until the film thickness of the SiN film formed by laminating the 2 nd layers becomes a desired film thickness.

(post purge and atmospheric pressure recovery)

after the film formation step is completed, N ₂ gas as a purge gas is supplied into the process chamber 201 from the nozzles 249a to 249c, respectively, and is discharged from the exhaust port 231a, whereby the process chamber 201 is purged, and the gas and/or the reaction by-product remaining in the process chamber 201 are removed from the process chamber 201 (post-purge), and thereafter, the atmosphere in the process chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the process chamber 201 is returned to normal pressure (atmospheric pressure recovery).

(Zhou Wai unload and wafer removal)

The sealing cap 219 is lowered by the dish elevator 115, and the lower end of the header 209 is opened. The processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 (unloaded) while being supported by the peripheral plate 217. After the vessel is unloaded, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (the shutter is closed). The processed wafer 200 is carried out to the outside of the reaction tube 203, and then taken out from the peripheral dish 217 (wafer take-out).

(3) Cleaning treatment Process

In the substrate processing, deposits including thin films such as SiN films may adhere to and accumulate inside the nozzle 249b for supplying HCDS gas, because even if N ₂ gas is supplied from the nozzle 249b for supplying NH ₃ gas in step 2 to prevent NH ₃ gas from penetrating into the nozzle 249b, a predetermined amount of NH ₃ gas may penetrate inside the nozzle 249 b.

Further, even if N ₂ gas is supplied from the nozzles 249a and 249c, respectively, to which HCDS gas is not supplied in step 1, and HCDS gas is prevented from intruding into the nozzles 249a and 249c, a predetermined amount of HCDS gas is also intruded into the nozzles 249a and 249c, and even if N ₂ gas is supplied from the nozzle 249c, to which NH ₃ gas is not supplied, and NH ₃ gas is prevented from intruding into the nozzle 249c, a predetermined amount of NH ₃ gas is also intruded into the nozzle 249c in step 2, deposits including thin films such as SiN films are accumulated not only in the nozzle 249b but also in the nozzles 249a and 249 c.

In the substrate processing, deposits including thin films such as SiN films may accumulate not only inside the nozzles 249a to 249c but also inside the processing container, for example, the inner wall of the reaction tube 203, the surfaces of the nozzles 249a to 249c, the surface of the peripheral dish 217, and the like.

further, inside the nozzle 249b to which the HCDS gas containing the element Si alone as a solid is supplied, deposits are more likely to accumulate than inside the nozzles 249a and 249c, and deposits rich in Si tend to accumulate.

In the present embodiment, at least when the amount of the deposit accumulated in the nozzle 249b and/or the amount of the deposit accumulated in the processing container (i.e., the accumulated film thickness) reaches a predetermined amount (thickness) before the deposit peels off and/or falls, the inside of the nozzle 249b and/or the inside of the processing container and the like are cleaned. In this specification, this process performed in the nozzle 249b is referred to as a 1 st cleaning process.

In the 1 st cleaning process of the present embodiment, a cycle including the following steps is performed a predetermined number of times (n times, n is an integer of 1 or more):

step a: supplying an HCDS gas as a process gas from a nozzle 249b as a supply part to the wafer 200 to process the wafer 200, and then supplying one of a cleaning gas and an additive gas reacting with the cleaning gas from the nozzle 249b into the process container after the wafer 200 is processed;

Step b: when a part of the one gas remains in the nozzle 249b after the supply of the one gas is stopped, the other gas different from the one gas, out of the purge gas and the additive gas, is supplied from the nozzle 249b into the processing chamber.

In the 1 st cleaning process of the present embodiment, there is no timing to supply the cleaning gas and the additive gas into the nozzle 249b at the same time. That is, when one of the purge gas and the additive gas is supplied into the nozzle 249b in step a, the flow rate of the other gas supplied into the nozzle 249b in step a is zero. When the other gas is supplied into the nozzle 249b in step b, the flow rate of the one gas supplied into the nozzle 249b in step b is zero.

An example of the 1 st cleaning process using F ₂ gas as the cleaning gas and NO gas as the additive gas, respectively, will be described below with reference to fig. 4 (a), in which fig. 4 (a) shows an example of using F ₂ gas as the one gas supplied in step a and NO gas as the other gas supplied in step b, respectively, fig. 4 (a) shows an example of a pressure adjusting step of adjusting the pressure in the process container using N ₂ gas before supplying F ₂ gas into the process container in step a, and fig. 4 (a) shows an example of performing step c of removing gas remaining in the nozzles 249b, preferably remaining in the nozzles 249a to 249c and in the process container after performing step b, when performing the above-described cycle.

In fig. 4 (a), for convenience, the implementation periods of steps a to c are denoted as a to c, and for convenience, the implementation period of the pressure adjustment step performed in step a is denoted as a ₀, and for convenience, the implementation periods of the steps 249a to 249c are denoted as R1 to R3, respectively, and the reference numerals of the respective nozzles are the same in fig. 4 (b), fig. 5 (a), fig. 5 (b), fig. 6, and fig. 7, which show the gas supply sequence of the modification described later.

In this specification, for convenience, the gas supply sequence of the 1 st cleaning process performed in the nozzle 249b is sometimes shown as follows. The same expressions are used in the following description of the modified examples.

R2：(N₂-Press.set→F₂→NO→PRG)×n

In the following description, the operations of the respective parts constituting the substrate processing apparatus are controlled by the controller 121.

(Zhou dish loading)

The shutter 219s is moved by the shutter opening/closing mechanism 115s, and the lower end opening of the manifold 209 is opened (the shutter is opened). Then, the empty boat 217, that is, the boat 217 not loaded with the wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201. In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220 b.

(pressure adjustment and temperature adjustment)

the processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (vacuum degree) is achieved. The inside of the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the components in the processing chamber 201, that is, the inner wall of the reaction tube 203, the surface and/or the interior (inner wall) of the nozzles 249a to 249c, the surface of the vessel 217, and the like are also heated to a desired temperature. After the temperature in the processing chamber 201 reaches a desired temperature, the temperature is controlled to be maintained until the 1 st to 3 rd cleaning processes described later are completed. Subsequently, the rotation of the dish 217 by the rotating mechanism 267 is started. The rotation of the peripheral dish 217 is continued until the 1 st to 3 rd cleaning processes described later are completed. The vessel 217 may not be rotated.

(1 st cleaning treatment)

Then, the following steps a to c are sequentially performed.

[ step a ]

First, step a. in this step, as will be described later, a pressure adjustment step and an F ₂ gas supply step are performed in this order.

First, N ₂ gas is supplied into the processing container from the nozzles 249a to 249c, and the pressure in the processing container is adjusted so that the pressure in the processing container becomes a predetermined processing pressure (pressure adjustment step). specifically, N ₂ gas is flowed into the gas supply pipes 232f to 232h by opening the valves 243f to 243h, N ₂ gas is flow-adjusted by the MFCs 241f to 241h, is supplied into the processing chamber 201 through the gas supply pipes 232a to 232c and the nozzles 249a to 249c, and is discharged from the exhaust port 231 a. at this time, the APC valve 244 is adjusted based on the pressure information detected by the pressure sensor 245, and the pressure in the processing chamber 201 is adjusted so that the pressure in the processing chamber 201 becomes the predetermined processing pressure, and after the pressure in the processing chamber 201 becomes the predetermined processing pressure, the valves 243f to 243h are closed, and the supply of the N ₂ gas into the processing chamber 201 is stopped.

Next, F ₂ gas is supplied into the process container from the nozzle 249b (F ₂ gas supply step) — that is, the gas supplied into the process container is switched from N ₂ gas to F ₂ gas, specifically, the valve 243d is opened to flow the F ₂ gas into the gas supply pipe 232d, the flow rate of the F ₂ gas is adjusted by the MFC241d, the gas is supplied into the process chamber 201 through the gas supply pipe 232b and the nozzle 249b, and the gas is discharged from the exhaust port 231a, the valve 243d is closed after a predetermined time has elapsed from the start of the supply of the F ₂ gas, and the supply of the F ₂ gas into the process chamber 201 through the nozzle 249b is stopped, at this time, at least any one of the valves 243F to 243h may be opened, and the N ₂ gas may be supplied into the process chamber 201 through at least any one of the nozzles 249a to 249 c.

By sequentially performing these steps, a state is achieved in which a part of the F ₂ gas supplied from the gas supply pipe 232d remains in the nozzle 249b, a state is achieved in which a part of the F ₂ gas remaining in the nozzle 249b floats in the nozzle 249b and moves from the nozzle 249b into the process chamber 201, a state is achieved in which another part of the F ₂ gas remaining in the nozzle 249b adheres to the inner wall of the nozzle 249b (physical adsorption), and a state is achieved in which another part of the F ₂ gas remaining in the nozzle 249b slightly reacts with quartz constituting the inner wall of the nozzle 249b and adheres to the inner wall of the nozzle 249b (chemical adsorption).

As the processing conditions in the pressure adjusting step of step a, the following conditions are exemplified:

N ₂ gas supply flow rate (each gas supply pipe) is 0.5-10 slm;

The supply time of the N ₂ gas is 10-180 seconds;

Treatment pressure: 133 to 26600Pa, preferably 6650 to 19950 Pa;

treatment temperature: 30 to 500 ℃, preferably 200 to 300 ℃.

As the process conditions in the F ₂ gas supply step in step a, the following conditions are exemplified:

The gas supply flow rate of F ₂ is 0.1-4 slm, preferably 0.5-2 slm;

N ₂ gas supply flow rate (each gas supply pipe) is 0-10 slm;

Supply time of each gas: 10 to 120 seconds, preferably 30 to 60 seconds.

the other processing conditions were the same as those in the pressure adjustment step.

[ step b ]

Next, step b is performed, in this step, in a state where a part of the F ₂ gas remains in the nozzle 249b, NO gas is supplied from the nozzle 249b into the process container (NO gas supply step), specifically, the valve 243e is opened to flow the NO gas into the gas supply pipe 232e, the flow rate of the NO gas is adjusted by the MFC241e, the NO gas is supplied into the process chamber 201 through the gas supply pipe 232b and the nozzle 249b, and is discharged from the exhaust port 231a, at this time, at least any one of the valves 243F to 243h may be opened, and the N ₂ gas may be supplied into the process chamber 201 through at least any one of the nozzles 249a to 249 c.

By performing this step, the F ₂ gas remaining in the nozzle 249b and the NO gas supplied into the nozzle 249b can be mixed and reacted in the nozzle 249b, and by this reaction, active species such as fluorine radicals (F) and/or nitrous Fluorine (FNO) (hereinafter, these may also be collectively referred to as FNO and the like) can be generated in the nozzle 249b, and in the nozzle 249b, there is a mixed gas formed by adding FNO and the like to the F ₂ gas, and the mixed gas formed by adding FNO and the like to the F ₂ gas comes into contact with the inside of the nozzle 249b, and at this time, deposits adhering to the inside of the nozzle 249b can be removed by a thermochemical reaction (etching reaction), and the FNO and the like function to promote the etching reaction by the F ₂ gas, increase the etching rate of the deposits, that is, to assist the etching.

in this step, the etching reaction can be performed by supplying the NO gas into the nozzle 249b in a state where a part of the F ₂ gas remains in the nozzle 249b and the inside of the process chamber 201 is exhausted, whereby a part of the F ₂ gas remaining in the nozzle 249b can move into the process chamber 201, that is, the etching reaction can be performed by decreasing the residual amount (concentration, partial pressure) of the F ₂ gas in the nozzle 249b with time in this step, in other words, the etching reaction can be performed by increasing the volume ratio of the NO gas to the F ₂ gas (hereinafter, also referred to as the NO gas/F ₂ gas volume ratio) in the nozzle 249b with time in this step.

Specifically, NO gas is present in the nozzle 249b before step b is started, so that the NO gas/F ₂ gas volume ratio in the nozzle 249b is zero and the etching reaction is hardly or not performed at all, after step b is started, when the NO gas/F ₂ gas volume ratio in the nozzle 249b is greater than zero, the etching reaction is started and the reaction is activated, the NO gas is continuously supplied into the nozzle 249b, when the NO gas/F ₂ gas volume ratio in the nozzle 249b reaches a predetermined size, the etching reaction is most activated and the reactivity of the reaction reaches a peak, when the NO gas/F ₂ gas volume ratio in the nozzle 249b is further increased, the etching reaction is further continued to the nozzle 249b, and when the NO gas/F ₂ gas volume ratio in the nozzle 249b is further increased, the etching reaction is attenuated (activation gas is not attenuated and the etching reaction is almost completely exhausted from the nozzle 249b, or when the NO gas remains almost NO gas is exhausted from the nozzle 249b, and the nozzle 249b is almost filled with NO gas, the NO gas is exhausted from the nozzle 249b, and the nozzle 249b is almost filled with NO gas in the NO gas 249b, the entire area 249b is almost infinite, when the NO gas is exhausted.

The reason why the reaction between the F ₂ gas and the NO gas in the nozzle 249b proceeds gently when the etching reaction proceeds such that the residual amount (concentration, partial pressure) of the F ₂ gas in the nozzle 249b decreases with time as compared with the case where the residual amount (concentration, partial pressure) of the F ₂ gas in the nozzle 249b is maintained constant as in the present embodiment, is that, when the etching reaction proceeds such that the residual amount (concentration, partial pressure) of the F ₂ gas in the nozzle 249b decreases with time, the period during which the reaction between the F ₂ gas and the NO gas in the nozzle 249b is most activated is limited to a period during which the volume ratio of the NO gas/F ₂ gas in the nozzle 249b reaches a predetermined size over the entire implementation period of step b, and therefore, the etching reaction proceeds gently from the nozzle 249b to the nozzle 249b while continuously supplying the F ₂ gas and the NO gas to the nozzle 249b so that the volume ratio of the NO gas/F ₂ gas in the nozzle 249b is maintained at a predetermined size, and the etching reaction proceeds from the nozzle 249b to the inside of the nozzle 249b, and the etching reaction proceeds infinitely over the nozzle 249b, thus, the etching reaction proceeds from the nozzle 249b to the inside ₂, which is prevented.

Further, as in the present embodiment, when the etching reaction is performed while moving a part of the F ₂ gas remaining in the nozzle 249b into the process chamber 201, the peak point of the reaction between the F ₂ gas and the NO gas in the nozzle 249b, that is, the position where the reaction between the F ₂ gas and the NO gas is most activated and the etching amount of the deposit is the largest, moves from the upstream side (the lower side in fig. 1, that is, the root side of the nozzle 249 b) to the downstream side (the upper side in fig. 1, that is, the tip side of the nozzle 249 b) of the gas flow in the nozzle 249b, and thus, in the present embodiment, the etching reaction can be performed while moving the peak point of the most activation of the etching reaction in the nozzle 249b, that is, the position where the etching rate of the deposit is the largest, from the root side to the tip side of the nozzle 249b as time after the step b is started, and as a result, the etching reaction can be performed intensively in a specific narrow region in the nozzle 249b, and preferably, without leaking from the root side 249b to the entire nozzle 249 b.

In the case where the etching reaction is performed while a part of the F ₂ gas remaining in the nozzle 249b is moved into the process chamber 201 as in the present embodiment, the position in the nozzle 249b where the amount of heat generation of the reaction heat generated by the reaction of the F ₂ gas and the NO gas is the largest, that is, the peak point of the amount of heat generation, can be moved from the root side to the tip side of the nozzle 249b with the lapse of time after the start of step b.

After a predetermined time has elapsed from the start of the supply of the NO gas, the valve 243e is closed, and the supply of the NO gas into the processing chamber 201 through the nozzle 249b is stopped. The nozzle 249b is in a state in which a part of the NO gas supplied from the gas supply pipe 232e remains therein. A part of the NO gas remaining in the nozzle 249b floats in the nozzle 249b and moves from the nozzle 249b into the processing chamber 201. Further, the other part of the NO gas remaining in the nozzle 249b is adhered (physically adsorbed) to the inner wall of the nozzle 249 b.

As the process conditions in step b, i.e., the NO gas supply step, the following conditions are exemplified:

NO gas supply flow rate: 0.05-2 slm, preferably 0.1-1 slm;

NO gas supply time: 10 to 120 seconds, preferably 30 to 60 seconds.

The other treatment conditions were the same as those in step a.

[ step c ]

Next, step c is performed, in this step, after the supply of the NO gas into the nozzle 249b is stopped, the gas remaining in the nozzle 249b, preferably in the nozzles 249a to 249c and in the process container is removed (residual gas removal step). specifically, in a state where the APC valve 244 is opened, the valves 243f to 243h are opened to flow the N ₂ gas into the gas supply pipes 232f to 232h, and the N ₂ gas is supplied into the process chamber 201 through the gas supply pipes 232a to 232c and the nozzles 249a to 249c, and is discharged from the exhaust port 231a, with the flow rate of the N ₂ gas being adjusted by the MFCs 241f to 241 h.

As the process conditions in step c, i.e., the residual gas removal step, the following conditions are exemplified:

The gas supply flow rate of N ₂ (per gas supply pipe) is 0.5-20 slm, preferably 1-10 slm;

The supply time of the N ₂ gas is 10 to 180 seconds, preferably 10 to 120 seconds.

The other treatment conditions were the same as those in step a.

By performing this step, the inside of the nozzle 249b can be purged, and the NO gas and the like remaining in the nozzle 249b can be removed from the inside of the nozzle 249b, and the atmosphere gas in the nozzle 249b can be replaced with N ₂ gas, and as a result, it is possible to avoid the above-mentioned etching reaction from being accidentally performed in the nozzle 249b when the F ₂ gas is supplied from the nozzle 249b into the processing chamber 201 in step a of the next cycle.

Further, by appropriately setting the process conditions in this step, the inside of the nozzles 249a and 249c and the inside of the process chamber 201 can also be purged, and the NO gas and the like remaining in the nozzles 249a and 249c and the inside of the process chamber 201 can be removed from the inside of the nozzles 249a and 249c and the inside of the process chamber 201, respectively, and the ambient gas in the nozzles 249a and 249c and the inside of the process chamber 201 can be replaced with N ₂ gas, respectively.

Further, by performing this step, the temperature of the nozzle 249b which is increased by the reaction heat of the F ₂ gas and the NO gas in step b can be appropriately lowered, and as a result, when the F ₂ gas is supplied from the nozzle 249b into the process chamber 201 in step a of the next cycle, the F ₂ gas can be prevented from contacting the inside of the nozzle 249b in a high temperature state, and the inner wall of the nozzle 249b can be prevented from being over-etched.

[ predetermined number of executions ]

Deposits adhering to the inside of the nozzle 249b can be removed by performing the cycle including the above steps a to c a predetermined number of times (1 or more).

As the cleaning gas, in addition to the F ₂ gas, Hydrogen Fluoride (HF) gas, chlorine fluoride (ClF ₃) gas, nitrogen fluoride (NF ₃) gas, or a mixed gas thereof can be used.

As the additive gas, besides NO gas, hydrogen (H ₂) gas, oxygen (O ₂) gas, nitrous oxide (N ₂ O) gas, isopropyl alcohol ((CH ₃) ₂ CHOH, abbreviated as IPA) gas, methanol (CH ₃ OH) gas, water vapor (H ₂ O gas), HF gas, or a mixed gas thereof can be used.

This point is also the same in the 2 nd cleaning process and the 3 rd cleaning process described later.

Further, when using an HF gas as the cleaning gas and an IPA gas, a methanol gas, an H ₂ O gas, or a mixed gas thereof as the additive gas, the processing temperature in the 1 st to 3 rd cleaning processes is preferably set to a predetermined temperature in a range of, for example, 30 to 300 ℃, preferably 50 to 200 ℃.

(No. 2 cleaning treatment)

₂However, there is a case where a part of the deposit adhered to the inside of the processing chamber 201 is not removed and remains in the processing chamber 201, and then, after the 1 st cleaning process is finished, the cleaning process in the processing chamber 201 is performed as necessary, and this process performed in the processing chamber 201 is referred to as a 2 nd cleaning process in this specification.

Specifically, the APC valve 244 is closed to stop the exhaust in the processing chamber 201, and the F ₂ gas and the NO gas are simultaneously supplied into the processing chamber 201 (step d). after the pressure in the processing chamber 201 has risen to the predetermined processing pressure, the supply of the F ₂ gas and the NO gas into the processing chamber 201 is stopped in a state where the exhaust in the processing chamber 201 is stopped, the state where the F ₂ gas and the NO gas are enclosed in the processing chamber 201 is maintained for a predetermined time (step e). after the predetermined enclosing time has elapsed, the APC valve 244 is opened to exhaust the processing chamber 201, and the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201 (step F). in the 2 nd cleaning process, steps d to F are performed as 1 cycle, and the cycle is performed a predetermined number of times (1 or more).

As a result, FNO and the like can be generated in the processing chamber 201, and a mixed gas obtained by adding FNO and the like to F ₂ gas can be brought into contact with the inside of the processing chamber 201, whereby an etching reaction can be performed in the inside of the processing chamber 201, and deposits adhering to the inside of the processing chamber 201 can be removed.

As the process conditions of the 2 nd cleaning process, the following conditions are exemplified:

F ₂ gas supply flow rate is 0.5-10 slm;

NO gas supply flow rate: 0.5-10 slm;

The supply flow rate of the N ₂ gas is 0.01 to 20slm, preferably 0.01 to 10 slm;

Gas supply time: 10-300 seconds, preferably 20-120 seconds;

Treatment pressure: 1330 to 53320Pa, preferably 9000 to 15000 Pa.

The other processing conditions were the same as those of the 1 st cleaning process.

(No. 3 cleaning treatment)

₂However, there is a case where a part of the deposit adhering to the exhaust pipe 231 is not removed and remains in the exhaust pipe 231, and after the 1 st cleaning process and the 2 nd cleaning process are finished, the cleaning process in the exhaust pipe 231 is performed as necessary.

Specifically, the APC valve 244 is opened to simultaneously supply the F ₂ gas and the NO gas into the process chamber 201 in a state where the process chamber 201 is exhausted (step g), after a predetermined time has elapsed, the supply of the F ₂ gas and the NO gas into the process chamber 201 is stopped in a state where the process chamber 201 is exhausted, the gas and the like remaining in the process chamber 201 and/or the exhaust pipe 231 are removed from the process chamber 201 and/or the exhaust pipe 231 (step h), and in the 3 rd cleaning process, the steps g and h are set to 1 cycle and the cycle is performed a predetermined number of times (1 or more).

The F ₂ gas and the NO gas can be mixed and reacted in the process chamber 201 and/or the exhaust pipe 231 by performing the 3 rd cleaning process, and as a result, FNO or the like can be generated in the process chamber 201 and/or the exhaust pipe 231, and the mixed gas obtained by adding FNO or the like to the F ₂ gas can be brought into contact with the inside of the exhaust pipe 231. thereby, the etching reaction can be performed in the inside of the exhaust pipe 231, and the deposit attached to the inside of the exhaust pipe 231 can be removed.

As the processing conditions of the 3 rd cleaning process, the following conditions are exemplified:

F ₂ gas supply flow rate is 0.5-10 slm;

NO gas supply flow rate: 0.5-10 slm;

The supply flow rate of the N ₂ gas is 0.01 to 20slm, preferably 0.01 to 10 slm;

supply time of each gas: 10-300 seconds, preferably 20-120 seconds;

The other processing conditions were the same as those of the 2 nd cleaning process.

(post purge and atmospheric pressure recovery)

After the 1 st to 3 rd cleaning processes are completed, the inside of the processing chamber 201 is purged (post-purge) by the same process steps as the post-purge in the substrate processing step. Then, the ambient gas 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 (atmospheric pressure recovery).

(Zhou Wa unloading)

The sealing cap 219 is lowered by the dish elevator 115, and the lower end of the header 209 is opened. Then, the empty cuvette 217 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 (cuvette unloading). When the series of processes is finished, the above-described substrate processing process is restarted.

(4) Effects according to the present embodiment

According to the present embodiment, one or more effects as shown below can be obtained.

(a) by performing a predetermined number of cycles including a step a of supplying F ₂ gas from the nozzle 249b into the processing chamber 201 after the wafer 200 is processed by supplying HCDS gas from the nozzle 249b to the wafer 200 and then supplying F ₂ gas from the nozzle 249b into the processing chamber 201 after the wafer 200 is processed, and a step b of supplying NO gas from the nozzle 249b into the processing chamber 201 in a state where a part of the F ₂ gas remains in the nozzle 249b after the supply of the F ₂ gas is stopped, the etching reaction can be appropriately performed inside the nozzle 249b by the aid of FNO or the like, and the deposit accumulated in the nozzle 249b can be removed at a practical rate without damaging the inner wall of the nozzle 249 b.

(b) In step b, by supplying NO gas from the nozzle 249b into the process chamber 201 while a part of the F ₂ gas remains in the nozzle 249b and while the process chamber 201 is exhausted, the residual amount (concentration and partial pressure) of the F ₂ gas in the nozzle 249b can be reduced with time, even if the NO gas/F ₂ gas volume ratio in the nozzle 249b increases with time, and thus the reaction between the F ₂ gas and the NO gas in the nozzle 249b can be gently progressed, the excessive progress of the internal etching reaction in the nozzle 249b can be suppressed, and the overetching of the inner wall of the nozzle 249b can be avoided.

further, when the F ₂ gas and the NO gas are supplied from the nozzle 249b into the process chamber 201 at the same time, the concentration and partial pressure of the F ₂ gas in the nozzle 249b are constant, and it is difficult to gently progress the reaction between the F ₂ gas and the NO gas in the nozzle 249 b.

(c) In step b, the NO gas can be supplied from the nozzle 249b into the process chamber 201 while a part of the F ₂ gas remains in the nozzle 249b and while the process chamber 201 is exhausted, so that a part of the F ₂ gas remaining in the nozzle 249b can be moved into the process chamber 201, whereby the peak point of the reaction between the F ₂ gas and the NO gas in the nozzle 249b can be moved from the root side to the tip side of the nozzle 249 b.

Further, when the F ₂ gas and the NO gas are supplied from the nozzle 249b into the process chamber 201 at the same time, the peak point of the reaction between the F ₂ gas and the NO gas in the nozzle 249b cannot be moved, and the etching reaction locally proceeds in a part of the nozzle 249b, so that a part of the inner wall of the nozzle 249b is partially over-etched in some cases.

(d) in step b, in a state where a part of the F ₂ gas remains in the nozzle 249b, and in a state where the inside of the process chamber 201 is exhausted, NO gas is supplied from the nozzle 249b into the process chamber 201, and a part of the F ₂ gas remaining in the nozzle 249b can be moved into the process chamber 201, whereby a peak point of a heat generation amount of reaction heat generated by a reaction between the F ₂ gas and the NO gas in the nozzle 249b can be moved from a root side to a tip side of the nozzle 249b, and as a result, a local temperature rise in the nozzle 249b can be suppressed, and thus, the F ₂ gas can come into contact with the inside of the nozzle 249b in a high temperature state, and overetching of a part of the inner wall of the nozzle 249b can be avoided.

Further, when the F ₂ gas and the NO gas are supplied from the nozzle 249b into the process chamber 201 at the same time, the peak point of the amount of heat generation of the reaction heat generated by the reaction between the F ₂ gas and the NO gas in the nozzle 249b may not be moved, and a part of the nozzle 249b may become locally high-temperature, and thus, the etching reaction may locally proceed in the nozzle 249b, and a part of the inner wall of the nozzle 249b may be partially over-etched.

(e) in step b, by supplying NO gas into the process chamber 201 through the gas supply pipe 232b and the nozzle 249b in a state where the inside of the process chamber 201 is exhausted, even when F ₂ gas remains in the gas supply pipe 232b, part of the remaining F ₂ gas can be moved from the inside of the gas supply pipe 232b into the process chamber 201, whereby, even when a reaction between F ₂ gas and NO gas occurs in the gas supply pipe 232b, a peak point of the reaction between F ₂ gas and NO gas in the gas supply pipe 232b, that is, a peak point of the amount of heat generation of reaction heat generated by the reaction between F ₂ gas and NO gas can be moved from the upstream side to the downstream side of the gas supply pipe 232 b.

Further, when the F ₂ gas and the NO gas are simultaneously supplied into the process chamber 201 through the gas supply pipe 232b and the nozzle 249b, the peak point of the reaction between the F ₂ gas and the NO gas in the gas supply pipe 232b may not be moved, and a part of the gas supply pipe 232b may be locally heated.

(f) The etching reaction can be prevented from being unexpectedly generated in the nozzle 249b when the F ₂ gas is supplied from the nozzle 249b into the process chamber 201 in step a of the next cycle, by performing step c of removing the NO gas remaining in the nozzle 249b and replacing the atmosphere gas in the nozzle 249b with the N ₂ gas after the supply of the NO gas into the nozzle 249b is stopped.

(g) When the process conditions in step c are appropriately set, the NO gas and the like remaining in the nozzles 249a and 249c and the process chamber 201 are removed from the nozzles 249a and 249c and the process chamber 201, respectively, and the atmosphere gas in the nozzles 249a and 249c and the process chamber 201 is replaced with N ₂ gas, respectively, the above-described etching reaction can be prevented from occurring unexpectedly in the nozzles 249a and 249c and the process chamber 201, respectively.

(h) By performing step c (after stopping the supply of the NO gas into the nozzle 249b, removing the NO gas remaining in the nozzle 249b, and replacing the atmosphere gas in the nozzle 249b with the N ₂ gas), the temperature of the nozzle 249b, which is increased by the reaction heat between the F ₂ gas and the NO gas, can be appropriately lowered, and thereby, it is possible to avoid overetching of the inner wall of the nozzle 249b due to the contact of the F ₂ gas with the inside of the nozzle 249b in a high temperature state when the F ₂ gas is supplied into the process chamber 201 from the nozzle 249b in step a of the next cycle.

(i) By performing the F ₂ gas supply step in a state where the supply of the N ₂ gas into the nozzle 249b is stopped, the movement of the F ₂ gas from the nozzle 249b into the processing chamber 201 is easily suppressed, and a part of the F ₂ gas remains in the nozzle 249 b.

in addition, the F ₂ gas supply step may be performed in a state where N ₂ gas is supplied into the nozzle 249b, and in this case, the concentration of the F ₂ gas supplied into the nozzle 249b can be easily reduced to a desired concentration.

Further, by performing the F ₂ gas supply step in a state where the supply of the N ₂ gas into the nozzles 249a and 249c is stopped, the F ₂ gas can be made to intrude into (reversely diffuse) the nozzles 249a and 249c, and when the cleaning process in the nozzle 249b is performed as described later, the cleaning process in the nozzles 249a and 249c can be performed all at once.

In this case, the penetration of the F ₂ gas into the nozzles 249a and 249c can be suppressed, and the cleaning process in the nozzles 249a and 249c can be suppressed when the cleaning process in the nozzle 249b is performed.

(j) by performing the NO gas supply step with the APC valve 244 opened to exhaust the interior of the process chamber 201, the movement of the F ₂ gas remaining in the nozzle 249b into the process chamber 201 can be promoted, whereby the above-described effects resulting from the increase in the NO gas/F ₂ gas volume ratio with time, the above-described effects resulting from the movement of the peak point of the reaction of the F ₂ gas and the NO gas, and the above-described effects resulting from the movement of the peak point of the heat generation amount of the reaction heat resulting from the reaction of the F ₂ gas and the NO gas can be reliably obtained.

In this case, the movement of the F ₂ gas remaining in the nozzle 249b into the processing chamber 201 can be appropriately suppressed, and the movement speed of the peak point of the reaction between the F ₂ gas and the NO gas can be appropriately reduced.

Further, by performing the NO gas supply step in a state where the supply of the N ₂ gas into the nozzle 249b is stopped, the movement of the F ₂ gas remaining in the nozzle 249b into the processing chamber 201 can be appropriately suppressed, and the movement speed of the peak point of the reaction between the F ₂ gas and the NO gas can be appropriately reduced.

In this case, the movement of the F ₂ gas remaining in the nozzle 249b into the process chamber 201 can be promoted, and thereby, the above-described effect by the increase in the NO gas/F ₂ gas volume ratio with time, the above-described effect by the movement of the peak point of the reaction of the F ₂ gas and the NO gas, and the above-described effect by the movement of the peak point of the heat generation amount of the reaction heat generated by the reaction of the F ₂ gas and the NO gas can be reliably obtained.

Further, by performing the NO gas supply step in a state where the supply of the N ₂ gas into the nozzles 249a, 249c is stopped, the NO gas can be caused to intrude (counter-diffuse) into the nozzles 249a, 249c, thereby, the F ₂ gas intruded into the nozzles 249a, 249c by performing the step a and the NO gas intruded into the nozzles 249a, 249c by performing the step b can be caused to react with each other, as a result, FNO and the like can be generated in the nozzles 249a, 249c, and the mixed gas obtained by adding the F ₂ gas with the 249 o and the like can be brought into contact with the insides of the nozzles 249a, 249c, thereby, the etching reaction can be caused to proceed in the insides of the nozzles 249a, 249c, and deposits adhering to the inside the nozzles 249a, 249c can be removed, that is, and the cleaning process in the nozzles 249a, 249c can be performed at once when the cleaning process in the nozzles 249b is performed.

in this case, the NO gas supply step may be performed in a state where the N ₂ gas is supplied into the nozzles 249a and 249c, and the progress of the cleaning process in the nozzles 249a and 249c may be suppressed by suppressing the intrusion of the NO gas into the nozzles 249a and 249 c.

₂(k) further, after the 1 st cleaning process, when a part of the deposit adhering to the inside of the processing chamber 201 remains in the processing chamber 201, the 2 nd cleaning process can be performed as necessary to remove the deposit remaining in the processing chamber 201, and when a part of the deposit adhering to the inside of the exhaust pipe 231 remains in the exhaust pipe 231 after the 1 st cleaning process, the 3 rd cleaning process can be performed as necessary to remove the deposit remaining in the exhaust pipe 231.

(1) the same effects can be obtained even when a cleaning gas other than F ₂ gas is used in the cleaning process, when an additive gas other than NO gas is used, and/or when an inert gas other than N ₂ gas is used, and the same effects can be obtained even when a process gas (raw material) other than HCDS gas, a process gas (reactant) other than NH ₃ gas, and/or an inert gas other than N ₂ gas are used in the substrate processing step.

(5) Modification example

the 1 st cleaning process is not limited to the mode shown in fig. 4 (a), and can be modified as in the modification shown below. These modifications can be combined arbitrarily. Unless otherwise specified, the processing steps and processing conditions of the respective steps in the respective modifications may be the same as those of the respective steps shown in fig. 4 (a).

(modification 1)

As shown in fig. 4 (b) and/or a gas supply sequence shown below, a cycle including step a of supplying NO gas from the nozzle 249b into the processing chamber 201 after the wafer 200 is processed by supplying HCDS gas from the nozzle 249b and supplying NO gas from the nozzle 249b into the processing chamber 201 after the wafer 200 is processed, and step b of supplying F ₂ gas from the nozzle 249b into the processing chamber 201 with a part of the NO gas remaining in the nozzle 249b after the supply of the NO gas is stopped, may be performed a predetermined number of times (n times, n being an integer of 1 or more), and in step a of the present modification, the pressure adjustment step shown in a ₀ in the figure may be performed before the supply of the NO gas, and the residual gas removal step shown in c in the figure may be performed after the supply of the F ₂ gas is stopped, as in the first cleaning process shown in fig. 4 (a).

R2：(N₂-Press.set→NO→F₂→PRG)×n

In this modification as well, the same effect as the 1 st cleaning process shown in fig. 4 (a) can be obtained.

That is, in the present modification, the NO gas remaining in the nozzle 249b and the F ₂ gas supplied into the nozzle 249b can be mixed and reacted in the nozzle 249b, whereby the etching reaction can be advanced inside the nozzle 249b by the aid of the FNO or the like, and the deposit accumulated in the nozzle 249b can be removed at a practical rate.

In the present modification, the etching reaction can be performed so that a part of the NO gas remaining in the nozzle 249b moves into the process chamber 201, that is, the etching treatment can be performed so that the residual amount (concentration and partial pressure) of the NO gas in the nozzle 249b decreases with time, in other words, the etching treatment can be performed so that the volume ratio of the F ₂ gas to the NO gas in the nozzle 249b (hereinafter, also referred to as the F ₂ gas/NO gas volume ratio) increases with time, and thus, the reaction between the NO gas and the F ₂ gas in the nozzle 249b can be performed gently, the etching reaction in the nozzle 249b can be prevented from proceeding excessively, and the inner wall of the nozzle 249b can be prevented from being over-etched.

In the present modification, the peak point of the reaction between the NO gas and the F ₂ gas in the nozzle 249b can be moved from the root side to the tip side of the nozzle 249b, and therefore, the cleaning process in the nozzle 249b can be performed uniformly without leakage over a wide range in the nozzle 249b, preferably over the entire region from the root side to the tip side of the nozzle 249b, that is, the uniformity of the cleaning process in the nozzle 249b can be improved.

In addition, in the present modification, the peak point of the amount of heat generation of the reaction heat generated by the reaction of the NO gas and the F ₂ gas in the nozzle 249b can be moved from the base side to the tip side of the nozzle 249b, and thus, a local temperature rise of a part of the nozzle 249b can be suppressed, and overetching of a part of the inner wall of the nozzle 249b due to contact of the F ₂ gas with the inside of the nozzle 249b in a high temperature state in step a of the next cycle can be avoided.

(modification 2)

as shown in fig. 5 (a) and/or the gas supply sequence described below, in the pressure adjustment step shown as a ₀ in the figure, the pressure in the processing chamber 201 may be adjusted using the F ₂ gas, and the processing chamber 201 may be filled with the F ₂ gas.

R2：(F₂-Press.set→F₂→NO→PRG)×n

In addition, in step a of this modification, the pressure in the process chamber 201 is adjusted using the F ₂ gas, so that the F ₂ gas fills the process chamber 201, and a part of the F ₂ gas is likely to remain in the nozzle 249b, whereby the F ₂ gas remaining in the nozzle 249b and the NO gas supplied to the nozzle 249b can be efficiently mixed and reacted in the nozzle 249b when step b is performed thereafter, and deposits accumulated in the nozzle 249b can be efficiently removed.

In the pressure adjusting step, the pressure in the processing chamber 201 may be adjusted using both the F ₂ gas and the N ₂ gas, and in this case, the time required for the pressure in the processing chamber 201 to reach the processing pressure can be shortened in addition to the above-described effects.

(modification 3)

As shown in fig. 5 (b) and/or the gas supply sequence described below, the pressure in the processing chamber 201 may be adjusted using the NO gas in the pressure adjustment step shown as a ₀ to fill the processing chamber 201 with the NO gas.

R2：(NO-Press.set→NO→F₂→PRG)×n

In addition, in the step a of the present modification, the pressure in the processing chamber 201 is adjusted using the NO gas, so that the processing chamber 201 is filled with the NO gas, and thus a part of the NO gas is likely to remain in the nozzle 249b, whereby the NO gas remaining in the nozzle 249b and the F ₂ gas supplied into the nozzle 249b can be efficiently mixed and reacted in the nozzle 249b when the step b is performed thereafter, and the deposit accumulated in the nozzle 249b can be efficiently removed, and the processing step in the step a can be simplified, and further, according to the present modification, the entire processing chamber 201 is filled with the NO gas in the step a, so that the removal efficiency (effect) of the deposit accumulated in the nozzle 249b can be improved, and the removal efficiency (effect) of the deposit accumulated in the nozzles 249a, 249c, the processing chamber 201, and the exhaust pipe 231 can be improved.

In addition, in the pressure adjusting step, the pressure in the processing chamber 201 may be adjusted using both the NO gas and the N ₂ gas, and in this case, the time required for the pressure in the processing chamber 201 to reach the processing pressure can be shortened in addition to the above-described effects.

(modification 4)

In the above embodiment, the example in which the F ₂ gas supply step is performed with the APC valve 244 opened and the process chamber 201 exhausted has been described, but the F ₂ gas supply step may be performed with the APC valve 244 closed and the process chamber 201 exhausted stopped, and the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications are obtained in the present modification, and further, the movement of the F ₂ gas from the nozzle 249b into the process chamber 201 is easily suppressed and a part of the F ₂ gas remains in the nozzle 249b in the present modification.

(modification 5)

The cleaning process in the nozzle 249a may be performed in accordance with, for example, the following gas supply procedure, such as connecting a gas supply system similar to the above-described cleaning gas supply system and a gas supply system similar to the above-described additive gas supply system to the gas supply pipe 232 a.

R1：(N₂-Press.set→F₂→NO→PRG)×n

R1：(N₂-Press.set→NO→F₂→PRG)×n

R1：(F₂-Press.set→F₂→NO→PRG)×n

R1：(NO-Press.set→NO→F₂→PRG)×n

according to this modification, deposits adhering to the inside of the nozzle 249a can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained.

(modification 6)

The cleaning process in the nozzle 249c may be performed in accordance with, for example, the following gas supply procedure, such as connecting a gas supply system similar to the above-described cleaning gas supply system and a gas supply system similar to the above-described additive gas supply system to the gas supply pipe 232 c.

R3：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

R3：(F₂-Press.set→F₂→NO→PRG)×n

R3：(NO-Press.set→NO→F₂→PRG)×n

according to this modification, deposits adhering to the inside of the nozzle 249c can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained.

(modification 7)

The cleaning process in at least 2 or more of the nozzles 249a to 249c may be performed sequentially in accordance with, for example, the 1 st cleaning process shown in fig. 4 (a) and/or the steps of the modifications described above, such as connecting a gas supply system similar to the above-described cleaning gas supply system and a gas supply system similar to the above-described additive gas supply system to at least one of the gas supply pipes 232a and 232 c.

In this case, the sequence of execution of the cleaning process in the nozzles 249a to 249c can be determined arbitrarily. For example, the cleaning treatment may be performed in the order of R2 → R1, the cleaning treatment may be performed in the order of R2 → R3, or the cleaning treatment may be performed in the order of R2 → R1 → R3.

According to this modification, deposits adhering to at least 2 or more nozzles among the nozzles 249a to 249c can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained.

(modification 8)

For example, a gas supply system similar to the purge gas supply system and a gas supply system similar to the additive gas supply system may be connected to the gas supply pipes 232a and 232c, respectively, and the purge process in at least 2 or more of the nozzles 249a to 249c may be performed simultaneously in the following gas supply order.

R1：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→F₂→NO→PRG)×n

R1：(N₂-Press.set→NO→F₂→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

R1：(N₂-Press.set→F₂→NO→PRG)×n

R2：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→F₂→NO→PRG)×n

R1：(N₂-Press.set→NO→F₂→PRG)×n

R2：(N₂-Press.set→NO→F₂→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

according to this modification, deposits adhering to at least 2 or more nozzles among the nozzles 249a to 249c can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the cleaning process in the plurality of nozzles is performed simultaneously, the time required for the cleaning process can be shortened.

(modification 9)

The cleaning process in the nozzles 249a and 249b or the cleaning process in the nozzles 249b and 249c may be performed simultaneously in the following gas supply sequence, for example, by connecting a gas supply system similar to the purge gas supply system or a gas supply system similar to the additive gas supply system to at least one of the gas supply pipes 232a and 232 c.

R1：(N₂-Press.set→NO→F₂→PRG)×n

R2：(N₂-Press.set→F₂→NO→PRG)×n

R2：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

R1：(N₂-Press.set→F₂→NO→PRG)×n

R2：(N₂-Press.set→NO→F₂→PRG)×n

R2：(N₂-Press.set→NO→F₂→PRG)×n

R3：(N₂-Press.set→F₂→NO→PRG)×n

That is, in the case where the F ₂ gas is supplied into the process chamber 201 from the nozzle 249b in step a, the NO gas may be supplied into the process chamber 201 from the nozzle 249a or the nozzle 249c different from the nozzle 249b in step a, or in the case where the NO gas is supplied into the process chamber 201 from the nozzle 249b in the state where a part of the F ₂ gas remains in the nozzle 249b in step b, the F ₂ gas may be supplied into the process chamber 201 from the nozzle 249a or the nozzle 249c in the state where a part of the NO gas remains in the nozzle 249a or the nozzle 249c after the supply of the NO gas is stopped in step b.

Further, in the case where the NO gas is supplied into the processing chamber 201 from the nozzle 249b in the step a, the F ₂ gas may be supplied into the processing chamber 201 from the nozzle 249a or the nozzle 249c different from the nozzle 249b in the step a, or in the case where the F ₂ gas is supplied into the processing chamber 201 from the nozzle 249b in the state where a part of the NO gas remains in the nozzle 249b in the step b, the NO gas may be supplied into the processing chamber 201 from the nozzle 249a or the nozzle 249c in the state where a part of the F ₂ gas remains in the nozzle 249a or the nozzle 249c after the supply of the F ₂ gas is stopped in the step b.

According to this modification, deposits adhering to the nozzles 249a and 249b, respectively, or deposits adhering to the nozzles 249b and 249c, respectively, can be removed. In this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the cleaning process in the plurality of nozzles is performed simultaneously, the time required for the cleaning process can be shortened.

Further, according to the present modification, in both of the steps a and b, the F ₂ gas and the NO gas are simultaneously supplied into the processing chamber 201, and therefore, the FNO and the like can be efficiently generated in the processing chamber 201, whereby the mixed gas obtained by adding the FNO and the like to the F ₂ gas can be reliably counterdiffused into the nozzle not subjected to the supply of the F ₂ gas and/or the NO gas and brought into contact with the inside of the nozzle, or diffused into the processing chamber 201 and/or the exhaust pipe 231 and brought into contact with the inside of the processing chamber 201 and/or the inside of the exhaust pipe 231.

(modification 10)

The cleaning process in the nozzles 249a and 249c may be performed simultaneously in the gas supply sequence shown in fig. 6 and/or below, for example, by connecting a gas supply system similar to the above-described cleaning gas supply system and a gas supply system similar to the above-described additive gas supply system to the gas supply pipes 232a and 232c, respectively.

R1：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

R1：(N₂-Press.set→NO→F₂→PRG)×n

R3：(N₂-Press.set→F₂→NO→PRG)×n

according to this modification, deposits adhering to the nozzles 249a and 249c can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the cleaning process in the plurality of nozzles is performed simultaneously, the time required for the cleaning process can be shortened.

Further, according to the present modification, since the F ₂ gas and the NO gas are supplied into the processing chamber 201 simultaneously in both of the steps a and b, the same effect as in modification 9 can be obtained.

(modification 11)

the cleaning process in the nozzles 249a to 249c may be performed simultaneously in the gas supply sequence shown in fig. 7 and/or below, for example, by connecting a gas supply system similar to the above-described cleaning gas supply system and a gas supply system similar to the above-described additive gas supply system to the gas supply pipes 232a and 232c, respectively.

R1：(N₂-Press.set→NO→F₂→PRG)×n

R2：(N₂-Press.set→F₂→NO→PRG)×n

R3：(N₂-Press.set→NO→F₂→PRG)×n

R1：(N₂-Press.set→F₂→NO→PRG)×n

R2：(N₂-Press.set→NO→F₂→PRG)×n

R3：(N₂-Press.set→F₂→NO→PRG)×n

According to this modification, deposits adhering to the inside of the nozzles 249a to 249c can be removed, and in this case, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the cleaning process in the plurality of nozzles is performed simultaneously, the time required for the cleaning process can be shortened.

further, according to the present modification, since the F ₂ gas and the NO gas are supplied into the processing chamber 201 simultaneously in both of the steps a and b, the same effect as in modification 9 can be obtained.

(modification 12)

For example, as in the gas supply sequence described below, step c may be performed only in the last cycle of the 1 st cleaning process or may be performed every predetermined number of cycles, and n, n ₁ to n ₃ described below are integers of 1 or more.

R2：(N₂-Press.set→F₂→NO)×n→PRG

R2：(N₂-Press.set→NO→F₂)×n→PRG

R2：(F₂-Press.set→F₂→NO)×n→PRG

R2：(NO-Press.set→NO→F₂)×n→PRG

R2：〔[(N₂-Press.set→F₂→NO)×n₁→PRG]×n₂〕×n₃

R2：〔[(N₂-Press.set→NO→F₂)×n₁→PRG]×n₂〕×n₃

R2：〔[(F₂-Press.set→F₂→NO)×n₁→PRG]×n₂〕×n₃

R2：〔[(NO-Press.set→NO→F₂)×n₁→PRG]×n₂〕×n₃

According to this modification, the same effects as those of the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the frequency of execution of step c is reduced, the time required for the cleaning process can be shortened.

(modification 13)

the 1 st to 3 rd cleaning processes can be performed in any order as described below. In addition, 2 of the 1 st to 3 rd cleaning processes including the 1 st cleaning process can be arbitrarily selected and performed in an arbitrary order.

cleaning treatment No. 1 → cleaning treatment No. 2 → cleaning treatment No. 3

cleaning process No. 1 → cleaning process No. 3 → cleaning process No. 2

Cleaning treatment No. 2 → cleaning treatment No. 1 → cleaning treatment No. 3

cleaning treatment No. 2 → cleaning treatment No. 3 → cleaning treatment No. 1

Cleaning treatment No. 3 → cleaning treatment No. 1 → cleaning treatment No. 2

cleaning treatment No. 3 → cleaning treatment No. 2 → cleaning treatment No. 1

Cleaning treatment No. 1 → cleaning treatment No. 2

Cleaning treatment No. 1 → cleaning treatment No. 3

cleaning treatment No. 2 → cleaning treatment No. 1

Cleaning treatment No. 3 → cleaning treatment No. 1

In this modification as well, the same effects as in the 1 st cleaning process shown in fig. 4 (a) and/or the above-described modifications can be obtained. Further, since the cleaning process in the exhaust pipe 231 can be performed in the 1 st cleaning process and/or the 2 nd cleaning process, the 1 st cleaning process and/or the 2 nd cleaning process can be performed earlier than the 3 rd cleaning process, and thus the time required for the 3 rd cleaning process can be shortened.

(modification 14)

in the above embodiment and/or each modification, the example in which the pressure adjusting step is performed using any one of the N ₂ gas, the F ₂ gas, the NO gas, the F ₂ gas + N ₂ gas, and the NO gas + N ₂ gas in the 1 st cleaning process was described, but the pressure adjusting step may be performed using at least any one of the N ₂ gas, the F ₂ gas, and the NO gas in the 2 nd cleaning process and/or the 3 rd cleaning process, and the effect of adjusting the pressure in the processing chamber 201 using any one of the F ₂ gas, the NO gas, the F ₂ gas + N ₂ gas, and the NO gas + N ₂ gas in the 2 nd cleaning process and/or the 3 rd cleaning process is the same as the effect of the above modifications 2 and 3.

In the case where the pressure in the processing chamber 201 is adjusted by using the F ₂ gas + NO gas + N ₂ gas in the 2 nd cleaning process and/or the 3 rd cleaning process, the same effect as that in the case where the pressure in the processing chamber 201 is adjusted by using the F ₂ gas + N ₂ gas or the NO gas + N ₂ gas can be obtained, and further, since the F ₂ gas and the NO gas can be mixed and reacted in the processing chamber 201 and/or the exhaust pipe 231 from the time of the pressure adjustment, the cleaning process in the processing chamber 201 and/or the exhaust pipe 231 can be performed from the time of the pressure adjustment, and the time required for each cleaning process (the 2 nd cleaning process and the 3 rd cleaning process) can be shortened, and in the case where the pressure in the processing chamber 201 is adjusted by using the F ₂ gas + NO gas in the 2 nd cleaning process and/or the 3 rd cleaning process, and the above-mentioned effect obtained in the case where the pressure in the processing chamber 201 is adjusted by using the F ₂ gas + NO gas + N ₂ gas, the latter effect, that is further improved, that is the effect required for each cleaning process can be further shortened.

< other embodiment >

The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention.

In the above embodiment, an example in which the nozzle interior and/or the process chamber interior is cleaned after the SiN film is formed on the wafer in the process chamber is described. However, the present invention is not limited to such an embodiment. For example, the above-described cleaning treatment can be preferably applied to the following cases: after forming various kinds of films including a silicon insulating film such as a silicon oxide film (SiO film), a silicon oxycarbide film (SiOCN film), a silicon oxycarbide film (SiOC film), a silicon oxynitride film (SiON film), a silicon carbonitride film (SiCN film), a silicon boron carbonitride film (SiBCN film), and a silicon boron nitride film (SiBN film) on the wafer in the processing chamber, the inside of the nozzle and/or the inside of the processing chamber are cleaned.

The recipes used for the substrate processing and/or cleaning process are preferably prepared individually according to the process contents and stored in advance in the storage device 121c via the electrical communication line and/or the external storage device 123. Further, it is preferable that at the start of the substrate processing and/or cleaning processing, the CPU121a appropriately selects an appropriate recipe in accordance with the contents of the substrate processing and/or cleaning processing from among the plurality of recipes stored in the storage device 121 c. Thus, films of various types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using 1 substrate processing apparatus. Further, the cleaning process can be appropriately performed according to deposits including various films attached in the processing container (the processing chamber 201) and/or the supply part (the nozzle). Further, the burden on the operator can be reduced, and the process can be started quickly while avoiding an operation error.

The recipe is not limited to the newly created recipe, and may be prepared by changing an existing recipe already installed in the substrate processing apparatus, for example. In the case of changing the recipe, the recipe after the change may be installed in the substrate processing apparatus via an electric communication line and/or a storage medium storing the recipe. Further, the input/output device 122 provided in the existing substrate processing apparatus may be operated to directly change the existing recipe already installed in the substrate processing apparatus.

In the above embodiment, an example was described in which the 1 st to 3 rd nozzles (nozzles 249a to 249c) as the 1 st to 3 rd supply units are linearly arranged along the lower portion to the upper portion of the inner wall of the reaction tube 203. However, the present invention is not limited to the above embodiment. For example, at least any one of the 1 st to 3 rd nozzles may be configured as a U-shaped nozzle (return nozzle) having a portion (bent portion) bent into, for example, a U-shape at an arbitrary position from a lower portion to an upper portion of the inner wall of the reaction tube 203. In the case of using a U-shaped nozzle, deposits accumulated in the nozzle can be removed at a practical rate from the entire region from the root side to the tip side of the nozzle by the aid of FNO or the like. In addition, the over-etching of the inner wall of the nozzle can be avoided, and the uniformity of the cleaning process can be improved.

In the above embodiment, an example was described in which the 1 st to 3 rd nozzles (nozzles 249a to 249c) as the 1 st to 3 rd supply units were provided in the process chamber so as to extend along the inner wall of the reaction tube. However, the present invention is not limited to the above embodiment. For example, as shown in fig. 8 (a), a buffer chamber may be provided in a side wall of the reaction tube, and the 1 st to 3 rd nozzles having the same configuration as in the above embodiment may be provided in the buffer chamber in the same arrangement as in the above embodiment. Fig. 8 (a) shows an example in which a supply buffer chamber and an exhaust buffer chamber are provided in the side wall of the reaction tube, and both chambers are disposed at positions facing each other with the wafer interposed therebetween. The supply buffer chamber and the exhaust buffer chamber are provided along the lower portion to the upper portion of the side wall of the reaction tube, i.e., along the wafer arrangement region. Fig. 8 (a) shows an example in which the supply buffer chamber is divided into a plurality of (3) spaces, and the nozzles are disposed in the respective spaces. The arrangement of the 3 spaces of the buffer chamber is the same as the arrangement of the 1 st to 3 rd nozzles. The spaces in which the 1 st to 3 rd nozzles are disposed may be referred to as a 1 st to a 3 rd buffer chamber. The 1 st nozzle and the 1 st buffer chamber, the 2 nd nozzle and the 2 nd buffer chamber, and the 3 rd nozzle and the 3 rd buffer chamber may be regarded as the 1 st supply unit, the 2 nd supply unit, and the 3 rd supply unit, respectively. Further, for example, like the cross-sectional structure of the vertical processing furnace shown in fig. 8 (b), a buffer chamber may be provided in the same arrangement as in fig. 8 (a), a 2 nd nozzle may be provided in the buffer chamber, and a 1 st nozzle and a 3 rd nozzle may be provided along the inner wall of the reaction tube with a communicating portion of the buffer chamber with the processing chamber interposed therebetween from both sides. The 1 st nozzle, the 2 nd nozzle, and the buffer chamber and the 3 rd nozzle may be referred to as a 1 st supply unit, a 2 nd supply unit, and a 3 rd supply unit, respectively. The configurations other than the buffer chamber and/or the reaction tube described in fig. 8 (a) and 8 (b) are the same as those of the respective portions of the processing furnace shown in fig. 1. Even when these processing furnaces are used, the cleaning process in the processing chamber and/or the supply portion (nozzle, buffer chamber) can be performed in the same manner as in the above-described embodiment, and the same effects as in the above-described embodiment can be obtained.

In the above embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at a time is described. However, the present invention is not limited to the above embodiment, and can be preferably applied to a case where a film is formed using a single-substrate processing apparatus that processes 1 or more substrates at a time. In the above-described embodiments, an example of forming a film using a substrate processing apparatus having a Hot Wall (Hot Wall) type processing furnace is described. However, the present invention is not limited to the above embodiment, and can be preferably applied to a case where a film is formed using a substrate processing apparatus having a Cold Wall (Cold Wall) type processing furnace.

Even in the case of using these substrate processing apparatuses, substrate processing and/or cleaning processing can be performed in the same order and under the same processing conditions as those of the above-described embodiment and/or modification, and the same effects as those of the above-described embodiment and/or modification can be obtained.

Further, the above embodiments and/or modifications and the like can be combined and used as appropriate. The processing steps and processing conditions in this case may be, for example, the same steps and conditions as those in the above-described embodiment.