WO2021181450A1

WO2021181450A1 - Substrate treatment device, production method for semiconductor device, and program

Info

Publication number: WO2021181450A1
Application number: PCT/JP2020/009978
Authority: WO
Inventors: 原　大介; 橘八幡; 剛竹田
Original assignee: 株式会社ＫｏｋｕｓａｉＥｌｅｃｔｒｉｃ
Priority date: 2020-03-09
Filing date: 2020-03-09
Publication date: 2021-09-16
Also published as: TW202145838A; TWI785510B

Abstract

Provided is a technology comprising: a treatment chamber in which a substrate is treated; a substrate support tool that supports a plurality of substrates at multiple levels in the vertical direction; and a plasma generation unit having a buffer structure that is provided inside the treatment chamber and that turns a gas into a plasma, and an external electrode that generates plasma and that is provided on the outside of the treatment chamber at a position corresponding to the position to which the buffer structure is provided.

Description

Substrate processing equipment, semiconductor equipment manufacturing methods and programs

This disclosure relates to a substrate processing apparatus, a manufacturing method and a program of a semiconductor apparatus.

In one of the manufacturing processes of semiconductor devices, raw material gas, reaction gas, etc. are activated by plasma and supplied to the substrate brought into the processing chamber of the substrate processing apparatus, and an insulating film, semiconductor film, conductor, etc. are supplied on the substrate. Substrate treatment may be performed to form various films such as films or remove various films. For example, in Patent Document 1, a buffer chamber for generating plasma is provided in the reaction tube.

Japanese Unexamined Patent Publication No. 2016-106415

An object of the present disclosure is to provide a technique capable of supplying a plasma active species gas formed with high efficiency to a substrate.

According to one aspect of the present disclosure
A processing room for processing the substrate and
A board support portion that holds a plurality of the boards in multiple stages in the vertical direction,
A plasma generating unit having a buffer structure provided in the processing chamber for converting gas into plasma, and an external electrode for generating plasma provided outside the processing chamber corresponding to the position where the buffer structure is provided. ,
Technology is provided.

According to the present disclosure, it is possible to provide a technique capable of supplying a plasma active species gas formed to a substrate with high efficiency.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus preferably used in embodiment of this disclosure, and is the figure which shows the processing furnace part in the vertical sectional view. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of this disclosure, and is the figure which shows the processing furnace part in the cross-sectional view taken along line AA of FIG. (A) FIG. 3 is an enlarged cross-sectional view for explaining a buffer structure of a substrate processing apparatus preferably used in the embodiment of the present disclosure. (B) It is a schematic diagram for demonstrating the buffer structure of the substrate processing apparatus preferably used in the embodiment of this disclosure. It is a schematic block diagram of the controller of the substrate processing apparatus preferably used in the embodiment of this disclosure, and is the figure which shows the control system of the controller by the block diagram. It is a flowchart of the substrate processing process which concerns on embodiment of this disclosure.

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

(1) Configuration of substrate processing device (heating device)
As shown in FIG. 1, the processing furnace 202 used for the substrate processing apparatus is a so-called vertical furnace capable of accommodating substrates in multiple stages in the vertical direction, and has a heater 207 as a heating apparatus (heating mechanism). .. The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate. The heater 207 also functions as an activation mechanism (excitation portion) for activating (exciting) the gas with heat, as will be described later.

(Processing room)
Inside the heater 207, a reaction tube 203 is arranged concentrically with 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 in a cylindrical shape with the upper end closed and the lower end open. Below the reaction tube 203, a manifold (inlet flange) 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. When the manifold 209 is supported by the heater base, the reaction tube 203 is in a vertically installed state. The processing vessel (reaction vessel) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the cylinder inside the processing container. The processing chamber 201 is configured to accommodate a plurality of wafers 200 as substrates. The processing container is not limited to the above configuration, and only the reaction tube 203 may be referred to as a processing container.

A nozzle 249a and a pipe 249b are provided in the processing chamber 201 so as to penetrate the side wall of the manifold 209.

Gas supply pipes

232a and 232b are connected to the nozzle 249a and the pipe 249b, respectively. As described above, the processing chamber 201 is provided with one nozzle 249a, one pipe 249b, and two

gas supply pipes

232a and 232b, and supplies a plurality of types of gas into the processing chamber 201. It is possible to do.

The

gas supply pipes

232a and 232b are provided with mass flow controllers (MFCs) 241a and 241b which are flow rate controllers (flow control units) and

valves

243a and 243b which are on-off valves, respectively, in order from the upstream side of the gas flow. ..

Gas supply pipes

232c and 232d for supplying the inert gas are connected to the downstream side of the

gas supply pipes

232a and 232b with respect to the

valves

243a and 243b, respectively. The

gas supply pipes

232c and 232d are provided with

MFCs

241c and 241d and

valves

243c and 243d, respectively, in this order from the upstream side of the gas flow.

As shown in FIG. 2, the nozzle 249a rises in the space between the inner wall of the reaction tube 203 and the wafer 200 along the upper part from the lower part of the inner wall of the reaction tube 203 toward the upper side in the loading direction of the wafer 200. It is provided in. That is, the nozzle 249a is provided along the wafer arrangement area in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area (placement area) on which the wafer 200 is arranged (placed). .. That is, the nozzle 249a is provided on the side of the end portion (peripheral portion) of each wafer 200 carried into the processing chamber 201 in a direction perpendicular to the surface (flat surface) of the wafer 200. A gas supply hole 250a for supplying gas is provided on the side surface of the nozzle 249a. The gas supply hole 250a is opened so as to face the center of the reaction tube 203, and gas can be supplied toward the wafer 200. A plurality of gas supply holes 250a are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided with the same opening pitch.

A pipe 249b is connected to the tip of the gas supply pipe 232b. The pipe 249b is connected in the buffer structure 237. In the present embodiment, two buffer structures 237 are arranged so as to sandwich a straight line passing through the center of the reaction tube 203 (processing chamber 201) and the nozzle 249a in a plan view, or the center of the reaction tube 203 (processing chamber 201). The buffer structure 237 is arranged symmetrically with respect to the line connecting the nozzle 249a and the exhaust pipe 231. The buffer structure 237 is provided with a partition plate 237a, which is partitioned by a partition plate 237a into a gas introduction area 237b for introducing gas from the pipe 249b and a plasma area 237c for converting gas into plasma. The plasma area 237c is also referred to as a buffer chamber 237c, which is a gas dispersion space. The buffer chamber 237c is arranged on the nozzle 249a side, and the gas introduction area 237b is arranged on the exhaust pipe 231 side.

As shown in FIG. 2, the buffer chamber 237c is formed in an annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, and in a portion extending above the lower part of the inner wall of the reaction tube 203. It is provided along the loading direction of. That is, the buffer chamber 237c is formed by the buffer structure 237 along the wafer arrangement region in the region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region. The buffer structure 237 is made of an insulator which is a heat-resistant material such as quartz or SiC, and

gas supply ports

302 and 304 for supplying gas are formed on the arcuate wall surface of the buffer structure 237. ing. A plurality of

gas supply ports

302 and 304 are provided in the horizontal direction of the plurality of wafers 200 loaded, and are opened so as to face the center of the reaction tube 203, and gas is supplied toward the wafer 200. It is possible. A plurality of

gas supply ports

302 and 304 are provided from the lower part to the upper part of the reaction tube 203 along the loading direction of the wafer 200, each having the same opening area, and further provided with the same opening pitch.

The gas introduction area 237b is provided so as to rise upward from the lower part of the inner wall of the reaction tube 203 toward the upper part in the loading direction of the wafer 200. The partition plate 237a is provided with a gas supply hole 237d for supplying gas from the gas introduction area 237b to the plasma area 237c. As a result, the reaction gas supplied to the gas introduction area 237b is dispersed in the buffer chamber 237c. Similar to the gas supply holes 250a, a plurality of gas supply holes 237d are provided from the lower part to the upper part of the reaction tube 203. Instead of the pipe 249b and the gas introduction area 237b, a nozzle, for example, a perforated nozzle similar to the nozzle 249a may be provided in the buffer chamber 237c to supply the processing gas.

As described above, in the present embodiment, in the plan view defined by the inner wall of the side wall of the reaction tube 203 and the end portions of the plurality of wafers 200 arranged in the reaction tube 203, that is, in the annular vertically long space, that is, Gas is conveyed via the nozzle 249a and the buffer chamber 237c arranged in the cylindrical space. Then, gas is ejected into the reaction tube 203 for the first time in the vicinity of the wafer 200 from the gas supply holes 250a and the

gas supply ports

302 and 304 opened in the nozzle 249a and the buffer chamber 237c, respectively. The main flow of gas in the reaction tube 203 is in the direction parallel to the surface of the wafer 200, that is, in the horizontal direction. With such a configuration, gas can be uniformly supplied to each wafer 200, and the uniformity of the film thickness of the film formed on each wafer 200 can be improved. The gas that has flowed on the surface of the wafer 200, that is, the residual gas after the reaction, flows toward the exhaust port, that is, the exhaust pipe 231 described later. However, the direction of the residual gas flow is appropriately specified by the position of the exhaust port, and is not limited to the vertical direction.

From the gas supply pipe 232a, as a raw material containing a predetermined element, for example, a silane raw material gas containing silicon (Si) as a predetermined element is supplied into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

The raw material gas is a raw material in a gaseous state, for example, a gas obtained by vaporizing a raw material in a liquid state under normal temperature and pressure, a raw material in a gaseous state under normal temperature and pressure, and the like. When the term "raw material" is used in the present specification, it means "liquid raw material in a liquid state", "raw material gas in a gaseous state", or both of them. There is.

As the silane raw material gas, for example, a raw material gas containing Si and a halogen element, that is, a halosilane raw material gas can be used. The halosilane raw material is a silane raw material having a halogen group. The halogen element contains at least one selected from the group consisting of chlorine (Cl), fluorine (F), bromine (Br) and iodine (I). That is, the halosilane raw material contains at least one halogen group selected from the group consisting of a chloro group, a fluoro group, a bromo group and an iodine group. The halosilane raw material can be said to be a kind of halide.

As the halosilane raw material gas, for example, a raw material gas containing Si and Cl, that is, a chlorosilane raw material gas can be used. As the chlorosilane raw material gas, for example, dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS) gas can be used.

From the gas supply pipe 232b, as a reactor containing an element different from the above-mentioned predetermined element, for example, a nitrogen (N) -containing gas as a reaction gas is MFC241b, a valve 243b, a pipe 249b, and a gas introduction area 237b. It is configured to be supplied into the buffer chamber 237c via. As the N-containing gas, for example, a hydrogen nitride-based gas can be used. The hydrogen nitride-based gas can be said to be a substance composed of only two elements, N and H, and acts as a nitride gas, that is, an N source. As the hydrogen nitride-based gas, for example, ammonia (NH ₃ ) gas can be used.

From the

gas supply pipes

232c and 232d, for example, nitrogen (N ₂ ) gas is processed as an inert gas via MFC241c, 241d,

valves

243c, 243d,

gas supply pipes

232a, 232b, nozzle 249a, and pipe 249b, respectively. It is supplied into the room 201.

Mainly, the gas supply pipe 232a, the MFC 241a, and the valve 243a form a raw material supply system as the first gas supply system. Mainly, the gas supply pipe 232b, the MFC 241b, and the valve 243b form a reactant supply system (reactant supply system) as the second gas supply system. Mainly, the

gas supply pipes

232c, 232d, MFC241c, 241d, and

valves

243c, 243d constitute an inert gas supply system. The raw material supply system, the reactant supply system and the inert gas supply system are also collectively referred to simply as a gas supply system (gas supply unit).

(Plasma generator)
Next, the plasma generation unit will be described with reference to FIGS. 1 to 3.

As shown in FIG. 2, a capacitively coupled plasma (Capacitively Coupled Plasma, abbreviated as CCP) is used as the plasma, and a buffer inside the reaction tube 203 (processing chamber 201), which is a vacuum partition made of quartz or the like when the reaction gas is supplied. Generated in structure 237.

As shown in FIGS. 2 and 3A, the external electrode 300 is made of a thin plate having a rectangular shape long in the arrangement direction of the wafer 200. As shown in FIGS. 1 and 3B, the external electrode 300 has a reference potential of 0 V and a first external electrode (Hot electrode) 300-1 to which the high frequency power supply 273 is connected via the matching unit 272. Second external electrodes (Ground electrodes) 300-2, which are grounded to the ground, are arranged at equal intervals. In the present disclosure, when it is not necessary to separately explain the description, the description will be described as the external electrode 300.

The external electrode 300 is provided between the reaction tube 203 and the heater 207 on the outside of the processing chamber 201 corresponding to the position where the buffer structure 237 is provided. Specifically, the buffer structure is provided with a plasma area (buffer chamber) 237c as an area for converting gas into plasma, and the external electrode 300 is the outer wall of the reaction tube 203 corresponding to the position where the buffer chamber 237c is provided. It is arranged in a substantially arc shape along (outside of the processing chamber 201). The external electrode 300 is fixedly arranged on the inner wall surface of a quartz cover formed in an arc shape having a central angle of 30 degrees or more and 240 degrees or less, for example. That is, the external electrode 300 is arranged on the outer periphery of the reaction tube 203 (outside the processing chamber 201) corresponding to the position where the buffer chamber (plasma area) 237c is provided. Further, the buffer structure 237 is provided with a gas supply unit (gas introduction area) 237b as an area for supplying gas to the buffer chamber 237c. The external electrode 300 is not arranged on the outer periphery of the reaction tube 203 (outside the processing chamber 201) corresponding to the position where the gas introduction area (gas supply unit) 237b is provided. The plasma active species 306 is generated in the buffer chamber 237c by inputting a high frequency of, for example, a frequency of 13.56 MHz from the high frequency power supply 273 to the external electrode 300 via the matching unit 272. The plasma generated in this way makes it possible to supply the plasma active species 306 for substrate treatment from the periphery of the wafer 200 to the surface of the wafer 200. The plasma generation unit is mainly composed of the buffer structure 237, the external electrode 300, and the high frequency power supply 273.

The external electrode 300 can be made of a metal such as aluminum, copper, or stainless steel, but by using an oxidation-resistant material such as nickel, it is possible to process the substrate while suppressing deterioration of electrical conductivity. In particular, by forming the nickel alloy material to which aluminum is added, an AlO film, which is an oxide film having high heat resistance and corrosion resistance, is formed on the electrode surface. Due to the effect of this film formation, the progress of deterioration inside the electrode can be suppressed, so that the decrease in plasma generation efficiency due to the decrease in electrical conductivity can be suppressed.

(Electrode fixing jig)
Next, the quartz cover 301 as an electrode fixing jig for fixing the external electrode 300 will be described with reference to FIG. As shown in FIGS. 3A and 3B, a plurality of external electrodes 300 are provided with notches (not shown) on the inner wall surface of a quartz cover 301 which is a curved electrode fixing jig. It is hooked on the protruding portion 310, slid and fixed, and unitized (hook type electrode unit) so as to be integrated with the quartz cover 301, and is installed on the outer periphery of the reaction tube 203. Here, the external electrode 300 and the quartz cover 301, which is an electrode fixing jig, are referred to as an electrode fixing unit. Quartz and nickel alloys are used as the materials for the quartz cover 301 and the external electrode 300, respectively.

In order to obtain high processing capacity at a substrate temperature of 500 ° C or less, the exclusive ratio of the quartz cover 301 should be an arc shape with a central angle of 30 degrees or more and 240 degrees or less, and an exhaust pipe which is an exhaust port to avoid generation of particles. It is desirable that the arrangement avoids 231 and the nozzle 249a. If the central angle is smaller than 30 degrees, the number of external electrodes 300 to be arranged is reduced, and the amount of plasma produced is reduced. If the central angle is larger than 240 degrees, the area covered by the quartz cover 301 on the side surface of the reaction tube 203 becomes too large, and the thermal energy from the heater 207 is cut off. In this embodiment, two quartz covers having a central angle of 110 degrees are arranged symmetrically.

The reaction pipe 203 is provided with an exhaust pipe 231 as an exhaust unit for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is provided with a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (AutoPressure Controller) valve 244 as an exhaust valve (pressure adjusting unit). A vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 operating, and further, with the vacuum pump 246 operating, the APC valve 244 can perform vacuum exhaust and vacuum exhaust stop. The valve is configured so that the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245. The exhaust system is mainly composed of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245. The vacuum pump 246 may be included in the exhaust system. The exhaust pipe 231 is not limited to the case where it is provided in the reaction pipe 203, and may be provided in the manifold 209 in the same manner as the nozzle 249a.

Below the manifold 209, a seal cap 219 is provided as a furnace palate body that can airtightly close the lower end opening of the manifold 209. The seal cap 219 is configured to come into contact with the lower end of the manifold 209 from below in the vertical direction. The seal cap 219 is made of a metal such as SUS and is formed in a disk shape. An O-ring 220b as a sealing member that comes into contact with the lower end of the manifold 209 is provided on the upper surface of the seal cap 219. On the side of the seal cap 219 opposite to the processing chamber 201, a rotation mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically lifted and lowered by a boat elevator 115 as a lifting mechanism vertically installed outside the reaction tube 203. The boat elevator 115 is configured so that the boat 217 can be carried in and out of the processing chamber 201 by raising and lowering the seal cap 219. The boat elevator 115 is configured as a transport device (convey mechanism) for transporting the boat 217, that is, the wafer 200, into and out of the processing chamber 201. Further, below the manifold 209, a shutter 219s is provided as a furnace palate body that can airtightly close the lower end opening of the manifold 209 while the seal cap 219 is lowered by the boat elevator 115. The shutter 219s is made of a metal such as SUS and is formed in a disk shape. An O-ring 220c as a sealing member that comes into contact with the lower end of the manifold 209 is provided on the upper surface of the shutter 219s. The opening / closing operation of the shutter 219s (elevating / lowering operation, rotating operation, etc.) is controlled by the shutter opening / closing mechanism 115s.

(Board support)
As shown in FIG. 1, the boat 217 as a substrate support supports a plurality of wafers, for example, 25 to 200 wafers, in a horizontal position and vertically aligned with each other in a multi-stage manner. That is, they are arranged so as to be arranged at predetermined intervals. The boat 217 is made of a heat resistant material such as quartz or SiC. In the lower part of the boat 217, a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages.

As shown in FIG. 1, a temperature sensor 263 as a temperature detector is installed inside the reaction tube 203. By adjusting the degree of energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 is set to a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203 like the nozzle 249a.

(Control device)
Next, the control device will be described with reference to FIG. As shown in FIG. 4, the controller 121, which is a control unit (control device), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. Has been done. The RAM 121b, the storage device 121c, and the I / O port 121d are configured so that data can be exchanged with the CPU 121a via the internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121.

The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing device, a process recipe in which the procedure and conditions of the film forming process described later are described, and the like are readablely stored. The process recipes are combined so that the controller 121 can execute each procedure in various processes (deposition process) described later and obtain a predetermined result, and functions as a program. Hereinafter, process recipes, control programs, etc. are collectively referred to simply as programs. In addition, a process recipe is also simply referred to as a recipe. When the term program is used in the present specification, it may include only a recipe alone, a control program alone, or both of them. The RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily held.

The I / O port 121d includes the above-mentioned MFC 241a to 241d, valves 243a to 243d, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, matching unit 272, high frequency power supply 273, rotation mechanism 267, and boat. It is connected to the elevator 115, the shutter opening / closing mechanism 115s, and the like.

The CPU 121a is configured to read and execute a control program from the storage device 121c and read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a controls the rotation mechanism 267, adjusts the flow rate of various gases by the MFCs 241a to 241d, opens and closes the valves 243a to 243d, adjusts the high frequency power supply 273 based on the impedance monitoring, and APC so as to follow the contents of the read recipe. Opening and closing operation of valve 244 and 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, forward / reverse rotation of boat 217 by rotation mechanism 267, It is configured to control the rotation angle and rotation speed adjusting operation, the raising and lowering operation of the boat 217 by the boat elevator 115, the plasma generation by the high frequency power supply 273 and the external electrode 300, and the like.

The controller 121 installs the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as MO, or a semiconductor memory such as a USB memory) 123 in a computer. Can be configured by. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, these are collectively referred to simply as a recording medium. When the term recording medium is used in the present specification, it may include only the storage device 121c alone, it may include only the external storage device 123 alone, or it may include both of them. The program may be provided to the computer by using a communication means such as the Internet or a dedicated line without using the external storage device 123.

(2) Substrate Processing Step Next, a step of forming a thin film on the wafer 200 as one step of the manufacturing process of the semiconductor device using the substrate processing apparatus will be described with reference to FIG. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

Here, the step of supplying the DCS gas as a source gas, and supplying the plasma-excited NH ₃ gas was allowed as a reaction gas in a non-simultaneous, i.e. a predetermined number of times (at least once) without synchronizing by performing the wafer An example of forming a silicon nitride film (SiN film) as a film containing Si and N on 200 will be described. Further, for example, a predetermined film may be formed in advance on the wafer 200. Further, a predetermined pattern may be formed in advance on the wafer 200 or a predetermined film.

In the present specification, the process flow of the film forming process shown in FIG. 5 may be shown as follows for convenience.
(DCS → NH ₃ *) × n ⇒ SiN

When the word "wafer" is used in the present specification, it may mean the wafer itself or a laminate of a wafer and a predetermined layer or film formed on the surface thereof. When the term "wafer surface" is used in the present specification, it may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In the present specification, when it is described that "a predetermined layer is formed on a wafer", it means that a predetermined layer is directly formed on the surface of the wafer itself, or a layer formed on the wafer or the like. It may mean forming a predetermined layer on top of it. The use of the term "wafer" in the present specification is also synonymous with the use of the term "wafer".

(Bring-in step: S1)
When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter opening / closing mechanism 115s moves the shutter 219s to open the lower end opening of the manifold 209 (shutter open). After that, 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 load). In this state, the seal cap 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b.

(Pressure / temperature adjustment step: S2)
Vacuum exhaust (vacuum exhaust) is performed by the vacuum pump 246 so that the inside of the processing chamber 201, that is, the space where the wafer 200 exists, has a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. The vacuum pump 246 is always kept in operation until at least the film forming step described later is completed.

Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the state of energization of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. The heating in the processing chamber 201 by the heater 207 is continuously performed at least until the film forming step described later is completed. However, when the film forming step is performed under a temperature condition of room temperature or lower, it is not necessary to heat the inside of the processing chamber 201 by the heater 207. When only the processing under such a temperature is performed, the heater 207 becomes unnecessary, and the heater 207 does not have to be installed in the substrate processing apparatus. In this case, the configuration of the substrate processing apparatus can be simplified.
Subsequently, the rotation mechanism 267 starts the rotation of the boat 217 and the wafer 200. The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continuously performed at least until the film forming step is completed.

(Raw material gas supply step: S3, S4)
In step S3, DCS gas is supplied to the wafer 200 in the processing chamber 201. The valve 243a is opened to allow DCS gas to flow into the gas supply pipe 232a. The flow rate of the DCS gas is adjusted by the MFC 241a, is supplied into the processing chamber 201 from the gas supply hole 250a via the nozzle 249a, and is exhausted from the exhaust pipe 231. Open At the same time the valve 243 c, flow the _{N 2} gas to the gas supply pipe 232c. The _{flow rate of the N 2} gas is adjusted by the MFC 241c, is supplied into the processing chamber 201 together with the DCS gas, and is exhausted from the exhaust pipe 231.

Further, in order to suppress the penetration of the DCS gas into the pipe 249 b, by opening the valve 243 d, flow the _{N 2} gas to the gas supply pipe 232 d. The N ₂ gas is supplied into the processing chamber 201 via the gas supply pipe 232b and the pipe 249b, and is exhausted from the exhaust pipe 231.

The supply flow rate of the DCS gas controlled by the MFC 241a is, for example, a flow rate within the range of 1 sccm or more and 6000 sccm or less, preferably 3000 sccm or more and 5000 sccm or less. _{The supply flow rate of the N 2} gas controlled by the

MFC

241c and 241d shall be, for example, a flow rate within the range of 100 sccm or more and 10000 sccm or less, respectively. The pressure in the processing chamber 201 is, for example, 1 Pa or more and 2666 Pa or less, preferably 665 Pa or more and 1333 Pa or less. The time for exposing the wafer 200 to the DCS gas is, for example, about 20 seconds per cycle. The time for exposing the wafer 200 to the DCS gas varies depending on the film thickness.

The temperature of the heater 207 is such that the temperature of the wafer 200 is, for example, 0 ° C. or higher and 700 ° C. or lower, preferably room temperature (25 ° C.) or higher and 550 ° C. or lower, and more preferably 40 ° C. or higher and 500 ° C. or lower. Set to temperature. By setting the temperature of the wafer 200 to 700 ° C. or lower, further to 550 ° C. or lower, and further to 500 ° C. or lower as in the present embodiment, the amount of heat applied to the wafer 200 can be reduced, and the heat history received by the wafer 200 can be reduced. Can be well controlled.

By supplying DCS gas to the wafer 200 under the above-mentioned conditions, a Si-containing layer is formed on the wafer 200 (the base film on the surface). The Si-containing layer may contain Cl and H in addition to the Si layer. The Si-containing layer is formed by physically adsorbing DCS on the outermost surface of the wafer 200, chemically adsorbing a substance obtained by partially decomposing DCS, or depositing Si by thermally decomposing DCS. Will be done. That is, the Si-containing layer may be an adsorption layer (physisorption layer or chemisorption layer) of a substance in which a part of DCS or DCS is decomposed, or may be a Si deposition layer (Si layer).

After the Si-containing layer is formed, the valve 243a is closed to stop the supply of DCS gas into the processing chamber 201. At this time, the APC valve 244 is left open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the DCS gas and the reaction sub-reaction after contributing to the formation of the unreacted or Si-containing layer remaining in the processing chamber 201. Products and the like are excluded from the processing chamber 201 (S4). Further, the

valves

243c and 243d 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. Note that this step S4 may be omitted.

As the raw material gas, in addition to DCS gas, tetrakis (dimethylamino) silane _{_{(Si [N (CH 3)}} 2] 4, abbreviation: 4DMAS) Gas, trisdimethylaminosilane _{_{(Si [N (CH 3)}} 2] 3 H, abbreviation: 3DMAS ) gas, bis (dimethylamino) silane _{_{_{(Si [N (CH 3)}}} 2] 2 H 2, abbreviation: BDMAS) gas, bis-diethylamino silane _{_{_{(Si [N (C 2 H}}} 5) 2] 2 H 2, abbreviation: BDEAS), Vista Shaributylaminosilane (SiH ₂ [NH (C ₄ H ₉ )] ₂ , abbreviation: BTBAS) gas, dimethylaminosilane (DMAS) gas, diethylaminosilane (DEAS) gas, dipropylaminosilane (DPAS) gas, diisopropylaminosilane (DIPAS) ) Gas, butylaminosilane (BAS) gas, various aminosilane raw material gases such as hexamethyldisilazane (HMDS) gas, monochlorosilane (SiH ₃ Cl, abbreviation: MCS) gas, trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas. , Tetrachlorosilane (SiCl ₄ , abbreviation: STC) gas, hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas, octachlorotrisilane (Si ₃ Cl ₈ , abbreviation: OCTS) gas and other inorganic halosilane raw material gas. , Monosilane (SiH ₄ , abbreviation: MS) gas, disilane (Si ₂ H ₆ , abbreviation: DS) gas, trisilane (Si ₃ H ₈ , abbreviation: TS) gas and other halogen group-free inorganic silane raw material gas. It can be preferably used.

As the inert gas, in addition to the N ₂ gas, a rare gas such as Ar gas, He gas, Ne gas, and Xe gas can be used.

(Reaction gas supply step: S5, S6)
After the deposition process has been completed, supplying NH ₃ gas is plasma-excited as the reaction gas to the wafer 200 in the process chamber 201 (S5).

In this step, the opening / closing control of the valves 243b to 243d is performed in the same procedure as the opening / closing control of the

valves

243a, 243c, 243d in step S3. The _{flow rate of the NH 3} gas is adjusted by the MFC 241b, and the NH 3 gas is supplied into the buffer chamber 237c via the pipe 249b. At this time, high frequency power is supplied to the external electrode 300. _{The NH 3} gas supplied into the buffer chamber 237c is excited to a plasma state (plasmaized and activated), _{supplied as an active species (NH 3} *) into the processing chamber 201, and exhausted from the exhaust pipe 231.

_{The supply flow rate of the NH 3} gas controlled by the MFC 241b is, for example, a flow rate within the range of 100 sccm or more and 10000 sccm or less, preferably 1000 sccm or more and 2000 sccm or less. The high frequency power applied to the external electrode 300 is, for example, power within the range of 50 W or more and 600 W or less. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 Pa or more and 500 Pa or less. By using the plasma, also the pressure in the processing chamber 201 as such a relatively low pressure zone, it is possible to activate the NH ₃ gas. NH ₃ time for supplying the active species obtained by the gas to plasma excitation to the wafer 200, i.e., the gas supply time (irradiation time), for example more than 1 second, 180 seconds or less, preferably 1 second or more, The time is within the range of 60 seconds or less. Other processing conditions are the same as those in S3 described above.

By supplying NH ₃ gas to the wafer 200 under the conditions described above, Si-containing layer formed on the wafer 200 is plasma nitriding. At this time, the energy of the plasma excited NH ₃ gas, Si-Cl bond Si-containing layer has, Si-H bond is cleaved. Cl and H from which the bond with Si has been separated will be desorbed from the Si-containing layer. Then, Si in the Si-containing layer having an unbonded hand (dangling bond) due to desorption of Cl and the like is _{bonded to N contained in the NH 3} gas, and a Si—N bond is formed. The Rukoto. As this reaction proceeds, the Si-containing layer is changed (modified) into a layer containing Si and N, that is, a silicon nitride layer (SiN layer).

Incidentally, in order modified Si-containing layer to the SiN layer, it is necessary to supply the NH ₃ gas by plasma excitation. Also NH ₃ gas was supplied under a non-plasma atmosphere, in a temperature zone above has insufficient energy required to nitride the Si-containing layer, sufficiently desorption of Cl or H from Si-containing layer This is because it is difficult to increase the Si—N bond by sufficiently nitriding the Si-containing layer.

After the Si-containing layer is changed into SiN layer, closing the valve 243b, to stop the supply of the NH ₃ gas. Further, the supply of high frequency power to the external electrode 300 is stopped. _{Then, the NH 3} gas and the reaction by-product remaining in the treatment chamber 201 are removed from the treatment chamber 201 by the same treatment procedure and treatment conditions as in step S4 (S6). Note that this step S6 may be omitted.

As the nitride, that is, the N-containing gas to be plasma-excited, in _{addition to NH 3} gas, diimide (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas and the like may be used.

As the inert gas, in addition to the N ₂ gas, for example, various rare gases exemplified in step S4 can be used.

(Implemented a predetermined number of times: S7)
Performing the above-mentioned S3, S4, S5, and S6 in this order non-simultaneously, that is, without synchronization is defined as one cycle, and this cycle is performed a predetermined number of times (n times), that is, one or more times (S7). Thereby, a SiN film 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 SiN layer formed per cycle is made smaller than the desired film thickness, and the film thickness of the SiN film formed by laminating the SiN layers becomes the desired film thickness. It is preferable to repeat the cycle multiple times.

(Atmospheric pressure return step: S8)
_{When the above-mentioned film forming process is completed, N 2} gas as an inert gas is supplied from each of the

gas supply pipes

232c and 232d into the processing chamber 201 and exhausted from the exhaust pipe 231. As a result, the inside of the processing chamber 201 is purged with the inert gas, and the gas or the like remaining in the processing chamber 201 is removed from the inside of the processing chamber 201 (inert gas purge). After that, the atmosphere in the treatment chamber 201 is replaced with the inert gas (replacement of the inert gas), and the pressure in the treatment chamber 201 is restored to the normal pressure (S8).

(Delivery step: S9)
After that, the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the manifold 209, and the processed wafer 200 is supported by the boat 217 from the lower end of the manifold 209 to the outside of the reaction tube 203. It is carried out (boat unloading) (S9). After the boat 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 (shutter close). The processed wafer 200 will be taken out from the boat 217 after being carried out of the reaction tube 203 (wafer discharge). After the wafer is discharged, the empty boat 217 may be carried into the processing chamber 201.

(3) Effects of the present embodiment According to the present embodiment, one or more of the following effects can be obtained.

(A) By providing an external electrode on the outer periphery of the reaction tube corresponding to the position where the plasma generating portion for converting the processing gas into plasma is formed, the processing gas supplied into the reaction tube by this external electrode is activated by plasma. , This activated processing gas can be supplied to the substrate.

(B) The external electrode is provided at a position where the plasma generation unit is formed and is provided at a position other than the gas supply unit that supplies gas to the plasma generation unit, thereby preventing plasma formation in the gas supply unit. be able to.

(C) A buffer chamber is provided along the inner wall of the reaction tube, and an external electrode for forming plasma is provided on the outer periphery of the reaction tube corresponding to the position where the buffer chamber is provided, and is supplied into the buffer chamber by this external electrode. By activating the processing gas with plasma and supplying the activated processing gas to the substrate, it is possible to form a highly efficient plasma in the buffer chamber, and the plasma active species formed with high efficiency on the substrate. Gas can be supplied.

(D) A plurality of processing gas supply ports for supplying activated processing gas to the substrate are provided in the horizontal direction of the substrate toward the center of the substrate, so that the gas is turned into plasma toward the center of the substrate. Supply can be increased.

(E) A partition plate is provided in the buffer structure forming the buffer chamber, and the processing gas introduction area and the plasma area are separated by partitioning the processing gas introduction area and the plasma area as the buffer chamber by the partition plate. Can be separated.

(F) The partition plate is provided with a gas supply hole for supplying gas from the processing gas introduction area to the plasma area, so that the processing gas is gas to the plasma area in a state where the processing gas introduction area and the plasma area are separated. Can be supplied.

(G) The partition plate is provided with a plurality of holes for supplying the processing gas to the plasma area, the processing gas is supplied from the lower part of the processing gas introduction area, and the processing gas is supplied to the plasma area from the plurality of holes. Thereby, the gas concentration in the buffer chamber can be made uniform.

(H) By not providing an external electrode on the outer periphery of the reaction tube corresponding to the position where the treated gas introduction area is provided, it is possible to prevent plasma formation in the treated gas introduction area.

(I) Plasma can be formed in the plasma area by providing an external electrode on the outer circumference of the reaction tube corresponding to the position where the plasma area is provided.

(J) The buffer structure is provided in a portion extending from the upper part to the lower part of the inner wall on the processing chamber side along the loading direction of the substrate, and a gas supply port for supplying plasmaized gas is provided in the processing chamber. The gas concentration in the processing chamber can be made uniform.

(K) In a plan view, a buffer chamber is provided across the raw material gas supply nozzle, and plasma is provided by providing an external electrode that forms plasma on the outer circumference of the reaction tube corresponding to the position where each buffer chamber is provided. The area can be expanded.

The embodiment of the present disclosure has been specifically described above. However, the present disclosure is not limited to the above-described embodiment, and various modifications can be made without departing from the gist thereof.

For example, in the above-described embodiment, an example in which the reaction gas is supplied after the raw material is supplied has been described. The present disclosure is not limited to such an embodiment, and the supply order of the raw material and the reaction gas may be reversed. That is, the raw material may be supplied after the reaction gas is supplied. By changing the supply order, it is possible to change the film quality and composition ratio of the formed film.

In the above-described embodiment and the like, an example of forming a SiN film on the wafer 200 has been described. The present disclosure is not limited to such an embodiment, and a silicon oxide film (SiO film), a silicon acid carbide film (SiOC film), a silicon acid carbonic nitride film (SiOCN film), and a silicon acid nitride film (SiON) are placed on the wafer 200. When forming a Si-based oxide film such as a film), or on a wafer 200, Si-based nitride such as a silicon carbonitride film (SiCN film), a silicon boron nitride film (SiBN film), or a silicon boron nitride film (SiBCN film) It is also suitably applicable when forming a film. In these cases, as the reaction gas, the other O-containing _gas, C 3 and C-containing gas, such as _{H 6,} and N-containing gas such as NH _3, it can be used B-containing gas such as BCl _3.

Further, in the present disclosure, titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W) are provided on the wafer 200. It is also suitably applicable to the case of forming an oxide film or a nitride film containing a metal element such as, that is, a metal-based oxide film or a metal-based nitride film. That is, in the present disclosure, on the wafer 200, a TiO film, a TiN film, a TiOC film, a TiOCN film, a TiON film, a TiBN film, a TiBCN film, a ZrO film, a ZrN film, a ZrOC film, a ZrOCN film, and Z
rON film, ZrBN film, ZrBCN film, HfO film, HfN film, HfOC film, HfOCN film, HfON film, HfBN film, HfBCN film, TaO film, TaOC film, TaOCN film, TaON film, TaBN film, TaBCN film, Nbo film. , NbN film, NbOC film, NbOCN film, NbON film, NbBN film, NbBCN film, AlO film, AlN film, AlOC film, AlOCN film, AlON film, AlBN film, AlBCN film, MoO film, MoN film, MoOC film, MoOCN. It can also be suitably applied when forming a film, a MoON film, a MoBN film, a MoBCN film, a WO film, a WN film, a WOC film, a WOCN film, a WON film, a MWBN film, a WBCN film, or the like.

In these cases, for example, as the raw material gas, tetrakis (dimethylamino) titanium (Ti [N (CH ₃ ) ₂ ] ₄ , abbreviation: TDMAT) gas, tetrakis (ethylmethylamino) hafnium (Hf [N (C ₂ H ₅₎₎ ) (CH ₃ )] ₄ , abbreviation: TEMAH gas, tetrakis (ethylmethylamino) zirconium (Zr [N (C ₂ H ₅ ) (CH ₃ )] ₄ , abbreviation: TEMAZ) gas, trimethylaluminum (Al (CH)) ₃ ) ₃ , abbreviation: TMA) gas, titanium tetrachloride (TiCl ₄ ) gas, hafnium tetrachloride (HfCl ₄ ) gas and the like can be used. As the reaction gas, the above-mentioned reaction gas can be used.

That is, the present disclosure can be suitably applied when forming a metalloid-based film containing a metalloid element or a metal-based film containing a metal element. The treatment procedure and treatment conditions for these film formation treatments can be the same treatment procedures and treatment conditions as those for the film formation treatments shown in the above-described embodiments and modifications. In these cases as well, the same effects as those of the above-described embodiments and modifications can be obtained.

It is preferable that the recipes used for the film forming process are individually prepared according to the processing content and stored in the storage device 121c via a telecommunication line or an external storage device 123. Then, when starting various processes, it is preferable that the CPU 121a appropriately selects an appropriate recipe from a plurality of recipes stored in the storage device 121c according to the processing content. This makes it possible to form thin films of various film types, composition ratios, film qualities, and film thicknesses with a single substrate processing device in a versatile and reproducible manner. In addition, the burden on the operator can be reduced, and various processes can be started quickly while avoiding operation mistakes.

The above recipe is not limited to the case of newly creating, for example, it may be prepared by changing an existing recipe already installed in the board processing apparatus. When changing the recipe, the changed recipe may be installed on the substrate processing apparatus via a telecommunication line or a recording medium on which the recipe is recorded. Further, the input / output device 122 included in the existing board processing device may be operated to directly change the existing recipe already installed in the board processing device.

200: Wafer (board)
201: Processing room 217: Boat (board support)
300: External electrode

Claims

A processing room for processing the substrate and
A board support that holds a plurality of the boards in multiple stages in the vertical direction,
A plasma generating unit having a buffer structure provided in the processing chamber for converting gas into plasma, and an external electrode for generating plasma provided outside the processing chamber corresponding to the position where the buffer structure is provided. ,
Substrate processing device.
The buffer structure includes a gas supply unit for supplying the gas.
The substrate processing apparatus according to claim 1, wherein the external electrode is provided at a position where the buffer structure is provided and is provided at a position other than the gas supply unit.
The substrate processing apparatus according to claim 2, wherein a buffer chamber is provided in the buffer structure as an area for converting the gas into plasma.
The substrate processing apparatus according to claim 3, wherein a partition plate is provided in the buffer structure, and the partition plate partitions the gas supply unit and the buffer chamber.
The substrate processing apparatus according to claim 4, wherein the partition plate is provided with a gas supply hole for supplying the gas from the gas supply unit to the buffer chamber.
The substrate processing apparatus according to claim 5, wherein the partition plate is provided with a plurality of gas supply holes in the vertical direction.
A claim that the buffer structure is provided in a portion extending from the upper part to the lower part of the inner wall of the processing chamber along the loading direction of the substrate, and a gas supply port for supplying the plasmaized gas is provided in the processing chamber. The substrate processing apparatus according to 1.
The substrate processing apparatus according to claim 7, wherein a plurality of the gas supply ports are provided toward the center of the substrate in the horizontal direction of the substrate.
A raw material gas supply unit for supplying a raw material gas and a plurality of the plasma generation units are provided.
The substrate processing apparatus according to claim 1, wherein the plurality of plasma generating units are arranged with a straight line passing through the center of the processing chamber and the raw material gas supply unit in a plan view.
It is provided with an exhaust unit for exhausting gas and a plurality of the plasma generation units.
The substrate processing apparatus according to claim 1, wherein a plurality of the plasma generating units are arranged so as to sandwich a straight line passing through the center of the processing chamber and the exhaust unit in a plan view.
A processing chamber for processing a substrate, a substrate support for holding a plurality of the substrates in multiple stages in the vertical direction, a buffer structure provided in the processing chamber for converting gas into plasma, and a position where the buffer structure is provided. A step of carrying the substrate into the processing chamber of a substrate processing apparatus including a plasma generating unit having an external electrode for generating plasma provided outside the processing chamber corresponding to the above.
The process of turning the gas into plasma and
A step of supplying the plasma-generated gas to the substrate and
A method for manufacturing a semiconductor device having.
A processing chamber for processing a substrate, a substrate support for holding a plurality of the substrates in multiple stages in the vertical direction, a buffer structure provided in the processing chamber for converting gas into plasma, and a position where the buffer structure is provided. A procedure for carrying the substrate into the processing chamber of a substrate processing apparatus including a plasma generating unit having an external electrode for generating plasma provided outside the processing chamber corresponding to the above.
The procedure for converting the gas into plasma and
The procedure for supplying the plasma-generated gas to the substrate and
A program that causes the board processing apparatus to execute the above.