TW202104654A - Semiconductor device manufacturing method, recording medium and substrate processing device - Google Patents

Abstract

Without unnecessarily lengthening the treatment gas supply time, this method enables reducing the amount of byproducts contained in a film to a level that does not pose problems in terms of characteristics. This method involves: a first step for starting the supply of treatment gas to the substrate in a treatment chamber; a second step for continuously measuring the amount of byproduct discharged from the treatment chamber; a third step for exerting control so as to stop the supply of treatment gas in the case that, during the decay process, the measured byproduct amount reaches a set threshold value; and a fourth step for evacuating the treatment chamber.

Description

Manufacturing method of semiconductor device, recording medium and substrate processing device

This case is about manufacturing methods of semiconductor devices, recording media and substrate processing equipment.

As one of the manufacturing processes of semiconductor devices, there is a process of forming a silicon nitride (SiN) film _{on a substrate using dichlorosilane (SiH 2} Cl ₂ ) gas and ammonia (NH _{3) gas (} For example, refer to Patent Document 1). In addition, there is a process of forming a film such as a titanium nitride (TiN) film _{using titanium tetrachloride (TiCl 4} ) gas and NH _{3 gas (for example, refer to Patent Document 2).} Prior Art Document Patent Document

Patent Document 1: Japanese Patent Application Publication No. 2018-10891 Patent Document 2: JP 2014-208883 A

(The problem to be solved by the invention)

The SiN film or TiN film formed as described above is in a state where by-products such as chlorine (Cl) or hydrogen chloride (HCl) remain in the film. If these by-products remain in the film, the resistivity will increase, or the film formation speed will decrease.

As long as the supply time of the processing gas is lengthened, the amount of by-products contained in the film can be reduced, but there is a problem that the processing time becomes longer. In addition, if conditions such as the number of wafers to be inserted (the number of wafers to be filled) or the surface area of the wafer are changed, the processing gas necessary to reduce the amount of by-products contained in the film to a level that is not problematic in terms of characteristics The supply time will change.

The purpose of this proposal is to provide a technology that can reduce the amount of by-products contained in the film to a level that is not problematic in terms of characteristics without extending the supply time of the processing gas more than necessary. (Means to solve the problem)

According to one form of this case, a technology with the following engineering can be provided, The first step is to start the supply of processing gas to the substrate in the processing chamber; The second project is to continue to measure the amount of by-products exhausted from the aforementioned processing chamber; The third step is to control to stop the supply of processing gas when the amount of by-products to be measured decays and reaches a set threshold value; and The fourth step is to exhaust the aforementioned treatment chamber. [Effects of the invention]

According to this proposal, the supply time of the processing gas is not extended beyond necessary, and the amount of by-products contained in the film can be reduced to a level with no problem in characteristics.

<An implementation form of this case>

The following describes one of the implementation modes of this case.

(1) Configuration of substrate processing equipment The substrate processing apparatus 10 is a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 has a cylindrical shape, and is installed vertically by being installed on the bottom of the heater (not shown) as a holding plate.

Inside the heater 207, an outer tube 203 constituting a reaction vessel (processing vessel) is arranged concentrically with the heater 207. The outer tube 203 is made of, for example _{, a heat-resistant material such as quartz (SiO 2} ) and silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (inlet flange) 209 is arranged concentrically with the outer tube 203. The collecting pipe 209 is made of, for example, a metal such as stainless steel (SUS), and has a cylindrical shape with an open upper end and a lower end. Between the upper end of the collecting pipe 209 and the outer pipe 203, an O-ring 220a as a sealing member is provided. With the manifold 209 being supported at the bottom of the heater, the outer tube 203 is in a vertically installed state.

Inside the outer tube 203 is an inner tube 204 constituting a reaction vessel. The inner tube 204 is made of, for example _{, a heat-resistant material such as quartz (SiO 2} ) or silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end. The outer tube 203, the inner tube 204, and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing container (inside the inner tube 204).

The processing chamber 201 is configured to be able to accommodate the wafer 200 as a substrate in a state where the wafer 200 is arranged in a vertical direction in a horizontal posture by a wafer boat 217 described later.

In the processing chamber 201, the nozzles 410, 420, and 430 are arranged to penetrate the side wall of the collecting pipe 209 and the inner pipe 204. The nozzles 410, 420, and 430 are connected to gas supply pipes 310, 320, and 330, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned form.

The gas supply pipes 310, 320, and 330 are mass flow controllers (MFC) 312, 322, and 332 provided with flow controllers (flow control units) in order from the upstream side. In addition, the gas supply pipes 310, 320, and 330 are provided with valves 314, 324, and 334 for opening and closing valves. On the downstream side of the valves 314, 324, and 334 of the gas supply pipes 310, 320, and 330, gas supply pipes 510, 520, and 530 for supplying inert gas are connected. In the gas supply pipes 510, 520, and 530, MFCs 512, 522, and 532 of the flow controller (flow control unit) and valves 514, 524, and 534 of the on-off valve are respectively provided in order from the upstream side.

The nozzles 410, 420, and 430 are connected to the front ends of the gas supply pipes 310, 320, and 330. The nozzles 410, 420, and 430 are nozzles configured in an L-shape, and the horizontal portion thereof is provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, and 430 are provided in the preparation chamber 201a, which is formed to protrude outward in the radial direction of the inner tube 204 and extends in the vertical direction, in the preparation chamber 201a. The inside of 201a is provided along the inner wall of the inner tube 204 facing upward (upward in the arrangement direction of the wafer 200).

The nozzles 410, 420, and 430 are provided to extend from the lower region of the processing chamber 201 to the upper region of the processing chamber 201, and a plurality of gas supply holes 410a, 420a, 430a are provided at positions opposite to the wafer 200. Thereby, the processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, respectively. The gas supply holes 410a, 420a, and 430a are provided in a plurality from the lower part to the upper part of the inner tube 204, each having the same opening area, and furthermore being provided with the same opening pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-mentioned forms. For example, the opening area may be gradually enlarged from the lower part of the inner tube 204 toward the upper part. Thereby, the flow rate of the gas supplied from the gas supply holes 410a, 420a, 430a can be more uniform.

The gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 are plurally provided at positions from the lower part to the upper part of the wafer boat 217 described later. Therefore, the processing gas supplied from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, 430 into the processing chamber 201 is supplied to the entire area of the wafer 200 accommodated from the lower part to the upper part of the wafer boat 217. The nozzles 410, 420, and 430 only need to be provided to extend from the lower region to the upper region of the processing chamber 201, but it is desirable to be provided to extend to the vicinity of the top of the wafer boat 217.

From the gas supply pipe 310, a metal element-containing raw material gas (metal-containing gas) is supplied as a processing gas into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410. As the raw material, for example, titanium (Ti) as a metal element, and titanium tetrachloride (TiCl ₄ ) as a halogen-based raw material (halide, halogen-based titanium raw material) can be used.

The reducing gas from the gas supply pipe 320 is used as the processing gas and is supplied into the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420. _{The reducing gas is, for example, a silane (SiH 4} ) gas, which is a reducing gas containing silicon (Si) and hydrogen (H) but not containing halogen. SiH ₄ acts as a reducing agent.

The reaction gas that reacts with the source gas from the gas supply pipe 330 is supplied as the processing gas into the processing chamber 201 via the MFC 332, the valve 334, and the nozzle 430. _{The reaction gas is, for example, an ammonia (NH 3} ) gas, which is an N-containing gas containing nitrogen (N), which can be used.

The gas supply pipes 510, 520, and 530 are inert gases, such as nitrogen (N ₂ ) gas, which is supplied into the processing chamber 201 via MFC 512, 522, 532, valves 514, 524, 534, and nozzles 410, 420, and 430, respectively. Hereinafter, an example of using N ₂ gas as the inert gas will be described, but in addition to N ₂ gas, the inert gas can also be used, for example, argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe). Rare gas such as gas.

The gas supply pipes 310, 320, 330, MFC312, 322, 332, valves 314, 324, 334, and nozzles 410, 420, 430 are mainly used to form the processing gas supply system. However, only the nozzles 410, 420, 430 may be used. Think of it as a processing gas supply system. The processing gas supply system may also be simply referred to as a gas supply system. When the source gas flows from the gas supply pipe 310, the source gas supply system is mainly constituted by the gas supply pipe 310, the MFC 312, and the valve 314. However, it is also conceivable to include the nozzle 410 in the source gas supply system. In addition, when the reducing gas flows from the gas supply pipe 320, the gas supply pipe 320, the MFC 322, and the valve 324 mainly constitute the reducing gas supply system. However, it is also conceivable to include the nozzle 420 in the reducing gas supply system. In addition, when the reaction gas flows from the gas supply pipe 330, the reaction gas supply system is mainly constituted by the gas supply pipe 330, the MFC 332, and the valve 334, but it is also conceivable to include the nozzle 430 in the reaction gas supply system. When a nitrogen-containing gas is supplied as a reaction gas from the gas supply pipe 330, the reaction gas supply system may also be referred to as a nitrogen-containing gas supply system. In addition, the gas supply pipes 510, 520, 530, MFC 512, 522, 532, and valves 514, 524, 534 mainly constitute an inert gas supply system.

The method of supplying gas in this embodiment is through the nozzle 410 arranged in the preparation chamber 201a in the annular lengthwise space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200. , 420, 430 to transport gas. Then, gas is ejected into the inner tube 204 from a plurality of gas supply holes 410a, 420a, and 430a provided at positions opposite to the wafer of the nozzles 410, 420, and 430. In more detail, the gas supply hole 410a of the nozzle 410, the gas supply hole 420a of the nozzle 420, and the gas supply hole 430a of the nozzle 430 are used to eject the source gas and the like in a direction parallel to the surface of the wafer 200.

The exhaust hole (exhaust port) 204a is a through hole formed in the side wall of the inner tube 204 at a position opposed to the nozzles 410, 420, and 430, for example, a slit-shaped through hole that is elongated and opened in the vertical direction. The gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, 430 are supplied into the processing chamber 201, and the gas flowing on the surface of the wafer 200 flows through the exhaust holes 204a to be formed in the inner tube 204 and Inside the exhaust passage 206 formed by the gap between the outer pipes 203. Then, the gas flowing into the exhaust passage 206 flows into the exhaust pipe 231 and is discharged out of the processing furnace 202a.

The exhaust hole 204a is provided at a position opposed to the plurality of wafers 200. The gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafer 200 in the processing chamber 201 flows in the horizontal direction and then passes through The exhaust hole 204 a flows into the exhaust passage 206. The exhaust hole 204a is not limited to the case where it is configured as a slit-shaped through hole, and may be configured by a plurality of holes.

The manifold 209 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is connected with a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201 sequentially from the upstream side, and a by-product monitor that measures the amount of by-products 500. APC (Auto Pressure Controller) valve 243, a vacuum pump 246 as a vacuum exhaust device. The by-product monitor 500 is provided in the vicinity of the exhaust port 231 a at the connection portion of the process pipe 203 and the exhaust pipe 231. For example, RGA (Residual Gas Analyzer) can be used as the by-product monitor 500. The APC valve 243 is a state where the vacuum pump 246 is activated to open and close the valve, and the vacuum exhaust and the vacuum exhaust stop in the processing chamber 201 can be performed. Furthermore, by adjusting the valve opening degree while the vacuum pump 246 is activated, The pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly constituted by the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. It is also conceivable to include the vacuum pump 246 and the by-product monitor 500 in the exhaust system. In addition, RGA is a measuring instrument that can use principles such as IR absorption, mass analysis, and NDIR (Nondispersive Infrared Spectroscopy).

Below the collecting pipe 209 is provided with a sealing cover 219 as a furnace mouth cover which can seal the lower end opening of the collecting pipe 209 airtightly. The sealing cap 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. The sealing cover 219 is made of, for example, a metal such as SUS, and is formed in a disc shape. On the upper surface of the sealing cap 219 is provided an O-ring 220b as a sealing member that abuts against the lower end of the manifold 209. On the opposite side of the sealing cover 219 from the processing chamber 201 is provided a rotation mechanism 267 that rotates the wafer boat 217 accommodating the wafer 200. The rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 to be connected to the wafer boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be raised and lowered in the vertical direction by a wafer boat elevator 115 which is a lifting mechanism vertically installed outside the outer tube 203. The wafer boat elevator 115 is configured to carry the wafer boat 217 in and out of the processing chamber 201 by raising and lowering the sealing cover 219. The wafer boat elevator 115 is a transport device (transport mechanism) configured to transport the wafer boat 217 and the wafer 200 accommodated in the wafer boat 217 to the inside and outside of the processing chamber 201.

The wafer boat 217 as a substrate support is configured such that a plurality of wafers 200 of, for example, 25 to 200 wafers 200 are arranged in a vertical direction at intervals in a state where the centers of the wafers 200 are aligned in a horizontal posture. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. In the lower part of the wafer boat 217, a heat-insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages (not shown) in a horizontal posture. With this configuration, the heat from the heater 207 is not easily transmitted to the sealing cover 219 side. However, this embodiment is not limited to the above-mentioned form. For example, the heat insulation plate 218 may not be provided at the lower part of the wafer boat 217, and a heat insulation tube configured as a cylindrical member made of a heat-resistant material such as quartz or SiC may be provided.

As shown in FIG. 2, the inner tube 204 is provided with a temperature sensor 263 as a temperature detector, and is configured to adjust the temperature to the heater 207 based on the temperature information detected by the temperature sensor 263 The electricity is supplied, whereby the temperature in the processing chamber 201 becomes the desired temperature distribution. The temperature sensor 263 has an L-shape like the nozzles 410, 420, and 430, and is provided along the inner wall of the inner tube 204.

As shown in FIG. 3, the controller 121 of the control unit (control means) is a computer configured with a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121d. The RAM 121b, the memory device 121c, and the I/O port 121d are configured to exchange data with the CPU 121a via the internal bus. 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 constituted by, for example, flash memory, HDD (Hard Disk Drive), or the like. In the memory device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe describing the procedure or conditions of the manufacturing method of the semiconductor device described later, and the like are readable and stored. The process recipe is combined so that each process (each step) of the semiconductor device manufacturing method described later is executed on the controller 121, and a predetermined result can be obtained as a programming function. Hereinafter, this process recipe, control program, etc. will also be referred to as “program” in general. When the language of the program is used in this manual, there are cases where only the single process recipe is included, only the single control program is included, or the combination of the process recipe and the control program is included. The RAM 121b is a memory area (work area) configured to temporarily hold programs, data, and the like read by the CPU 121a.

The I/O port 121d is connected to the aforementioned MFC312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heating 207, temperature sensor 263, by-product monitor 500, rotating mechanism 267, wafer boat elevator 115, and the like.

The CPU 121a is configured to read a control program from the storage device 121c and execute it, and read prescriptions and the like from the storage device 121c in accordance with the input of an operation command from the input/output device 122 and the like. The CPU121a is configured to control the flow adjustment operations of various gases and the opening and closing operations of the valves 314, 324, 334, 514, 524, and 534 by the MFC 312, 322, 332, 512, 522, 532 according to the contents of the read prescription , The opening and closing operation of the APC valve 243 and the pressure adjustment operation of the pressure sensor 245 by the APC valve 243, the temperature adjustment operation of the heater 207 of the temperature sensor 263, and the auxiliary by-product monitor 500 The measurement action of the amount of living beings, the start and stop of the vacuum pump 246, the rotation and rotation speed adjustment action of the wafer boat 217 by the rotating mechanism 267, the lifting action of the wafer boat 217 by the wafer boat elevator 115, and the movement of the wafer boat 217 to the wafer boat 217. Storage operation of the wafer 200, etc.

The controller 121 can be stored in an external memory device (such as magnetic disks such as magnetic tapes, floppy disks or hard disks, optical disks such as CDs or DVDs, optical disks such as MO, USB memory or memory cards, etc. The above-mentioned program of semiconductor memory) 123 is installed in a computer to be constituted. The storage device 121c or the external storage device 123 is configured as a computer-readable recording medium. Hereinafter, these collectives are also referred to as recording media. In this specification, the recording medium may include only the memory device 121c alone, may include only the external memory device 123 alone, or may include both of them. The program to the computer can be provided without using the external memory device 123, and using communication means such as the Internet or a dedicated line.

(2) Substrate processing engineering (film forming engineering) As a first embodiment, an example of a process of forming, for example, a metal film constituting a gate electrode on a wafer 200 will be described with reference to FIG. 4 as a process of manufacturing a semiconductor device (device). The process of forming the metal film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121.

In this specification, when the term "wafer" is used, it means "wafer itself" or "a laminate of a wafer and a predetermined layer or film formed on its surface". When the term "surface of the wafer" is used in this specification, it means "the surface of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer". When the term "substrate" is used in this manual, it is also synonymous with the term "wafer".

(Wafer loading) Once a plurality of wafers 200 are loaded on the wafer boat 217 (wafer filling), as shown in FIG. 1, the wafer boat 217 supporting the plural wafers 200 is lifted by the wafer boat elevator 115. Carry into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 is in a state in which the lower end opening of the outer tube 203 is closed with the O-ring 220 interposed therebetween.

(Pressure adjustment and temperature adjustment) The vacuum pump 246 is used for vacuum exhaust, so that the inside of the processing chamber 201 becomes a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and based on the measured pressure information, the APC valve 243 is feedback controlled (pressure adjustment). The vacuum pump 246 is maintained in a constantly operated state at least until the processing of the wafer 200 is completed. In addition, the heater 207 heats the interior of the processing chamber 201 to a desired temperature. At this time, based on the temperature information detected by the temperature sensor 263, the amount of electricity supplied to the heater 207 is feedback controlled (temperature adjustment), so that the inside of the processing chamber 201 has a desired temperature distribution. The heating in the processing chamber 201 by the heater 207 continues at least until the processing of the wafer 200 is completed.

[First Process] (TiCl ₄ Gas Supply) The valve 314 is opened, and TiCl ₄ gas, which is a raw material gas, flows through the gas supply pipe 310. The _{flow rate of TiCl 4} gas is adjusted by the MFC 312, is supplied into the processing chamber 201 from the gas supply hole 410 a of the nozzle 410, and is exhausted from the exhaust pipe 231. At this time, TiCl ₄ gas is supplied to the wafer 200. At this time, the valve 514 is simultaneously opened, and an inert gas such as _{N 2 gas flows through the gas supply pipe 510. The N 2} gas flowing in the gas supply pipe 510 is adjusted by the MFC 512 in flow rate, is supplied into the processing chamber 201 together _{with the TiCl 4 gas, and is exhausted from the exhaust pipe 231.} At this time, in order to prevent _{the intrusion of TiCl 4 gas into the nozzles 420 and 430, the valves 524 and 534 are opened, and N 2} gas is flowed into the gas supply pipes 520 and 530. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430 and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 3990 Pa. _{The supply flow rate of the TiCl 4} gas controlled by the MFC312 is, for example, a flow rate in the range of 0.1 to 2.0 slm. _{The supply flow rate of N 2} gas controlled by MFC 512, 522, and 532 is set to a flow rate in the range of, for example, 0.1 to 20 slm, respectively. The temperature of the heater 207 at this time is set such that the temperature of the wafer 200 becomes a temperature in the range of 300 to 600° C., for example.

At this time, the gases flowing in the processing chamber 201 are only TiCl ₄ gas and N ₂ gas. With _{the supply of TiCl 4} gas, a Ti-containing layer is formed on the wafer 200 (the underlying film on the surface). The Ti-containing layer may be a Ti layer containing Cl, or may be _{an adsorption layer of TiCl 4} , or may include both of these.

[Second process] (Measurement of the amount of by-products) TiCl ₄ gas is supplied to the wafer 200 of the first process described above and exhausted from the exhaust pipe 231, and the by-product monitor 500 is used to continue the measurement of the exhaust gas. The amount of HCl which is a by-product exhausted from the air pipe 231.

[Third Process] (TiCl ₄ Gas Supply Stop) Figs. 5(A) and 5(B) are diagrams for explaining the TiCl ₄ gas supply stop operation in the substrate processing process of one embodiment of the present case.

As shown in FIG. 5(A) and FIG. 5(B), it can be seen that _{the HCl concentration measured by the by-product sensor 500 when the TiCl 4} gas is supplied increases, reaches the peak value P1, and then decreases. In addition, it can be seen that if by-products such as HCl are contained in the film, the film formation rate will decrease and the resistivity of the film will increase.

In this process, as shown in FIG. 5(A), the controller 121 is controlled so that the amount of HCl measured by the by-product monitor 500 at the time of _{TiCl 4 gas is attenuated from the peak value P1,} When the threshold value P2 set in advance is reached, the valve 314 of the gas supply pipe 310 is closed, and the supply of _{TiCl 4 gas is stopped.}

In addition, _{when the amount of HCl measured by the by-product monitor 500 at the time of TiCl 4} gas supply decays from the peak value P1, even if it does not reach the preset threshold value P2, as shown in Figure 5(B) As shown, the controller 121 controls to close the valve of the gas supply pipe 310 when the time for the measured amount of HCl to attenuate after reaching the peak value P1 and drop to the critical value P2 exceeds a predetermined time T1 set in advance for a certain time 314, and stop the supply of _{TiCl 4 gas.}

Here, the predetermined time T1 is a supply time set in advance. In addition, it is desirable that the predetermined time T1 is an integral multiple (N times) of the time until the measured amount of by-product reaches the peak value P1 after the supply of _{TiCl 4 gas is started.} N is appropriately set according to the desired processing. Moreover, N is the range of 2-15, and it is desirable to set it as 10.

In addition, the critical value P2 is set based on the peak value P1 of the amount of by-products to be measured, and is appropriately set to any value such as half or one-third of the peak value P1 of the amount of by-products, for example.

In addition, the threshold P2 is set in advance for each process recipe, and is stored in the memory device 121c. In addition, the threshold P2 corresponding to the prescription read during the substrate processing process is set according to the table provided with the threshold. That is, the threshold value is set according to the prescription. In addition, when the by-products remain in the film to perform the treatment prescription, the threshold value can be set high, and when the by-products are removed from the film to perform the treatment as a better prescription, the threshold value can be set low.

In addition, the threshold value P2 is set according to the number of filled wafers, the surface area of the wafer, or the like. In addition, the threshold value P2 corresponding to the number of filled wafers or the surface area of the wafer is set according to a table in which each threshold value is set. That is, the threshold value is set according to the number of filled wafers or the surface area of the wafer.

That is, the memory device 121c stores a table indicating the relationship between the prescription and the threshold value, or a table indicating the relationship between the number of wafers filled and the threshold value, or a table indicating the relationship between the surface area of the wafer and the threshold value, etc. .

[Fourth process] (Removal of residual gas) Then, the APC valve 243 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246, and the remaining in the processing chamber 201 is removed from the processing chamber 201 The unreacted or contributed to reaction by-products such as _{TiCl 4} gas or HCl after the formation of the Ti-containing layer. At this time, the valves 514, 524, and 534 are kept open to maintain _{the supply of N 2} gas into the processing chamber 201. The N _{2 gas acts as a purge gas, and can improve the effect of removing the unreacted TiCl 4} gas or reaction by-products remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer from the processing chamber 201.

[Fifth Process] (NH ₃ Gas Supply) After removing the residual gas in the processing chamber 201, the valve 334 is opened, and NH ₃ gas is flowed into the gas supply pipe 330 as a reaction gas. The _{flow rate of NH 3} gas is adjusted by the MFC 332, is supplied into the processing chamber 201 from the gas supply hole 430 a of the nozzle 430, and is exhausted from the exhaust pipe 231. At this time, the wafer 200 is supplied with NH ₃ gas. At this time, the valve 534 is opened at the same time, and N ₂ gas flows in the gas supply pipe 530. _{The flow rate of the N 2} gas flowing in the gas supply pipe 530 is adjusted by the MFC532. The N ₂ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231. At this time, in order to prevent _{the intrusion of NH 3} gas into the nozzles 410 and 420, the valves 514 and 524 are opened, and N ₂ gas flows into the gas supply pipes 510 and 520. The N ₂ gas is supplied into the processing chamber 201 via the gas supply pipes 310 and 320 and the nozzles 410 and 420, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 3990 Pa. _{The supply flow rate of the NH 3} gas controlled by the MFC332 is, for example, a flow rate in the range of 0.1 to 30 slm. _{The supply flow rate of N 2} gas controlled by MFC 512, 522, and 532 is set to a flow rate in the range of, for example, 0.1 to 30 slm, respectively. The time for supplying the NH ₃ gas to the wafer 200 is, for example, a time in the range of 0.01 to 30 seconds. The temperature of the heater 207 at this time is set to the same temperature as the _{TiCl 4 gas supply step.}

At this time, the gases flowing in the processing chamber 201 are only NH ₃ gas and N ₂ gas. The NH ₃ gas is a substitution reaction with at least a part of the Ti-containing layer formed on the wafer 200 in the first step. During the replacement reaction, Ti contained in the Ti-containing layer and _{N contained in the NH 3} gas are combined to form a TiN layer on the wafer 200.

[Step 6] (Measurement of the amount of by-products) The wafer 200 of the above-mentioned fifth step is supplied with NH ₃ gas and is evacuated from the exhaust pipe 231. The by-product monitor 500 is used to continue the measurement of the amount of the by-products. The amount of HCl which is a by-product exhausted from the air pipe 231.

[Step 7] ( _{Stopping of NH 3} gas supply) Then, similar to the third step described above, the controller 121 controls so that the amount of by-products measured by the by-product monitor 500 attenuates from the peak value P1 In the process, when the preset threshold value P2 is reached, the valve 334 of the gas supply pipe 330 is closed, and the supply of _{NH 3 gas is stopped.}

Also, as in the third process described above, while the amount of by-products measured by the by-product monitor 500 attenuates from the peak value P1, even if it does not reach the threshold value P2 set in advance, control The device 121 is controlled to close the valve 334 of the gas supply pipe 330 when the time for the measured amount of by-products to reach the peak value P1 and then attenuate to the critical value P2 exceeds a predetermined time T1 set in advance for a certain time Stop the supply of _{NH 3 gas.}

[Step 8] (Removal of residual gas) Then, the APC valve 243 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246, and the remaining in the processing chamber 201 is removed from the processing chamber 201 The unreacted or contributed to the NH ₃ gas or reaction by-products after the formation of the TiN layer. At this time, the valves 514, 524, and 534 are kept open to maintain _{the supply of N 2} gas into the processing chamber 201. The N _{2 gas acts as a purge gas, and can improve the effect of removing unreacted NH 3} gas or reaction by-products remaining in the processing chamber 201 or contributing to the formation of the TiN layer from the processing chamber 201.

(Implemented scheduled times) The cycles of the first to eighth steps described above are sequentially performed one or more times (predetermined number of times (n times)) to form a TiN film with a predetermined thickness on the wafer 200. It is ideal to repeat the above cycle multiple times.

The formation of a TiN film on such a wafer 200 is shown in FIGS. 6 and 7. FIG. 6(A) is a model diagram showing the surface of a wafer 200 on which a Ti-containing layer before exposure supplied _{by NH 3 gas is formed, and FIG. 6(B) is a model diagram showing the surface of wafer 200 after exposure by NH 3} gas supply. A model diagram of the surface of the wafer 200. 7(A) is a model diagram showing the surface of the wafer 200 on which the TiN layer before exposure supplied _{by TiCl 4 gas is formed, and FIG. 7(B) is a model diagram showing the surface after exposure by TiCl 4} gas supply. A model diagram of the surface of the wafer 200.

_{As shown in FIG. 6(A), if NH 3} gas is supplied to the surface of the wafer 200 on which the Ti-containing layer is formed, as shown in FIG. 6(B), a TiN layer is formed on the surface of the wafer 200 to generate HCl, Reaction byproducts such as ammonium chloride (NH _{4 Cl).}

_{Then, as shown in FIG. 7(A), if TiCl 4} gas is supplied to the surface of the wafer 200 on which the TiN layer is formed, a TiN layer is laminated on the surface of the wafer 200 as shown in FIG. 7(B) to generate HCl , Cl ₂ and other reaction by-products.

It can be seen that if by-products such as HCl are contained in the Ti-containing layer or TiN layer, the film formation rate decreases and the resistivity of the film increases.

FIG. 8 is a graph comparing _{the growth rate of the TiN film when the HCl gas is deliberately added and supplied in each of the TiCl 4} gas and the NH ₃ gas, and the film formation rate of the TiN film when the HCl gas is supplied without the addition of the HCl gas . As shown in Fig. 8, it was confirmed that _{adding HCl when TiCl 4} gas was supplied would reduce the film formation rate by about 25%. In addition, it was confirmed that _{adding HCl when supplying NH 3} gas reduced the film formation rate by about 15%.

That is, HCl, which is a byproduct of the reaction, has the effect of hindering the film formation rate of the TiN layer. Therefore, in order to remove by-products such as HCl from the Ti-containing layer or TiN layer, the by-product monitor 500 is used to measure the amount of by-products during the supply of processing gas, and the amount of by-products is attenuated to a threshold value or less. When the amount of by-products to be measured decays and drops to a critical value for more than a predetermined time, the by-products such as HCl are removed from the film, and the supply of _{TiCl 4} gas or NH _{3 gas is stopped.}

That is, the controller 121 controls to supply the processing gas (for film formation) while measuring the amount of by-products generated on the surface of the wafer 200 when supplying processing gas such as raw material gas or reaction gas, When the product decays and reaches a critical value or the amount of by-products to be measured decays and drops to the critical value for more than a predetermined time, the supply of the processing gas is stopped.

_{(Post-purification and atmospheric pressure restoration) N 2} gas is supplied into the processing chamber 201 from each of the gas supply pipes 510, 520, and 530, and exhausted from the exhaust pipe 231. The N ₂ gas acts as a purge gas, whereby the processing chamber 201 is purified with an inert gas, and the gas or by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purification). Then, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure return).

(Wafer out) Then, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafer 200 is carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). Then, the processed wafer 200 is taken out from the wafer boat 217 (wafer release).

In addition, the setting of the secondary biological monitor 500 is reset at the timing when the prescription is restarted, the number of filling tablets, and the like are changed.

(3) Effects according to this embodiment According to this embodiment, one or more effects shown below can be obtained. (a) Without increasing the supply time of the processing gas more than necessary, the amount of by-products contained in the film can be reduced to a level with no problem in characteristics. (b) It can be discharged efficiently: HCl, which is generated during film formation and reduces the film formation speed, can increase the film formation speed. (c) Resistivity can be reduced. (d) Compared with the case where the supply time of the processing gas is determined while monitoring the supply time and film formation speed of the processing gas, the experimental data can be reduced. Specifically, to determine the supply time of the processing gas while monitoring the supply time of the processing gas and the film formation speed, the experimental data corresponding to the surface area of the wafer or the number of filling sheets is required. However, according to this embodiment, it is not necessary. Need experimental data. (e) In addition, if the supply of the processing gas is stopped under the condition that the amount of HCl generated is large, the Cl content in the film increases, and there is a problem that the resistance value becomes high. However, as in this embodiment, by reducing the preset value After the critical value, the supply of processing gas is stopped, and stable film quality can be obtained regardless of the surface area or the number of filling sheets. (f) In addition, by arbitrarily setting the threshold value, different film qualities can be obtained, and the threshold value can be set according to the application.

<The second embodiment> Next, the second embodiment of this case will be explained.

The second embodiment of this case is implemented using the processing furnace 202 of the substrate processing apparatus 10 of the first embodiment described above. The second embodiment of this case is different from the substrate processing process of the above-mentioned embodiment only in the film forming process, and therefore only the film forming process will be described with reference to FIG. 9.

(1) Film formation process [first process] (TiCl _{4 gas supply) The TiCl 4} gas is supplied into the process chamber 201 by the same processing procedure as the _{TiCl 4} gas supply step of the above-mentioned first process. At this time, the gases flowing into the processing chamber 201 are only TiCl ₄ gas and N ₂ gas. With _{the supply of TiCl 4} gas, a Ti-containing layer is formed on the wafer 200 (the underlying film on the surface).

[Second Process] (Measurement of the amount of by-products) Continue to measure the amount of by-products through the same processing procedure as in the second step described above.

[Third process] (TiCl ₄ gas supply stop) Then, the controller 121 controls to close the valve 314 of the gas supply pipe 310 and stop the supply of _{TiCl 4 gas by the same processing procedure as in the third process described above.}

[Fourth process] (Removal of residual gas) Then, by the same processing procedure as the above-mentioned fourth process, unreacted remaining in the process chamber 201 or contribution to the formation of the Ti-containing layer are removed from the process chamber 201 TiCl ₄ gas or reaction by-product.

[The first process of the fourth] (SiH ₄ gas supply) After the residual gas in the processing chamber 201 is removed, the valve 324 is opened, and SiH ₄ gas, which is a reducing gas, flows through the gas supply pipe 320. The SiH ₄ gas is adjusted in flow rate by MFC 322, is supplied into the processing chamber 201 from the gas supply hole 420 a of the nozzle 420, and is exhausted from the exhaust pipe 231. At this time, the valve 524 is opened at the same time, and an inert gas such as _{N 2 gas flows through the gas supply pipe 520. The N 2} gas flowing in the gas supply pipe 520 is adjusted in flow rate by the MFC 522, is supplied into the processing chamber 201 together _{with the SiH 4 gas, and is exhausted from the exhaust pipe 231.} At this time, in order to prevent SiH ₄ gas from intruding into the nozzles 410 and 430, the valves 514 and 534 are opened, and N ₂ gas flows into the gas supply pipes 510 and 530. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 310 and 330 and the nozzles 410 and 430 and is exhausted from the exhaust pipe 231. _{At this time, SiH 4} gas and N ₂ gas are simultaneously supplied to the wafer 200.

At this time, the APC valve 243 is adjusted to set the pressure in the processing chamber 201 to, for example, 130 to 3990 Pa, preferably 500 to 2660 Pa, and more preferably a pressure in the range of 900 to 1500 Pa. Once the pressure in the processing chamber 201 is lower than 130 Pa, _{the Si contained in the SiH 4} gas enters the Ti-containing layer, and the Si content of the TiN film to be formed becomes high, which may become a TiSiN film. . When the pressure in the processing chamber 201 is higher than 3990 Pa, _{the Si contained in the SiH 4} gas enters the Ti-containing layer, and the Si content in the film of the TiN film to be formed becomes high and may become TiSiN. membrane. In this way, if the pressure in the processing chamber 201 is too low or too high, the elemental composition of the film to be formed will change. _{The supply flow rate of the SiH 4} gas controlled by MFC322 is set to, for example, 0.1 to 5 slm, preferably 0.5 to 3 slm, and more preferably a flow rate in the range of 1 to 2 slm. _{The supply flow rate of the N 2} gas controlled by MFC512, 522, and 532 is set to, for example, 0.01 to 20 slm, preferably 0.1 to 10 slm, and more preferably a flow rate in the range of 0.1 to 1 slm. The temperature of the heater 207 at this time is set to the same temperature as the _{TiCl 4 gas supply step.}

At this time, the gases flowing into the processing chamber 201 are only SiH ₄ gas and N ₂ gas. By supplying the SiH ₄ gas, HCl will react with SiH _4, SiCl ₄ and H ₂ as the processing chamber 201 from the discharge.

[Process of the 4th of 2] (Measurement of the amount of by-products) The wafer 200 of the above-mentioned 4th of the 1st process is supplied with SiH ₄ gas and is exhausted from the exhaust pipe 231 by the by-product monitor 500 continues to measure the amount of by-products exhausted from the exhaust pipe 231.

[The fourth of the third process] (SiH ₄ gas supply is stopped) Then, similar to the above-mentioned third process, the controller 121 controls the amount of by-products measured by the by-product monitor 500 from When the peak value P1 decays and reaches the threshold value P2 set in advance, the valve 324 of the gas supply pipe 320 is closed, and the supply of _{SiH 4 gas is stopped.}

Also, as in the third process described above, while the amount of by-products measured by the by-product monitor 500 attenuates from the peak value P1, even if it does not reach the threshold value P2 set in advance, control The device 121 is controlled to close the valve 324 of the gas supply pipe 320 when the time for the measured amount of by-products to reach the peak value P1 and then decay to the critical value P2 exceeds a predetermined time T1 set in advance for a certain time, and Stop the supply of _{SiH 4 gas.}

[Process 4 of 4] (Removal of residual gas) After that, the APC valve 243 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove the residual gas from the processing chamber 201 _{The unreacted or contributed SiH 4} gas or reaction byproducts in the chamber 201 after the Ti-containing layer is formed. At this time, the valves 514, 524, and 534 are kept open to maintain _{the supply of N 2} gas into the processing chamber 201. The N _{2 gas acts as a purge gas and can improve the effect of removing unreacted SiH 4} gas or reaction byproducts remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer from the processing chamber 201.

[Fifth Step] (NH ₃ Gas Supply) _{The NH 3} gas is supplied into the processing chamber 201 by the same processing procedure as the _{NH 3 gas supply step of the fifth step described above.} At this time, the gases flowing into the processing chamber 201 are only NH ₃ gas and N ₂ gas. With _{the supply of NH 3} gas, a TiN layer is formed on the wafer 200 (the underlying film on the surface).

[The sixth process] (Measurement of the amount of by-products) Continue to measure the amount of by-products through the same processing procedure as in the sixth process described above.

[Seventh Process] ( _{Stopping of NH 3} Gas Supply) Then, by the same processing procedure as in the seventh process described above, the valve 334 of the gas supply pipe 330 is closed and the supply of _{NH 3 gas is stopped.}

[Eighth Process] (Removal of Residual Gas) Then, by the same processing procedure as the above-mentioned eighth process, the unreacted NH remaining in the process chamber 201 or contributed to the formation of the TiN layer is removed from the process chamber 201 ₃ Gas or reaction by-products.

(Implemented scheduled times) By performing more than one time (predetermined number of times (n times)), the first to fourth steps above, the fourth step 1, the fourth second step, the fourth third step, and the fourth step are performed in sequence by performing more than one time (predetermined number of times (n times)). In the fourth process and the fifth to eighth process cycles, a TiN film with a predetermined thickness is formed on the wafer 200. It is ideal to repeat the above cycle multiple times.

In addition, FIG. 9 shows an example in which _{the supply of TiCl 4} gas and the supply of SiH ₄ gas are carried out sandwiching the fourth process (residual gas removal process), but it is not limited to this, and the supply of _{TiCl 4 gas may also be used.} The supply of SiH ₄ gas is started, and after the supply of TiCl ₄ gas is stopped, _{the supply of SiH 4} gas is stopped to constitute a gas supply sequence. In other words, it is configured such _{that the supply of TiCl 4} gas and the supply of SiH ₄ gas partially overlap. With this configuration, by reacting HCl generated during the supply of _{TiCl 4 gas with SiH 4} gas, SiCl _{4 is} generated, and the HCl removal efficiency can be improved.

In the case of this supply sequence, the amount of by-products is continuously measured by the same processing procedure as in the second step described above, and the supply of _{TiCl 4 gas is stopped by the same processing procedure as in the third step described above.}

Next, in the fourth and second process, the SiCl ₄ concentration is measured by the same processing procedure as in the second process above, and the amount of by-products is continuously measured, and then, by the same process as the fourth and third process The processing procedure is to stop the supply of _{SiH 4 gas.}

(2) Effects according to the second embodiment According to this embodiment, in addition to the same effects as those according to the above-mentioned embodiment, HCl generated after the supply of _{TiCl 4 gas can be reacted with SiH 4} to make Drain toward the outside of the reaction tube.

The following describes experimental examples, but this case is not limited by these experimental examples.

<Experimental Example> FIG. 10 is a diagram showing the relationship between the time when a TiCl ₄ gas supply TiCl ₄ gas is supplied to the wafer 200 with different surface areas HCl concentration.

In this experimental example, the above-mentioned substrate processing apparatus 10 and the substrate processing process shown in FIG. 4 are used to form TiN films on wafers W1 with surface area S1 and wafers W2 with surface area S2, respectively. Set S1<S2 here.

As shown in FIG. 10, in the film formation process of the wafer W1, after the TiCl ₄ gas supply is started, after t1 seconds, it attenuates from the peak value P1-1 and reaches the critical value P2. In addition, in the film formation process of the wafer W2, _{after the TiCl 4} gas supply was started, it decayed from the peak P1-2 and reached the critical value P2 after t2 seconds. That is, the peak value P1 of the amount of by-products confirmed varies depending on the surface area, and the wafer W2 with a large surface area has a longer time to reach the critical value than the wafer W1 with a small surface area. That is, until the amount of HCl in the film reaches the critical value, the wafer W2 with a large surface area takes more time than the wafer W1 with a small surface area, and it takes time to release the HCl.

Therefore, even when the surface area of the wafer is different, it was confirmed that by measuring the amount of HCl during the supply of the processing gas and stopping the supply of the processing gas, a film with a low HCl concentration can be formed.

<Modifications> In addition, in the above-mentioned embodiment, the amount of by-products measured after starting the supply of the raw gas and the reaction gas is described. When the amount of the by-products decays and reaches a critical value, or the amount of the measured by-products becomes the peak value. When the time after which it decays and falls to a critical value exceeds a predetermined time set in advance for a certain time, the supply of the source gas and the reaction gas is stopped, but it is not limited to this. Measure the amount of by-products after starting the supply of raw gas or reaction gas. When the amount of by-products decays and reaches a critical value, or the amount of by-products measured reaches a peak and then decays and falls to the critical value for longer than the time beforehand This case can also be applied to the case where the supply of the raw material gas or the reaction gas is stopped at a predetermined time set for a certain period of time.

In addition, in the above-mentioned embodiment, the description is given by setting the gas supply time after the start of the supply of the processing gas to the stop of the supply of the processing gas for each cycle. However, the present case is not limited to this, and may be set for each cycle. Cycle setting, or can also be set as a predetermined cycle period.

Specifically, for example, the first process to the third process may be performed in the first cycle, and the time from the start of the supply of the processing gas of the first process to the stop of the supply of the process gas of the third process may be set as the gas supply time. Use the set gas supply time to perform multiple cycles after the second cycle.

Here, when multiple cycles are performed, the amount of by-products generated every cycle may change. FIG. 11 is a graph showing the relationship between the film formation process time and the concentration of HCl discharged during the supply of _{NH 3 gas.} As shown in FIG. 11, it can be seen that _{the HCl discharged during the NH 3} gas supply decreases every time the number of cycles increases. When using such a prescription in which the amount of by-products changes in each cycle, the amount of change in the by-products per cycle may be stored in the memory device 121c in advance, and each cycle corresponding to the prescription read from the memory device 121c may be used. The gas supply time.

In addition, in the above-mentioned embodiment, the description is made by measuring the amount of HCl generated in the process of forming the TiN film, but this case is not limited to this, and hexachlorosilane (Si ₂ Cl ₆ ) is used for the measurement. The amount of HCl generated in the process of forming the SiN film with gas and NH _{3 gas can also be applied.}

In addition, in the above-mentioned embodiment, the description was made by measuring the amount of HCl as a by-product, but the present case is not limited to this. For example, it can be applied to measuring the formation of a zirconium oxide (ZrO) film, a hafnium oxide (HfO) film, _{Measurement of the amount of carbon dioxide (CO 2} ) generated by the process of using amine ligand-containing raw materials and ozone (O ₃ ) to form a silicon oxide (SiO) film, etc., hindering the reaction of one gas The amount of gas.

In addition, in the above-mentioned embodiment, by measuring the amount of by-products, when the amount of by-products decays and reaches a critical value, or the amount of by-products to be measured decays after reaching a peak and then decays and falls to the critical value for longer than the time required in advance. The case of stopping the supply of processing gas at a predetermined time set for a certain period of time will be explained. However, this case is not limited to this. The gas supply flow rate, the temperature of the processing room, or the processing room can also be controlled according to the amount of by-products to be measured. pressure.

In addition, in this case, the above-mentioned control may be performed based on the absolute amount of by-products, but it is desirable to perform the control based on the relative amount. In addition, it may be configured to measure the concentration ratio of the source gas and the by-products, but it is not necessary to measure the concentration ratio.

In addition, in the above-mentioned embodiment, an example of film formation using a substrate processing apparatus using a batch-type vertical apparatus that processes a plurality of substrates at a time is described, but the present case is not limited to this, and it is used to process one or more substrates at a time. It can also be suitably applied when forming a film with a single-chip substrate processing apparatus for several substrates. In addition, in the above-mentioned embodiment, an example in which a substrate processing apparatus having a hot wall type processing furnace is used to form a thin film is described, but this case is not limited to this, and a cold wall type is used. The substrate processing apparatus of the processing furnace can also be appropriately applied to the case of forming a thin film. In these cases, the processing conditions can be set to, for example, the same processing conditions as in the above-mentioned embodiment.

For example, when a substrate processing apparatus equipped with the processing furnace 302 shown in FIG. 12(A) is used to form a film, this case can also be suitably applied. The processing furnace 302 is equipped with: a processing container 303 forming a processing chamber 301, a shower head 303s that supplies gas in a shower-like manner in the processing chamber 301, a support stand 317 that supports one or several wafers 200 in a horizontal position, and from below The rotating shaft 355 supporting the support base 317 and the heater 307 provided on the support base 317. The inlet (gas inlet) of the shower head 303s is connected to the gas supply port 332a for supplying the above-mentioned raw material gas and the gas supply port 332b for supplying the above-mentioned reaction gas. The gas supply port 332a is connected to the same source gas supply system as the source gas supply system of the above-mentioned embodiment. The gas supply port 332b is connected to the reaction gas supply system similar to the reaction gas supply system of the above-mentioned embodiment. The outlet (gas discharge port) of the shower head 303s is provided with a gas dispersion plate for supplying gas in a shower-like manner in the processing chamber 301. The processing container 303 is provided with an exhaust port 331 for exhausting the inside of the processing chamber 301. The exhaust port 331 is connected to the same exhaust system as the exhaust system of the above-mentioned embodiment.

Moreover, for example, when a substrate processing apparatus equipped with the processing furnace 402 shown in FIG. 12(B) is used to form a film, this aspect can also be suitably applied. The processing furnace 402 is equipped with: a processing container 403 forming a processing chamber 401, a support table 417 that supports one or several wafers 200 in a horizontal position, a rotating shaft 455 that supports the support table 417 from below, and a wafer facing the processing container 403 The lamp heater 407 through which light is irradiated by the circle 200 and the quartz window 403w through which the light of the lamp heater 407 is transmitted. The processing container 403 is connected to a gas supply port 432a for supplying the above-mentioned raw material gas and a gas supply port 432b for supplying the above-mentioned reaction gas. The gas supply port 432a is connected to the same source gas supply system as the source gas supply system of the above-mentioned embodiment. The gas supply port 432b is connected to the reaction gas supply system similar to the reaction gas supply system of the above-mentioned embodiment. The processing container 403 is provided with an exhaust port 431 for exhausting the inside of the processing chamber 401. The exhaust port 431 is connected to the same exhaust system as the exhaust system of the above-mentioned embodiment.

In the case of using these substrate processing apparatuses, film formation can be performed in the same order and processing conditions as in the above-mentioned embodiment.

The process recipes used in the formation of these various thin films (programs that record processing procedures or processing conditions) are based on the content of substrate processing (film species, composition ratio, film quality, film thickness, processing procedures, It is ideal to prepare separately (preparation of a plurality of processing conditions, etc.) separately. Then, when starting substrate processing, it is ideal to appropriately select an appropriate process recipe from a plurality of process recipes according to the content of the substrate processing. Specifically, a plurality of process recipes prepared individually according to the content of substrate processing are pre-stored (installed) in the substrate processing apparatus via a telecommunication line or a recording medium (external memory device 123) in which the process recipe is recorded. The memory device 121c is ideal. Then, when the substrate processing is started, the CPU 121a included in the substrate processing apparatus will appropriately select an appropriate process recipe from among the plurality of process recipes stored in the memory device 121c according to the content of the substrate processing. With such a configuration, it is possible to form thin films of various film types, composition ratios, film qualities, and film thicknesses in a single substrate processing apparatus widely and with good reproducibility. In addition, it is possible to reduce the operator's operational burden (input burden of processing programs, processing conditions, etc.), and it is possible to quickly start substrate processing while avoiding operational errors.

In addition, this proposal can be realized even if the process recipe of the existing substrate processing apparatus is changed, for example. When changing the process recipe, install the process recipe of this case on the existing substrate processing device via the telecommunication line or the recording medium on which the process recipe is recorded, and it is also possible to operate the I/O device of the existing substrate processing device to change the process recipe itself The manufacturing process prescription of the cost case.

In the foregoing, various typical embodiments of this case have been described, but this case is not limited to these embodiments, and may be used in combination as appropriate.

10: Substrate processing equipment 121: Controller 200: Wafer (substrate) 201: Processing Room 500: By-product monitor

Fig. 1 is a schematic longitudinal sectional view showing a vertical processing furnace of a substrate processing apparatus according to an embodiment of the present invention. [Fig. 2] is a schematic cross-sectional view taken along the line AA in Fig. 1. [Fig. Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus according to an embodiment of this case, and a block diagram showing the control system of the controller. [Fig. 4] is a diagram showing the timing of gas supply in the first embodiment of the present invention. [FIG. 5] (A) and (B) are diagrams for explaining the TiCl ₄ gas supply stop operation in the substrate processing process of one embodiment of this case. [FIG. 6] (A) is a model diagram showing the surface of the wafer 200 on which the Ti-containing layer before exposure supplied _{by NH 3} gas is formed, and (B) is the surface after exposure _{by NH 3 gas supply} A model diagram of the surface of the wafer 200. [FIG. 7] (A) is a model diagram showing the surface of a wafer 200 on which a TiN layer before exposure supplied _{by TiCl 4} gas is formed, and (B) is a model diagram showing the surface of the wafer 200 after exposure supplied _{by TiCl 4 gas} A model diagram of the surface of the circle 200. Fig. 8 is a graph comparing the film formation rate in the case where a small amount of HCl gas is added and supplied to each of _{TiCl 4} gas and NH _{3 gas, and the case where HCl gas is supplied without adding HCl gas.} [Fig. 9] Fig. 9 is a diagram showing the timing of gas supply in the second embodiment of the present invention. Fig. 10 is a graph showing the relationship between the TiCl ₄ gas supply time, _{the HCl concentration measured when the TiCl 4} gas is supplied, and the size of the surface area of the wafer 200. Fig. 11 is a graph showing the relationship between the film formation processing time of the substrate processing process of one embodiment of the present case and the HCl concentration measured when _{NH 3 gas is supplied.} [Fig. 12] (A) and (B) are schematic longitudinal cross-sectional views showing a processing furnace of a substrate processing apparatus according to another embodiment of the present application.

10: Substrate processing equipment

115: Crystal Boat Lift

121: Controller

200: Wafer (substrate)

201: Processing Room

201a: Preparation room

202: Treatment furnace

203: Outer Tube

204: inner tube

204a: Exhaust hole (exhaust port)

206: Exhaust Path

207: heater

209: Collecting Tube

217: Crystal Boat

218: Insulation Board

219: Seal cover

220a, 220b: O-ring

231: Exhaust Pipe

231a: exhaust port

243: APC valve

245: Pressure sensor

246: Vacuum pump

255: Rotation axis

267: Rotating Mechanism

310, 320, 330, 510, 520, 530: gas supply pipe

312,322,332,512,522,532: Mass Flow Controller (MFC)

314,324,334,514,524,534: Valve

410,420,430: nozzle

410a, 420a, 430a: gas supply hole

500: By-product monitor

Claims (16)

A method for manufacturing a semiconductor device, which is characterized by: The first step is to start the supply of processing gas to the substrate in the processing chamber; The second project is to continue to measure the amount of by-products exhausted from the aforementioned processing chamber; The third step is to control to stop the supply of processing gas when the amount of by-products to be measured decays and reaches a set threshold value; and The fourth step is to exhaust the aforementioned treatment chamber. The method for manufacturing a semiconductor device according to claim 1, wherein the threshold value is set based on the peak value of the amount of the by-product to be measured. The method of manufacturing a semiconductor device according to claim 1, wherein the recipe including the aforementioned processes 1, 2, 3, and 4 is read from the memory device, and The threshold value corresponding to the prescription read from the aforementioned memory device is set according to a table in which threshold values are set for each prescription. The method for manufacturing a semiconductor device according to claim 1, wherein, in the third step, when the amount of by-products to be measured reaches a peak and then attenuates and falls to a critical value for more than a predetermined time, the process gas is controlled to stop Supply. The method for manufacturing a semiconductor device according to claim 4, wherein the predetermined time is a predetermined time set in advance. The method of manufacturing a semiconductor device according to claim 4, wherein the predetermined time is a time that is an integral multiple of a time at which the measured amount of by-products reaches a peak after the supply of the processing gas is started. Such as claim 1, the method of manufacturing a semiconductor device, which further has: The fifth step is to start the supply of reaction gas that reacts with the processing gas to the substrate in the processing chamber; The sixth project, which is to continue to measure the amount of by-products exhausted from the aforementioned processing chamber; The seventh step is to control to stop the supply of reactant gas when the amount of by-products to be measured decays and reaches the set threshold value; and The eighth process is to exhaust the aforementioned treatment chamber. The method of manufacturing a semiconductor device according to claim 1, wherein the gas supply time from the start of the supply of the processing gas from the first step to the third step to the stop of the supply of the processing gas may be set for each cycle , Or it can be set every multiple cycles, or it can be set as a predetermined cycle period. The method for manufacturing a semiconductor device according to claim 8, wherein when the gas supply time is set per plural cycles, the use starts after the supply of the processing gas from the first step to the third step until the supply of the processing gas is stopped The gas supply time to carry out multiple cycles. The method for manufacturing a semiconductor device according to claim 8, wherein when using a prescription that changes the amount of by-products generated in each cycle, the amount of change in the by-products for each cycle is memorized in the memory device in advance, and the use corresponds to The gas supply time per cycle of the prescription read from the aforementioned memory device. The method of manufacturing a semiconductor device according to claim 8, wherein resetting at the timing when the prescription is restarted or the number of filling sheets is changed: the setting of the by-product monitor that measures the amount of the by-product. The method for manufacturing a semiconductor device according to claim 1, wherein, in the third step, the gas supply flow rate, the temperature in the processing chamber, or the pressure in the processing chamber are controlled in accordance with the amount of by-products to be measured. The method for manufacturing a semiconductor device according to claim 1, wherein in the second step, the amount of gas that inhibits the reaction of other gases is measured. The method for manufacturing a semiconductor device according to claim 1, wherein, in the second step, a by-product monitor that measures the amount of by-products provided near the exhaust port of the reaction tube is used. A recording medium characterized by recording a program for executing the following program on the aforementioned substrate processing apparatus by a computer, The first procedure is to start the supply of processing gas for the substrate in the processing chamber of the substrate processing apparatus; The second procedure is to continue to measure the amount of by-products exhausted from the aforementioned processing chamber; The third program, which is in the process of attenuation of the measured by-products, when reaching the set threshold, the control is made to stop the supply of processing gas; The fourth procedure is to exhaust the aforementioned processing chamber. A substrate processing device characterized by: Processing room, which processes substrates; Processing gas supply system, which supplies processing gas to the aforementioned substrate; Exhaust system, which exhausts the aforementioned processing chamber; By-product monitor, which measures the amount of by-products exhausted from the aforementioned processing chamber; and The control unit is configured to control the processing gas supply system, the exhaust system, and the by-product monitor. After the supply of the processing gas is started, the amount of the by-products is attenuated to reach the setting. When the critical value is reached, the supply of the aforementioned processing gas is stopped.

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