JP2011058031A - Method for producing semiconductor device and substrate treatment apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor device and a substrate processing apparatus capable of increasing the apparatus operating rate and excellent in mass productivity.
A process for carrying a substrate into a processing container, a process for supplying a raw material containing nickel into the processing container and forming a film containing nickel on the substrate, and a processed substrate from the processing container. In the process of unloading and with no substrate in the processing container, a halogen-based gas is supplied into the processing container to react with deposits containing nickel adhering to the processing container to generate nickel halide, and then processing A gas containing a cyclopenta group is supplied into the container and reacted with nickel halide to produce a nickel compound. The nickel compound is heated and vaporized and discharged from the processing container, so that the nickel adhering to the processing container is removed. Removing the deposits that contain them.
[Selection] Figure 1

Description

  The present invention relates to a method for manufacturing a semiconductor device having a step of processing a substrate in a processing container and a step of cleaning the inside of the processing container, and a substrate processing apparatus suitably used in the method.

When cleaning the inside of a processing container of a film forming apparatus for forming a film containing a metal such as nickel on a substrate, deposition is carried out by introducing ClF ₃ gas or F ₂ gas into the processing container and adhering to the gas contact part. There is a method of washing with water or an acidic aqueous solution after contacting with an object (for example, see Patent Document 1).

JP-A-5-263281

  However, in that case, it is necessary to stop the operation of the film forming apparatus and perform the work. That is, it is necessary to open the reaction chamber to the atmosphere in order to remove the susceptors installed in the processing vessel (reaction chamber) and to clean the inner wall of the processing vessel, the exhaust pipe, and the like.

  As a result, the temperature rise and fall of the heater (temperature rise and fall), airtightness check, temperature adjustment by re-installation of susceptors, and conveyance adjustment lead to an increase in downtime (device non-operational state), resulting in a decrease in device operation rate and mass production. It becomes scarce.

  It is an object of the present invention to provide a method for manufacturing a semiconductor device and a substrate processing apparatus that can increase the device operation rate and are excellent in mass productivity.

  According to one aspect of the present invention, a step of carrying a substrate into a processing vessel, a step of supplying a raw material containing nickel into the processing vessel and forming a film containing nickel on the substrate, A step of unloading the processed substrate from the processing container, and a reaction with a deposit containing nickel attached to the processing container by supplying a halogen-based gas into the processing container without the substrate in the processing container A nickel halide is formed, and then a gas containing a cyclopenta group is supplied into the processing vessel to react with the nickel halide to form a nickel compound, and the nickel compound is heated and vaporized to form the processing vessel. And a step of removing the deposit containing nickel adhering to the inside of the processing container by discharging from the inside.

  According to another aspect of the present invention, a processing container for processing a substrate, a raw material supply system for supplying a raw material containing nickel into the processing container, and a halogen-based gas supply for supplying a halogen-based gas into the processing container. A system, a cyclopenta group-containing gas supply system for supplying a gas containing a cyclopenta group into the processing container, an exhaust system for exhausting the processing container, a heater for heating the processing container, and the processing container After performing the process of supplying the raw material and forming a film containing nickel on the substrate, the halogen-based gas is supplied into the processing container and is attached to the processing container without the substrate in the processing container. A nickel halide is produced by reacting with the deposited nickel-containing deposit, and then a gas containing a cyclopenta group is supplied into the processing vessel to react with the nickel halide to cause nickel nickel. Generating the compound, heating and vaporizing the nickel compound, and discharging the nickel compound from the processing container, thereby removing the deposit containing the nickel adhering to the processing container, the raw material supply system, the halogen There is provided a substrate processing apparatus having a system gas supply system, the cyclopenta group-containing gas supply system, the exhaust system, and a control unit for controlling the heater.

  According to the present invention, it is possible to provide a method of manufacturing a semiconductor device and a substrate processing apparatus that can increase the apparatus operation rate and are excellent in mass productivity.

It is a flowchart of the cleaning process concerning embodiment of this invention. It is a block diagram of the gas supply system and exhaust system which the substrate processing apparatus concerning embodiment of this invention has. It is a section lineblock diagram at the time of wafer processing of a substrate processing device concerning an embodiment of the present invention. It is a section lineblock diagram at the time of wafer conveyance of a substrate processing device concerning an embodiment of the present invention. It is a flowchart of the substrate processing process concerning embodiment of this invention. It is a schematic block diagram of the vertical processing furnace of the vertical CVD apparatus used suitably by other embodiment of this invention, (a) shows the processing furnace 302 part in a longitudinal cross-section, (b) is the processing furnace 302 part. Is shown by a cross-sectional view along line AA in FIG.

(1) Configuration of Substrate Processing Apparatus First, the configuration of the substrate processing apparatus according to the present embodiment will be described with reference to FIGS. FIG. 3 is a cross-sectional configuration diagram of the substrate processing apparatus according to one embodiment of the present invention during wafer processing, and FIG. 4 is a cross-sectional configuration diagram of the substrate processing apparatus according to one embodiment of the present invention during wafer transfer. is there.

<Processing chamber>
As shown in FIGS. 3 and 4, the substrate processing apparatus according to this embodiment includes a processing container 202. The processing container 202 is configured as a flat sealed container having a circular cross section, for example. Moreover, the processing container 202 is comprised, for example with metal materials, such as aluminum (Al) and stainless steel (SUS). A processing chamber 201 for processing a wafer 200 such as a silicon wafer as a substrate is formed in the processing container 202.

<Support stand>
A support table 203 that supports the wafer 200 is provided in the processing chamber 201. On the upper surface of the support table 203 that the wafer 200 is in direct contact with, for example, a support plate made of quartz (SiO 2), carbon, ceramics, silicon carbide (SiC), aluminum oxide (Al 2 O 3), aluminum nitride (AlN), or the like. Susceptor 217 is provided. In addition, the support base 203 incorporates a heater 206 as a heating means (heating source) for heating the wafer 200. Note that the lower end portion of the support base 203 passes through the bottom portion of the processing container 202.

<Elevating mechanism>
Outside the processing chamber 201, an elevating mechanism 207b for elevating the support base 203 is provided. The wafer 200 supported on the susceptor 217 can be moved up and down by operating the lifting mechanism 207 b to raise and lower the support base 203. The support table 203 is lowered to the position shown in FIG. 4 (wafer transfer position) when the wafer 200 is transferred, and is raised to the position shown in FIG. 3 (wafer processing position) when the wafer 200 is processed. The periphery of the lower end portion of the support base 203 is covered with a bellows 203a, and the inside of the processing chamber 201 is kept airtight.

<Lift pin>
In addition, on the bottom surface (floor surface) of the processing chamber 201, for example, three lift pins 208b are provided so as to rise in the vertical direction. Further, the support base 203 (including the susceptor 217) is provided with through holes 208a through which the lift pins 208b pass, at positions corresponding to the lift pins 208b. When the support table 203 is lowered to the wafer transfer position, as shown in FIG. 4, the upper ends of the lift pins 208b protrude from the upper surface of the susceptor 217, and the lift pins 208b support the wafer 200 from below. Yes. When the support table 203 is raised to the wafer processing position, as shown in FIG. 3, the lift pins 208b are buried from the upper surface of the susceptor 217, and the susceptor 217 supports the wafer 200 from below. In addition, since the lift pins 208b are in direct contact with the wafer 200, it is desirable to form the lift pins 208b with a material such as quartz or alumina.

<Wafer transfer port>
On the inner wall side surface of the processing chamber 201 (processing container 202), a wafer transfer port 250 for transferring the wafer 200 into and out of the processing chamber 201 is provided. The wafer transfer port 250 is provided with a gate valve 251. By opening the gate valve 251, the processing chamber 201 and the transfer chamber (preliminary chamber) 271 communicate with each other. The transfer chamber 271 is formed in a transfer container (sealed container) 272, and a transfer robot 273 that transfers the wafer 200 is provided in the transfer chamber 271. The transfer robot 273 includes a transfer arm 273 a that supports the wafer 200 when the wafer 200 is transferred. By opening the gate valve 251 while the support table 203 is lowered to the wafer transfer position, the transfer robot 273 can transfer the wafer 200 between the processing chamber 201 and the transfer chamber 271. Yes. The wafer 200 transferred into the processing chamber 201 is temporarily placed on the lift pins 208b as described above. Note that a load lock chamber (not shown) is provided on the opposite side of the transfer chamber 271 from the side where the wafer transfer port 250 is provided, and the transfer robot 273 moves the wafer 200 between the load lock chamber and the transfer chamber 271. Can be transported. The load lock chamber functions as a spare chamber for temporarily storing unprocessed or processed wafers 200.

<Exhaust system>
An exhaust port 260 for exhausting the atmosphere in the processing chamber 201 is provided on the inner wall side surface of the processing chamber 201 (processing container 202) on the opposite side of the wafer transfer port 250. An exhaust pipe 261 is connected to the exhaust port 260 via an exhaust chamber 260a. The exhaust pipe 261 has a pressure regulator 262 such as an APC (Auto Pressure Controller) that controls the inside of the processing chamber 201 at a predetermined pressure. A raw material recovery trap 263 and a vacuum pump 264 are connected in series in this order. An exhaust system (exhaust line) is mainly configured by the exhaust port 260, the exhaust chamber 260a, the exhaust pipe 261, the pressure regulator 262, the raw material recovery trap 263, and the vacuum pump 264.

<Gas inlet>
A gas inlet 210 for supplying various gases into the processing chamber 201 is provided on the upper surface (ceiling wall) of a shower head 240 described later provided in the upper portion of the processing chamber 201. The configuration of the gas supply system connected to the gas inlet 210 will be described later.

<Shower head>
A shower head 240 as a gas dispersion mechanism is provided between the gas inlet 210 and the processing chamber 201. The shower head 240 disperses the gas introduced from the gas introduction port 210 and the gas that has passed through the dispersion plate 240 a are more uniformly dispersed and supplied to the surface of the wafer 200 on the support table 203. A shower plate 240b. The dispersion plate 240a and the shower plate 240b are provided with a plurality of vent holes. The dispersion plate 240 a is disposed so as to face the upper surface of the shower head 240 and the shower plate 240 b, and the shower plate 240 b is disposed so as to face the wafer 200 on the support table 203. Note that spaces are provided between the upper surface of the shower head 240 and the dispersion plate 240a, and between the dispersion plate 240a and the shower plate 240b, respectively, and the spaces are supplied from the gas inlet 210. Function as a first buffer space (dispersion chamber) 240c for dispersing the gas and a second buffer space 240d for diffusing the gas that has passed through the dispersion plate 240a.

<Exhaust duct>
A step portion 201a is provided on the side surface of the inner wall of the processing chamber 201 (processing vessel 202). The step portion 201a is configured to hold the conductance plate 204 in the vicinity of the wafer processing position. The conductance plate 204 is configured as a single donut-shaped (ring-shaped) disk in which a hole for accommodating the wafer 200 is provided in the inner periphery. A plurality of discharge ports 204 a arranged in the circumferential direction with a predetermined interval are provided on the outer periphery of the conductance plate 204. The discharge port 204 a is formed discontinuously so that the outer periphery of the conductance plate 204 can support the inner periphery of the conductance plate 204.

  On the other hand, a lower plate 205 is locked to the outer peripheral portion of the support base 203. The lower plate 205 includes a ring-shaped concave portion 205b and a flange portion 205a provided integrally on the inner upper portion of the concave portion 205b. The recess 205 b is provided so as to close a gap between the outer peripheral portion of the support base 203 and the inner wall side surface of the processing chamber 201. A part of the bottom of the recess 205b near the exhaust port 260 is provided with a plate exhaust port 205c for discharging (circulating) gas from the recess 205b to the exhaust port 260 side. The flange portion 205 a functions as a locking portion that locks on the upper outer periphery of the support base 203. When the flange portion 205 a is locked on the upper outer periphery of the support base 203, the lower plate 205 is moved up and down together with the support base 203 as the support base 203 is moved up and down.

  When the support table 203 is raised to the wafer processing position, the lower plate 205 is also raised to the wafer processing position. As a result, the conductance plate 204 held in the vicinity of the wafer processing position closes the upper surface portion of the recess 205b of the lower plate 205, and the exhaust duct 259 having the gas passage region inside the recess 205b is formed. . At this time, due to the exhaust duct 259 (the conductance plate 204 and the lower plate 205) and the support base 203, the inside of the processing chamber 201 is above the processing chamber above the exhaust duct 259 and the processing chamber below the exhaust duct 259. It will be partitioned into a lower part. The conductance plate 204 and the lower plate 205 are made of materials that can be kept at a high temperature, for example, high temperature and high load resistance, in consideration of etching reaction products deposited on the inner wall of the exhaust duct 259 (self cleaning). Preferably, it is made of quartz for use.

  Here, the flow of gas in the processing chamber 201 during wafer processing will be described. First, the gas supplied from the gas inlet 210 to the upper portion of the shower head 240 enters the second buffer space 240d through the first buffer space (dispersion chamber) 240c through a large number of holes in the dispersion plate 240a, and further into the shower. It passes through a large number of holes in the plate 240 b and is supplied into the processing chamber 201, and is uniformly supplied onto the wafer 200. The gas supplied onto the wafer 200 flows radially outward of the wafer 200 in the radial direction. Then, surplus gas after contacting the wafer 200 flows radially on the exhaust duct 259 located on the outer peripheral portion of the wafer 200, that is, on the conductance plate 204 toward the radially outer side of the wafer 200. Is discharged into the gas flow path region (in the recess 205b) in the exhaust duct 259. Thereafter, the gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260 via the plate exhaust port 205c. By flowing the gas in this way, gas wraparound to the lower part of the processing chamber, that is, the back surface of the support base 203 or the bottom surface side of the processing chamber 201 is suppressed.

<Gas supply system>
Next, the configuration of the gas supply system connected to the gas inlet 210 described above will be described with reference to FIG. FIG. 2 is a configuration diagram of a gas supply system and an exhaust system included in the substrate processing apparatus according to the embodiment of the present invention.

  A gas supply system of a substrate processing apparatus according to an embodiment of the present invention includes a bubbler as a vaporizing unit that vaporizes a liquid material containing nickel (Ni) that is in a liquid state at room temperature, and vaporizes the liquid material using the bubbler. A raw material gas supply system that supplies the obtained raw material gas into the processing chamber 201, a cleaning gas supply system that supplies a cleaning gas (etching gas) into the processing chamber 201, and a purge gas supply system that supplies a purge gas into the processing chamber 201 And have. Furthermore, the substrate processing apparatus according to the embodiment of the present invention has a vent (bypass) system that exhausts the processing gas to bypass the processing chamber 201 without supplying the raw material gas from the bubbler into the processing chamber 201. Below, the structure of each part is demonstrated.

<Bubbler>
Outside the processing chamber 201, a bubbler 220a is provided as a raw material container for storing a liquid raw material. The bubbler 220a is configured as a tank (sealed container) capable of containing (filling) a liquid source therein, and is also configured as a vaporizing unit that generates a source gas by vaporizing the liquid source by bubbling. A sub-heater 206a for heating the bubbler 220a and the liquid material inside is provided around the bubbler 220a. As the raw material, for example, Ni (PF ₃ ) ₄ which is a metal liquid raw material containing a nickel (Ni) element is used.

A carrier gas supply pipe 237a is connected to the bubbler 220a. A carrier gas supply source (not shown) is connected to the upstream end of the carrier gas supply pipe 237a. Further, the downstream end of the carrier gas supply pipe 237a is immersed in the liquid raw material accommodated in the bubbler 220a. The carrier gas supply pipe 237a is provided with a mass flow controller (MFC) 222a as a flow rate controller for controlling the supply flow rate of the carrier gas, and valves va1 and va2 for controlling the supply of the carrier gas. As the carrier gas, a gas that does not react with the liquid raw material is preferably used. For example, an inert gas such as N ₂ gas, Ar gas, or He gas is preferably used. A carrier gas supply system (carrier gas supply line) is mainly configured by the carrier gas supply pipe 237a, the MFC 222a, and the valves va1 and va2.

  With the above configuration, by opening the valves va1 and va2 and supplying the carrier gas whose flow rate is controlled by the MFC 222a from the carrier gas supply pipe 237a into the bubbler 220a, the liquid raw material stored in the bubbler 220a is vaporized by bubbling. Source gas can be generated.

<Raw gas supply system>
A raw material gas supply pipe 213a for supplying the raw material gas generated in the bubbler 220a into the processing chamber 201 is connected to the bubbler 220a. The upstream end of the source gas supply pipe 213a communicates with the space existing above the bubbler 220a. The downstream end of the source gas supply pipe 213a is connected to the gas inlet 210. The source gas supply pipe 213a is provided with valves va5 and va3 in order from the upstream side. The valve va5 is a valve for controlling the supply of the source gas from the bubbler 220a into the source gas supply pipe 213a, and is provided in the vicinity of the bubbler 220a. The valve va3 is a valve that controls the supply of the source gas from the source gas supply pipe 213a into the processing chamber 201, and is provided in the vicinity of the gas inlet 210. The valve va3 and a valve ve3 described later are configured as a highly durable high-speed gas valve. The high durability high-speed gas valve is an integrated valve configured so that gas supply can be switched and gas exhausted quickly in a short time. The valve ve3 is a valve that controls the introduction of a purge gas for purging the inside of the processing chamber 201 after purging the space between the valve va3 of the source gas supply pipe 213a and the gas inlet 210 at high speed.

  With the above configuration, it is possible to supply the source gas from the source gas supply pipe 213a into the processing chamber 201 by opening the valves va5 and va3 while vaporizing the liquid source in the bubbler 220a. Become. A source gas supply system (source gas supply line) is mainly configured by the source gas supply pipe 213a and the valves va5 and va3.

  Further, a raw material supply system (raw material supply line) is mainly configured by the carrier gas supply system, the bubbler 220a, and the raw material gas supply system.

<Cleaning gas supply system>
Further, outside the processing chamber 201, cleaning gas supply sources 220b and 220d for supplying a cleaning gas are provided. The upstream ends of the cleaning gas supply pipes 213b and 213d are connected to the cleaning gas supply sources 220b and 220d, respectively. The downstream end portions of the cleaning gas supply pipes 213b and 213d are connected to the gas inlet 210 through valves vb3 and vd3, respectively. The cleaning gas supply pipe 213b is provided with a mass flow controller (MFC) 222b as a flow rate controller for controlling the supply flow rate of the cleaning gas, and valves vb1, vb2, and vb3 for controlling the supply of the cleaning gas. The cleaning gas supply pipe 213d is provided with a mass flow controller (MFC) 222d as a flow rate controller for controlling the supply flow rate of the cleaning gas, and valves vd1, vd2, and vd3 for controlling the supply of the cleaning gas. As the cleaning gas, a halogen-based gas is used as the first cleaning gas, and a gas containing a cyclopenta group is used as the second cleaning gas. That is, two types of gases are used as the cleaning gas. In the present embodiment, the cleaning gas supply sources 220b and 220d are configured as a halogen-based gas supply source and a cyclopenta group-containing gas supply source, respectively. A cleaning gas supply source 220b, a cleaning gas supply pipe 213b, an MFC 222b, and valves vb1, vb2, and vb3 are mainly used to provide a first cleaning gas supply system (first cleaning gas supply line), that is, a halogen-based gas supply system (halogen). System gas supply line). The second cleaning gas supply system (second cleaning gas supply line), that is, the cyclopenta group-containing gas supply system is mainly constituted by the cleaning gas supply source 220d, the cleaning gas supply pipe 213d, the MFC 222d, and the valves vd1, vd2, and vd3. (Cyclopentagroup-containing gas supply line) is configured. The first cleaning gas supply system and the second cleaning gas supply system constitute a cleaning gas supply system (cleaning gas supply line).

<Purge gas supply system>
In addition, purge gas supply sources 220 c and 220 e for supplying purge gas are provided outside the processing chamber 201. The upstream ends of the purge gas supply pipes 213c and 213e are connected to the purge gas supply sources 220c and 220e, respectively. The downstream end of the purge gas supply pipe 213c is connected to the gas inlet 210 through the valve vc3. The downstream end of the purge gas supply pipe 213e joins a portion between the valve va3 and the gas inlet 210 of the source gas supply pipe 213a via the valve ve3 and is connected to the gas inlet 210. The purge gas supply pipes 213c and 213e include mass flow controllers (MFC) 222c and 222e as flow rate controllers that control the supply flow rate of the purge gas, and valves vc1, vc2, vc3, ve1, ve2, and ve3 that control the supply of the purge gas. Each is provided. Further, for maintenance, a purge gas supply pipe 213f is connected via a valve vc4 between the cleaning gas supply source 220b of the cleaning gas supply pipe 213b and the valve vb1, and a cleaning gas of the cleaning gas supply pipe 213d. A purge gas supply pipe 213g is connected between the supply source 220d and the valve vd1 through a valve vc5. The purge gas supply pipes 213f and 213g are branched from the portion between the mass flow controller 222c and the valve vc2 of the purge gas supply pipe 213c. As the purge gas, for example, an inert gas such as N ₂ gas, Ar gas, or He gas is used. Purge gas supply sources 220c and 220e, purge gas supply pipes 213c, 213e, 213f and 213g, MFC 222c and 222e, valves vc1, vc2, vc3, vc4, vc5, ve1, ve2 and ve3 ) Is configured.

<Vent (bypass) system>
The upstream end of the vent pipe 215a is connected to the upstream side of the valve va3 of the source gas supply pipe 213a. Further, the downstream end of the vent pipe 215 a is connected to the downstream side of the pressure regulator 262 of the exhaust pipe 261 and to the upstream side of the raw material recovery trap 263. The vent pipe 215a is provided with a valve va4 for controlling the gas flow.

  With the above configuration, by closing the valve va3 and opening the valve va4, the processing chamber 201 is bypassed through the vent pipe 215a without supplying the gas flowing in the raw material gas supply pipe 213a into the processing chamber 201, Exhaust from the exhaust pipe 261 becomes possible. A vent system (vent line) is mainly configured by the vent pipe 215a and the valve va4.

  Although the sub-heater 206a is provided around the bubbler 220a as described above, the carrier gas supply pipe 237a, the source gas supply pipe 213a, the purge gas supply pipe 213e, the vent pipe 215a, the exhaust pipe 261, the processing A sub-heater 206a is also provided around the container 202, the shower head 240, and the like. The sub-heater 206a is configured to prevent re-liquefaction of the source gas inside these members by heating these members to a temperature of, for example, 100 ° C. or less.

<Control unit>
The substrate processing apparatus according to the present embodiment includes a controller 280 as a control unit that controls the operation of each unit of the substrate processing apparatus. The controller 280 includes a gate valve 251, an elevating mechanism 207b, a transport robot 273, a heater 206, a sub heater 206a, a pressure regulator (APC) 262, a vacuum pump 264, valves va1 to va5, vb1 to vb3, vc1 to vc5, vd1 to vd3. , Ve1 to ve3, and the operations of the flow controllers 222a, 222b, 222c, 222d, and 222e.

(2) Substrate Processing Step Subsequently, as a step of manufacturing the semiconductor device, a substrate processing step of forming a metal film on the wafer in the processing container using the above-described substrate processing apparatus, and cleaning the inside of the processing container. The cleaning process will be described with reference to FIGS. FIG. 5 is a flowchart of the substrate processing process according to the embodiment of the present invention. FIG. 1 is a flowchart of a cleaning process according to an embodiment of the present invention. First, the substrate processing process 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 280.

Here, the step of supplying Ni (PF ₃ ) ₄ as a raw material containing nickel (Ni) into a processing container containing the substrate and forming a nickel film (Ni film) as a metal film containing nickel on the substrate. An example in which a nickel film is formed on a substrate by a CVD method will be described in which a purge gas is supplied into the processing container and the inside of the processing container is purged as one cycle.

  Note that in this specification, the term metal film means a conductive substance containing a metal atom. In addition to a film made of a single metal, a conductive metal nitride film, a conductive metal Also included are metal oxide films, conductive metal composite films, conductive metal alloy films, and the like. The Ni film is a conductive metal film. This will be described in detail below.

<Substrate Loading Step (S1), Substrate Placement Step (S2)>
First, the elevating mechanism 207b is operated to lower the support table 203 to the wafer transfer position shown in FIG. Then, the gate valve 251 is opened to allow the processing chamber 201 and the transfer chamber 271 to communicate with each other. Then, the wafer 200 to be processed is loaded from the transfer chamber 271 into the processing chamber 201 by the transfer robot 273 while being supported by the transfer arm 273a (S1). The wafer 200 carried into the processing chamber 201 is temporarily placed on the lift pins 208 b protruding from the upper surface of the support table 203. When the transfer arm 273a of the transfer robot 273 returns from the processing chamber 201 to the transfer chamber 271, the gate valve 251 is closed.

  Subsequently, the elevating mechanism 207b is operated to raise the support table 203 to the wafer processing position shown in FIG. As a result, the lift pins 208b are buried from the upper surface of the support table 203, and the wafer 200 is placed on the susceptor 217 on the upper surface of the support table 203 (S2).

<Pressure adjustment step (S3), temperature adjustment step (S4)>
Subsequently, the pressure regulator (APC) 262 controls the pressure in the processing chamber 201 to be a predetermined processing pressure (S3). Further, the power supplied to the heater 206 is adjusted to control the surface temperature of the wafer 200 to a predetermined processing temperature (S4). The temperature adjustment step (S4) may be performed in parallel with the pressure adjustment step (S3), or may be performed prior to the pressure adjustment step (S3). Here, the predetermined processing temperature and processing pressure are processing temperature and processing pressure at which a Ni film can be formed by a CVD method in a raw material supply step described later. That is, the processing temperature and the processing pressure are such that the raw material used in the raw material supply process is self-decomposed.

In the substrate loading step (S1), the substrate placement step (S2), the pressure adjustment step (S3), and the temperature adjustment step (S4), the valves va3, vb3, vd3 are closed while the vacuum pump 264 is operated. The valves vc 1, vc 2, vc 3, ve 1, ve 2, and ve 3 are opened, so that the N ₂ gas always flows into the processing chamber 201. Thereby, adhesion of particles on the wafer 200 can be suppressed.

In parallel with the steps S1 to S4, the raw material (Ni (PF ₃ ) ₄ ) is vaporized to generate a raw material gas (preliminary vaporization). That is, by opening the valves va1, va2, va5 and supplying the carrier gas whose flow rate is controlled by the MFC 222a from the carrier gas supply pipe 237a into the bubbler 220a, the raw material stored in the bubbler 220a is vaporized by bubbling. A gas is generated (preliminary vaporization step). In this preliminary vaporization step, while the vacuum pump 264 is operated, the valve va4 is opened while the valve va3 is closed, thereby bypassing and exhausting the processing chamber 201 without supplying the source gas into the processing chamber 201. deep. A predetermined time is required to stably generate the source gas in the bubbler. For this reason, in this embodiment, the raw material gas is generated in advance, and the flow path of the raw material gas is switched by switching the opening and closing of the valves va3 and va4. As a result, it is preferable that the stable supply of the source gas into the processing chamber 201 can be started or stopped quickly by switching the valve.

<Ni film forming step (S5)>
[Raw material supply step (S5a)]
Subsequently, the valve va4 is closed and the valve va3 is opened while the vacuum pump 264 is operated, and supply of the source gas (Ni source) into the processing chamber 201 is started. The source gas is dispersed by the shower head 240 and is uniformly supplied onto the wafer 200 in the processing chamber 201. Excess source gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260 and the exhaust pipe 261. At this time, since the processing temperature and the processing pressure are set to a processing temperature and processing pressure at which the source gas is self-decomposed, the source gas supplied onto the wafer 200 is thermally decomposed to cause a CVD reaction. A Ni film is formed thereon.

Note that when the source gas is supplied into the processing chamber 201, the valve vc1 is used to prevent the source gas from entering the cleaning gas supply pipe 213b and to promote the diffusion of the source gas in the processing chamber 201. , Vc2 and vc3 are preferably kept open, and N ₂ gas is always allowed to flow into the processing chamber 201.

  When a predetermined time has elapsed after opening the valve va3 and starting the supply of the raw material gas, the valve va3 is closed and the valve va4 is opened to stop the supply of the raw material gas into the processing chamber 201.

[Purge process (S5b)]
After the valve va3 is closed and the supply of the raw material gas is stopped, the valves vc1, vc2, vc3, ve1, ve2, ve3 are opened, and N ₂ gas is supplied into the processing chamber 201. The N ₂ gas is dispersed by the shower head 240 and supplied into the processing chamber 201, flows through the exhaust duct 259, and is exhausted to the exhaust port 260 and the exhaust pipe 261. Thereby, the source gas remaining in the processing chamber 201 is removed, and the inside of the processing chamber 201 is purged with N ₂ gas.

[Predetermined number of steps (S5c)]
A nickel film (Ni film) having a predetermined film thickness is formed on the wafer 200 by performing the above-described source gas supply process and purge process as one cycle and performing this cycle a predetermined number of times.

[Residual gas removal step (S6)]
After the Ni film having a predetermined thickness is formed on the wafer 200, the processing chamber 201 is evacuated, the valves vc1, vc2, vc3, ve1, ve2, and ve3 are opened, and the N ₂ gas is supplied into the processing chamber 201. Supply. The N ₂ gas is dispersed by the shower head 240 and supplied into the processing chamber 201, flows through the exhaust duct 259, and is exhausted to the exhaust port 260 and the exhaust pipe 261. As a result, gas and reaction byproducts remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with N ₂ gas.

<Substrate unloading step (S7)>
Thereafter, the wafer 200 after the Ni film having a predetermined film thickness is formed from the inside of the processing chamber 201 by a procedure opposite to the procedure shown in the substrate loading step (S1) and the substrate placing step (S2). Then, the substrate processing step according to the present embodiment is completed.

In addition, as processing conditions of the wafer 200 in the Ni film forming step (S5) in the present embodiment,
Process temperature: 150-250 degreeC,
Processing pressure: 50 to 5000 Pa,
Bubbling carrier gas supply flow rate: 10 to 1000 sccm,
(Nickel raw material (Ni (PF ₃ ) ₄ ) gas supply flow rate: 0.1 to 2 sccm)
Purge gas (N ₂ ) supply flow rate: 10 to 10,000 sccm,
Raw material (Ni (PF ₃ ) ₄ ) supply time per cycle: 0.1 to 600 seconds,
Purge time per cycle: 0.1 to 600 seconds,
Number of cycles: 1 to 400 times
Ni film thickness: 20-50 nm
Is exemplified.

If the processing temperature is less than 150 ° C., the raw material (Ni (PF ₃ ) ₄ ) does not self-decompose in the raw material supply step (S5a), and the film formation reaction by CVD does not occur. On the other hand, when the processing temperature exceeds 250 ° C., the film formation rate increases excessively, making it difficult to control the film thickness. Therefore, in the raw material supply step (S5a), in order to cause a film formation reaction by CVD and to control the film thickness, the processing temperature needs to be 150 ° C. or higher and 250 ° C. or lower.

(3) Cleaning Step When the above-described substrate processing step is repeated, Ni accumulates on members around the wafer in the processing chamber 201 such as the inner wall of the processing vessel 202, the shower plate 240b, the susceptor 217, and the conductance plate 204. That is, a deposit (film) containing Ni adheres to the inner wall or the like of the processing container 202. When the thickness of the deposit attached to the inner wall exceeds a certain thickness, the deposit is peeled off due to the stress of the deposit (film stress), and the generated particles adhere to the substrate, and the production yield increases. Incurs a decline. Therefore, when the thickness of the deposit adhered to the inner wall or the like reaches a predetermined thickness before the deposit is peeled off or dropped, the inside of the processing container 202 is cleaned.

In the present embodiment, cleaning is performed in two stages using two types of cleaning gases. That is, deposition containing Ni adhering to the processing container 202 by supplying a halogen-based gas (a gas containing chlorine (Cl), fluorine (F), or bromine (Br)) as a first cleaning gas into the processing container 202. Ni halide is produced by reacting with a product, and then a gas containing a cyclopenta group is supplied as a second cleaning gas into the processing vessel 202 to react with Ni halide to produce a Ni compound. By heating, vaporizing, and discharging from the inside of the processing container 202, the deposit containing Ni adhering to the inside of the processing container 202 is removed.
Hereinafter, the cleaning process 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 280.

<Temperature adjustment step (S101)>
First, in a state where there is no wafer 200 (processed wafer, processed wafer) in the processing container 202, the power supplied to the heater 206 is adjusted to control the temperature in the processing container 202 to a predetermined cleaning temperature. .

<Pressure adjustment step (S102)>
Subsequently, the pressure regulator (APC) 262 performs control so that the pressure in the processing chamber 201 becomes a predetermined cleaning pressure. In addition, you may make it perform a pressure adjustment process (S102) in parallel with a temperature adjustment process (S101).

  Here, the predetermined cleaning temperature and the cleaning pressure refer to reacting a deposit containing Ni adhering in the processing container 202 with the cleaning gas in a cleaning process described later to generate a predetermined compound and vaporize it. Possible temperature and pressure. That is, the temperature and pressure at which Ni deposits adhering to the inside of the processing vessel 202 and the halogen-based gas that is the first cleaning gas can be reacted to generate Ni halide. The temperature and pressure at which the Ni halide can be reacted with the cyclopentagroup-containing gas as the second cleaning gas to produce a Ni compound. Furthermore, it is also the temperature and pressure at which this Ni compound can be vaporized.

In the temperature adjustment step (S101) and the pressure adjustment step (S102), the valves va3, vb3, vd3 are closed and the valves vc1, vc2, vc3, ve1, ve2, ve3 are opened while operating the vacuum pump 264. Thus, N ₂ gas is always allowed to flow into the processing chamber 201.

<Cleaning step (S103)>
[Halogen gas supply step (S103a)]
Subsequently, while operating the vacuum pump 264, the valves vb1, vb2, and vb3 are opened, and supply of the halogen-based gas as the first cleaning gas into the processing chamber 201 is started. The halogen-based gas is dispersed by the shower head 240 and is uniformly supplied onto the susceptor 217 and the conductance plate 204 in the processing chamber 201. Excess halogen-based gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260 and the exhaust pipe 261.

At this time, the deposit containing Ni adhering to the inside of the processing container 202, that is, the inner wall of the processing container 202, the members in the processing chamber 201 such as the shower plate 240b, the susceptor 217, and the conductance plate 204 is halogenated gas (Cl, F Or a gas containing Br), Ni halide (NiCl ₂ , NiF ₂ , or NiBr ₂ ) is generated.

Note that when the halogen-based gas is supplied into the processing chamber 201, intrusion of the halogen-based gas into the source gas supply pipe 213a is prevented, and diffusion of the halogen-based gas in the processing chamber 201 is promoted. The valves ve1, ve2, and ve3 are preferably kept open, and the N ₂ gas is always allowed to flow into the processing chamber 201.

When a predetermined time elapses after the valves vb1, vb2, and vb3 are opened and the supply of the halogen-based gas is started, the valves vb1, vb2, and vb3 are closed, and the supply of the halogen-based gas into the processing chamber 201 is stopped. Thereafter, with the valves (not shown) provided in the cleaning gas supply source 220b closed, the valves vc1, vc4, vb1, vb2, and vb3 are opened to supply N ₂ gas into the cleaning gas supply pipe 213b, and the cleaning gas The supply pipe 213b is purged.

[Purge process (S103b)]
Thereafter, the processing chamber 201 is evacuated, the valves vc 1, vc 2, vc 3, ve 1, ve 2 and ve 3 are opened, and N ₂ gas is supplied into the processing chamber 201. The N ₂ gas is dispersed by the shower head 240 and supplied into the processing chamber 201, flows through the exhaust duct 259, and is exhausted to the exhaust port 260 and the exhaust pipe 261. As a result, the halogen-based gas and reaction byproducts remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with N ₂ gas.

[Cyclopenta group-containing gas supply step (S103c)]
Subsequently, while the vacuum pump 264 is operated, the valves vd1, vd2, and vd3 are opened, and the supply of the cyclopenta group-containing gas as the second cleaning gas into the processing chamber 201 is started. The cyclopenta group-containing gas is dispersed by the shower head 240 and is uniformly supplied onto the susceptor 217 and the conductance plate 204 in the processing chamber 201. Excess cyclopenta group-containing gas flows through the exhaust duct 259 and is exhausted to the exhaust port 260 and the exhaust pipe 261.

At this time, in the halogen-based gas supply step (S103a), the Ni generated in the processing container 202, that is, on the inner wall of the processing container 202, the members in the processing chamber 201 such as the shower plate 240b, the susceptor 217, and the conductance plate 204. Halides (NiCl ₂ , NiF ₂ , or NiBr ₂ ) react with the cyclopenta group-containing gas to produce Ni compounds (Ni (C ₅ H ₅ ) ₂ , Ni (C ₅ H ₄ CH ₃ ) _2, etc.). The The Ni compound is heated and vaporized under the above-described cleaning temperature and cleaning pressure, and is discharged from the processing container 202. That is, the heated and vaporized Ni compound flows through the exhaust duct 259 together with the cyclopentagroup-containing gas, and is exhausted to the exhaust port 260 and the exhaust pipe 261.

Note that when the cyclopenta group-containing gas is supplied into the processing chamber 201, the cyclopenta group-containing gas is diffused in the processing chamber 201 so as to prevent the cyclopenta group-containing gas from entering the source gas supply pipe 213a. It is preferable to keep the valves ve 1, ve 2 and ve 3 open so that the N ₂ gas always flows into the processing chamber 201 so as to facilitate the operation.

After the valves vd1, vd2, vd3 are opened and the supply of the cyclopenta group-containing gas is started, when a predetermined time has elapsed, the valves vd1, vd2, vd3 are closed, and the supply of the cyclopenta group-containing gas into the processing chamber 201 is stopped. Thereafter, with the valves (not shown) provided in the cleaning gas supply source 220d closed, the valves vc1, vc5, vd1, vd2, and vd3 are opened to supply N ₂ gas into the cleaning gas supply pipe 213d, and the cleaning gas The supply pipe 213d is purged.

[Purge process (S103d)]
Thereafter, the processing chamber 201 is evacuated, the valves vc 1, vc 2, vc 3, ve 1, ve 2 and ve 3 are opened, and N ₂ gas is supplied into the processing chamber 201. The N ₂ gas is dispersed by the shower head 240 and supplied into the processing chamber 201, flows through the exhaust duct 259, and is exhausted to the exhaust port 260 and the exhaust pipe 261. Thereby, the cyclopenta group-containing gas and reaction byproducts remaining in the processing chamber 201 are removed, and the inside of the processing chamber 201 is purged with N ₂ gas.

[Predetermined number of steps (S103e)]
The above halogen-based gas supply step (S103a), purge step (S103b), cyclopentagroup-containing gas supply step (S103c), and purge step (S103d) are set as one cycle, and this cycle is performed a predetermined number of times, thereby processing container 202. Etching of the deposit containing Ni adhering to the inside is performed. This cycle may be performed only once or may be repeated a plurality of times. By repeating this cycle a plurality of times, it becomes possible to etch the deposit containing Ni adhering in the processing vessel 202 more uniformly.
As described above, in the present embodiment, the etching of the deposit containing Ni adhering to the inside of the processing vessel 202 in the two stages of the halogen-based gas supply process (S103a) and the cyclopentagroup-containing gas supply process (S103c) is performed. Done. The etching performed in these two stages is performed at least once, preferably a plurality of times.

Thus, the cleaning inside the processing container 202 is completed.
After the cleaning is completed, pre-coating is performed in order to make the environment in the processing chamber 201 the same as that in the Ni film forming step (S5). That is, film formation is performed in the same manner as in the Ni film formation step (S5) using a dummy wafer as a dummy substrate. Thereafter, film formation is performed on the wafer in the same manner as in the Ni film formation step (S5), and the film formation characteristics are confirmed. When the environment in the processing chamber 201 becomes the same state as that in the Ni film forming step (S5), the above-described substrate processing step is repeated again.

The first cleaning condition in this embodiment, that is, the cleaning process condition in the halogen-based gas supply process (S103a) and the purge condition in the purge process (S103b) are as follows:
Processing chamber temperature: 150-400 ° C.
Processing chamber pressure: 50-3990 Pa,
Halogen-based gas supply flow rate: 100 to 1000 sccm,
Dilution gas (N ₂ ) supply flow rate: 500 to 1000 sccm,
Purge gas (N ₂ ) supply flow rate: 10 to 10,000 sccm,
Halogen gas supply time per cycle: 60 to 1800 seconds,
Purge time per cycle: 60-600 seconds,
Is exemplified.

In addition, the second cleaning condition in this embodiment, that is, the cleaning process condition in the cyclopentagroup-containing gas supply process (S103c) and the purge condition in the purge process (S103d) are as follows:
Processing chamber temperature: 150-400 ° C.
Processing chamber pressure: 50-3990 Pa,
Cyclopenta group-containing gas supply flow rate: 100 to 1000 sccm,
Dilution gas (N ₂ ) supply flow rate: 500 to 1000 sccm,
Purge gas (N ₂ ) supply flow rate: 10 to 10,000 sccm,
Gas supply time of cyclopenta group-containing gas per cycle: 60 to 1800 seconds,
Purge time per cycle: 60-600 seconds,
Is exemplified.
The number of cycles in the predetermined number of execution steps (S103e) is exemplified by 1 to 100 times.

  The cleaning conditions are generally preferably high temperature, high pressure, and high cleaning gas concentration with a high etching rate in consideration of mass productivity. However, in consideration of restrictions on the substrate processing apparatus, total downtime, etc., the cleaning process (S103 It is desirable that the temperature in the processing chamber at (1) is the same as the temperature in the processing chamber in the Ni film forming step (S5). That is, the processing chamber temperature in the cleaning step (S103) is preferably 150 to 250 ° C. If the processing chamber temperature in the cleaning step (S103) is set to such a temperature, it is not necessary to change the temperature in the processing chamber during the cleaning step, so that the downtime of the substrate processing apparatus can be shortened. The apparatus operating rate can be increased. In addition, by setting the processing chamber temperature in the cleaning step (S103) to 200 to 400 ° C., the etching rate can be increased, and deposits containing Ni adhering to the processing chamber can be efficiently removed. Furthermore, by setting the processing chamber temperature in the cleaning step (S103) to 200 to 250 ° C., it is not necessary to change the temperature in the processing chamber during the cleaning step, and deposits containing Ni adhering to the processing chamber. Can be efficiently removed.

By the way, in order to remove the deposit containing Ni, it is necessary that the gas containing a cyclopenta group reacts with nickel halide (Ni halide) and the deposit containing Ni is gasified. The vaporization temperature (vapor pressure) of Ni halide (NiCl ₂ , NiF ₂ , or NiBr ₂ ) or Ni compound (Ni (C ₅ H ₅ ) ₂ or Ni (C ₅ H ₄ CH ₃ ) ₂ ) is as follows. is there.
NiBr ₂ :-
NiCl ₂ : 760 @ 973 ° C
NiF ₂ : 760 @ 1750 ° C
Ni (C ₅ H ₅ ) ₂ : 10 @ 200 ° C.
Ni (C ₅ H ₄ CH ₃ ) ₂ : 100 @ 200 ° C.

These vapor pressures serve as an indicator of whether or not the Ni compound generated in the cleaning process can be vaporized and removed. As described above, the temperature in the processing chamber in the cleaning process is near the Ni film forming temperature (the processing chamber temperature in the Ni film forming process (S5)), and the temperature rise / fall time (temperature rise / fall time) is smaller. Since it is desirable, it can be estimated that the vapor pressures of NiCl ₂ and NiF ₂ described above are not practical with respect to the Ni film formation temperature (150 to 250 ° C.). On the other hand, the vapor pressures of Ni (C ₅ H ₅ ) ₂ and Ni (C ₅ H ₄ CH ₃ ) ₂ are values that can be sufficiently vaporized and discharged, and gas cleaning is performed at substantially the same temperature as the Ni film deposition temperature. Suggests that it is possible. That is, no temperature increase or decrease occurs in the cleaning process, and the downtime of the substrate processing apparatus can be shortened.

Note that, under the above-described cleaning conditions (first cleaning condition, second cleaning condition), a deposit containing Ni and a gas containing a cyclopenta group are directly reacted to form Ni (C ₅ H ₅ ) ₂ , Ni ( C ₅ H ₄ CH ₃₎ it is difficult to produce a Ni compound of _2. Therefore, in the present embodiment, the deposit containing Ni is reacted with the halogen-based gas under the above-described cleaning condition (first cleaning condition) to temporarily convert the deposit containing Ni into NiCl ₂ and NiF _2. Or after changing to Ni halide such as NiBr _2, the Ni halide is reacted with a gas containing a cyclopenta group under the above-described cleaning condition (second cleaning condition) to convert the Ni halide into Ni ( _{C 5 H 5) 2, Ni} (C 5 H 4 CH 3) so that changes in the Ni compound such as _2. As the halogen-based gas, a gas containing chlorine (Cl), fluorine (F), or bromine (Br) is preferably used. For example, ClF ₃ , Cl ₂ , HCl, NF ₃ , F ₂ , BCl ₃ , BBr ₃ and at least one gas selected from the group consisting of HBr is used. As the gas containing a cyclopenta group, a gas such as cyclopentadiene (C ₅ H ₆ ), dicyclopentadiene (C ₁₀ H ₁₂ ), or methylcyclopentadiene (C ₆ H ₈ ) is used. The deposit containing Ni chemically changes to NiCl ₂ , NiF ₂ , and NiBr ₂ when reacted with a gas containing Cl, a gas containing F, and a gas containing Br, respectively. Furthermore, NiCl ₂ , NiF ₂ , and NiBr ₂ chemically change to Ni (C ₅ H ₅ ) ₂ , Ni (C ₅ H ₄ CH ₃ ) _2, etc., when reacted with a gas containing a cyclopenta group. Ni compounds such as Ni (C ₅ H ₅ ) ₂ and Ni (C ₅ H ₄ CH ₃ ) ₂ are heated and vaporized to be discharged from the processing chamber.

In the above-described embodiment, the case where the film containing Ni or the deposit containing Ni is Ni has been described. However, the film containing Ni or the deposit containing Ni is Ni, Ni _x Si _y , or Ni _x. O _y (wherein x and y represent integers or fractions) may be used. The present invention can be similarly applied to the case where a film containing Ni or a deposit containing Ni is used.

  In the above-described embodiment, the example in which the processing container is cleaned without the wafer 200 (processed wafer, processed wafer) in the processing container has been described. However, a dummy wafer is carried into the processing container and the susceptor 217 is loaded. You may make it perform cleaning in the state which mounted the dummy wafer on it. In this manner, the wafer placement area of the susceptor 217 can be protected in the cleaning process, and the cleaning gas can be circulated to the lower portion of the processing chamber via the support base 203 and the through hole 208a of the susceptor 217. Can be suppressed. In this case, a dummy wafer carrying-in process into the processing container is performed before the temperature adjustment process (S101), and a dummy wafer carrying-out process from the processing container is performed after the cleaning process (S103). In addition to silicon, the dummy wafer may be made of quartz or SiC. Further, a disc-shaped cover member may be used instead of the dummy wafer. The cover member can be made of, for example, high temperature resistant high load quartz.

<Other Embodiments of the Present Invention>
In the above-described embodiment, an example of forming a film using a single-wafer type CVD apparatus that processes one substrate at a time as a substrate processing apparatus (film forming apparatus) has been described. It is not limited to. For example, the film may be formed using a batch type vertical CVD apparatus that processes a plurality of substrates at a time as a substrate processing apparatus. Hereinafter, this vertical CVD apparatus will be described.

  FIG. 6 is a schematic configuration diagram of a vertical processing furnace of a vertical CVD apparatus preferably used in the present embodiment. FIG. 6A shows a processing furnace 302 portion in a vertical cross section, and FIG. 6B shows a processing furnace. A portion 302 is shown in the cross-sectional view along the line AA in FIG.

  As shown in FIG. 6A, the processing furnace 302 has a heater 307 as a heating means (heating mechanism). The heater 307 has a cylindrical shape and is vertically installed by being supported by a heater base as a holding plate.

Inside the heater 307, a process tube 303 as a reaction tube is disposed concentrically with the heater 307. The process tube 303 is made of a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and has a cylindrical shape with the upper end closed and the lower end opened. A processing chamber 301 is formed in a cylindrical hollow portion of the process tube 303 so that wafers 200 as substrates can be accommodated in a state of being aligned in multiple stages in a vertical posture in a horizontal posture by a boat 317 described later.

  A manifold 309 is disposed below the process tube 303 concentrically with the process tube 303. The manifold 309 is made of, for example, stainless steel and is formed in a cylindrical shape with an upper end and a lower end opened. The manifold 309 is engaged with the process tube 303 and is provided to support the process tube 303. An O-ring 320a as a seal member is provided between the manifold 309 and the process tube 303. Since the manifold 309 is supported by the heater base, the process tube 303 is vertically installed. A reaction vessel is formed by the process tube 303 and the manifold 309.

  A first nozzle 333 a as a first gas introduction part and a second nozzle 333 b as a second gas introduction part are connected to the manifold 309 so as to penetrate the side wall of the manifold 309. Each of the first nozzle 333a and the second nozzle 333b has an L shape having a horizontal portion and a vertical portion, the horizontal portion is connected to the manifold 309, and the vertical portion is between the inner wall of the process tube 303 and the wafer 200. It is provided in an arc-shaped space so as to rise in the stacking direction of the wafer 200 along the inner wall above the lower part of the process tube 303. A first gas supply hole 348a and a second gas supply hole 348b, which are supply holes for supplying gas, are provided on the side surfaces of the vertical portions of the first nozzle 333a and the second nozzle 333b, respectively. The first gas supply hole 348a and the second gas supply hole 348b have the same opening area from the lower part to the upper part, and are provided at the same opening pitch.

  The gas supply system connected to the first nozzle 333a and the second nozzle 333b is the same as in the above-described embodiment. However, the present embodiment is different from the above-described embodiment in that the source gas supply system is connected to the first nozzle 333a and the cleaning gas supply system is connected to the second nozzle 333b. That is, in this embodiment, the source gas and the cleaning gas are supplied by separate nozzles. The source gas and the cleaning gas may be supplied from the same nozzle. If the source gas and the cleaning gas are supplied from the same nozzle, the cleaning in the nozzle can be performed in parallel.

  The manifold 309 is provided with an exhaust pipe 331 that exhausts the atmosphere in the processing chamber 301. A vacuum pump 346 as an evacuation device is connected to the exhaust pipe 331 through a pressure sensor 345 as a pressure detector and an APC (Auto Pressure Controller) valve 342 as a pressure regulator. By adjusting the APC valve 342 based on the detected pressure information, the processing chamber 301 is configured to be evacuated so that the pressure in the processing chamber 301 becomes a predetermined pressure (degree of vacuum). Note that the APC valve 342 is configured to open and close the valve to evacuate / stop evacuation in the processing chamber 301, and to adjust the valve opening to adjust the pressure in the processing chamber 301. Open / close valve.

  Below the manifold 309, a seal cap 319 is provided as a furnace port lid that can airtightly close the lower end opening of the manifold 309. The seal cap 319 is brought into contact with the lower end of the manifold 309 from the lower side in the vertical direction. The seal cap 319 is made of a metal such as stainless steel and is formed in a disk shape. On the upper surface of the seal cap 319, an O-ring 320b is provided as a seal member that contacts the lower end of the manifold 309. On the opposite side of the seal cap 319 from the processing chamber 301, a rotation mechanism 367 for rotating a boat 317 described later is installed. A rotation shaft 355 of the rotation mechanism 367 passes through the seal cap 319 and is connected to the boat 317, and is configured to rotate the wafer 200 by rotating the boat 317. The seal cap 319 is configured to be moved up and down in a vertical direction by a boat elevator 315 as an elevating mechanism disposed outside the process tube 303, and thereby the boat 317 is carried into and out of the processing chamber 301. It is possible.

  The boat 317 as a substrate holder is made of a heat-resistant material such as quartz or silicon carbide, and is configured to hold a plurality of wafers 200 in a horizontal posture and in a state where the centers are aligned with each other and held in multiple stages. Yes. A heat insulating member 318 made of a heat resistant material such as quartz or silicon carbide is provided at the lower part of the boat 317 so that heat from the heater 307 is not easily transmitted to the seal cap 319 side. A temperature sensor 363 as a temperature detector is installed in the process tube 303, and the temperature in the processing chamber 301 is adjusted by adjusting the power supply to the heater 307 based on the temperature information detected by the temperature sensor 363. Is configured to have a predetermined temperature distribution. The temperature sensor 363 is provided along the inner wall of the process tube 303, similarly to the first nozzle 333a and the second nozzle 333b.

  The controller 380 which is a control unit (control means) includes an APC valve 342, a heater 307, a temperature sensor 363, a vacuum pump 346, a rotation mechanism 367, a boat elevator 315, valves va1 to va5, vb1 to vb3, vc1 to vc5, vdl1. Controls the operations of vd3, ve1 to ve3, flow rate controllers 222a, 222b, 222c, 222d, and 222e.

  Next, using the processing furnace 302 of the vertical CVD apparatus according to the above configuration, as a process of a semiconductor device manufacturing process, a substrate processing process for forming a metal film on the wafer 200 by a CVD method, The cleaning process for cleaning will be described. In the following description, the operation of each unit constituting the vertical CVD apparatus is controlled by the controller 380.

First, the substrate processing process will be described.
A plurality of wafers 200 are loaded into the boat 317 (wafer charge). Then, as shown in FIG. 6A, the boat 317 holding the plurality of wafers 200 is lifted by the boat elevator 315 and loaded into the processing chamber 301 (boat loading). In this state, the seal cap 319 is in a state of sealing the lower end of the manifold 309 via the O-ring 320b.

  The inside of the processing chamber 301 is evacuated by a vacuum pump 346 so that the inside of the processing chamber 301 has a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 301 is measured by the pressure sensor 345, and the APC valve 342 is feedback-controlled based on the measured pressure. In addition, heating is performed by the heater 307 so that the inside of the processing chamber 301 has a desired temperature. At this time, feedback control of the power supply to the heater 307 is performed based on the temperature information detected by the temperature sensor 363 so that the inside of the processing chamber 301 has a desired temperature distribution. Then, the wafer 200 is rotated by rotating the boat 317 by the rotation mechanism 367.

  Thereafter, the Ni film forming step is performed in the same procedure as the Ni film forming step (S5) in the above-described embodiment. After the Ni film having a predetermined thickness is formed on the wafer 200, the residual gas removal step is performed in the same procedure as the residual gas removal step (S6) in the above-described embodiment.

  Thereafter, the seal cap 319 is lowered by the boat elevator 315 to open the lower end of the manifold 309, and the wafer 200 after the Ni film having a predetermined film thickness is formed on the manifold 309 while being held by the boat 317. Unload from the lower end of the process tube 303 (boat unload). Thereafter, the processed wafer 200 is taken out from the boat 317 (wafer discharge).

  The above-described substrate processing step is repeated, and when the thickness of the deposit attached to the inner wall of the process tube 303, the boat 317, etc. reaches a predetermined thickness before the deposit is peeled off or dropped, the process tube 303 is reached. Inside cleaning is performed. Hereinafter, the cleaning process will be described.

  An empty boat 317 not loaded with a wafer 200 (wafer charge) is lifted by the boat elevator 315 and loaded into the processing chamber 301 (boat loading). In this state, the seal cap 319 is in a state of sealing the lower end of the manifold 309 via the O-ring 320b.

  The inside of the processing chamber 301 is evacuated by a vacuum pump 346 so that the inside of the processing chamber 301 has a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 301 is measured by the pressure sensor 345, and the APC valve 342 is feedback-controlled based on the measured pressure. In addition, heating is performed by the heater 307 so that the inside of the processing chamber 301 has a desired temperature. At this time, feedback control of the power supply to the heater 307 is performed based on the temperature information detected by the temperature sensor 363 so that the inside of the processing chamber 301 has a desired temperature distribution. Then, the wafer 200 is rotated by rotating the boat 317 by the rotation mechanism 367.

  Thereafter, the cleaning process is performed in the same procedure as the cleaning process (S103) in the above-described embodiment.

  After the cleaning step (S103) is completed, the seal cap 319 is lowered by the boat elevator 315 to open the lower end of the manifold 309, and the empty boat 317 is carried out of the process tube 303 from the lower end of the manifold 309 (boat) Unload).

Thus, the cleaning in the processing chamber 301 is completed.
After the cleaning is completed, as in the above-described embodiment, pre-coating is performed, film formation is performed on the wafer, and film formation characteristics are confirmed. When the environment in the processing chamber 301 becomes the same state as that in the Ni film forming step, the above-described substrate processing step is repeated again.

<Preferred embodiment of the present invention>
Hereinafter, preferred embodiments of the present invention will be additionally described.

According to one aspect of the invention,
A step of carrying the substrate into the processing container;
Supplying a raw material containing nickel into the processing container and performing a process of forming a film containing nickel on the substrate;
Unloading the processed substrate from the processing container;
In a state where the substrate is not present in the processing container, a halogen-based gas is supplied into the processing container to react with a deposit containing nickel adhering to the processing container to generate nickel halide, and then the processing A gas containing a cyclopenta group is supplied into the container and reacted with the nickel halide to form a nickel compound. The nickel compound is heated and vaporized and discharged from the processing container, thereby adhering to the processing container. Removing the nickel-containing deposit,
A method of manufacturing a semiconductor device having the above is provided.

Preferably, the nickel-containing film or the nickel-containing deposit is Ni, Ni _x Si _y , or Ni _x O _y (wherein x and y represent integers or fractions).
Preferably, the nickel compound is Ni (C ₅ H ₅ ) ₂ or Ni (C ₅ H ₄ CH ₃ ) ₂ .
Further preferably, the halogen-based gas is a gas containing chlorine, fluorine, or bromine.
Preferably, the halogen gas is at least one gas selected from the group consisting of ClF ₃ , Cl ₂ , HCl, NF ₃ , F ₂ , BCl ₃ , BBr ₃ , and HBr.
Preferably, the gas containing a cyclopenta group is cyclopentadiene, dicyclopentadiene, or methylcyclopentadiene.

According to another aspect of the invention,
A processing vessel for processing a substrate;
A raw material supply system for supplying a raw material containing nickel into the processing vessel;
A halogen-based gas supply system for supplying a halogen-based gas into the processing vessel;
A cyclopenta group-containing gas supply system for supplying a gas containing a cyclopenta group into the processing vessel;
An exhaust system for exhausting the inside of the processing vessel;
A heater for heating the inside of the processing container;
After performing the process of supplying the raw material into the processing container and forming a film containing nickel on the substrate, the halogenated gas is supplied into the processing container without the substrate in the processing container. A nickel halide is produced by reacting with a deposit containing nickel adhering to the inside of the processing vessel, and then a gas containing a cyclopenta group is supplied into the processing vessel to react with the nickel halide to produce a nickel compound. The raw material supply system, the halogen-based gas supply system so as to remove the deposits containing nickel adhering to the processing container by heating and vaporizing the nickel compound and discharging it from the processing container. A control unit for controlling the cyclopenta group-containing gas supply system, the exhaust system, and the heater;
A substrate processing apparatus is provided.

200 wafer (substrate)
201 processing chamber 202 processing container 203 support stand 206 heater 213a raw material gas supply pipe 213b cleaning gas supply pipe 213c purge gas supply pipe 213d cleaning gas supply pipe 213e purge gas supply pipe 237a carrier gas supply pipe 220a bubbler 261 exhaust pipe 280 controller

Claims (7)

A step of carrying the substrate into the processing container;
Supplying a raw material containing nickel into the processing container and performing a process of forming a film containing nickel on the substrate;
Unloading the processed substrate from the processing container;
In a state where the substrate is not present in the processing container, a halogen-based gas is supplied into the processing container to react with a deposit containing nickel adhering to the processing container to generate nickel halide, and then the processing A gas containing a cyclopenta group is supplied into the container and reacted with the nickel halide to form a nickel compound. The nickel compound is heated and vaporized and discharged from the processing container, thereby adhering to the processing container. Removing the nickel-containing deposit,
A method for manufacturing a semiconductor device, comprising: The nickel-containing film or the nickel-containing deposit is Ni, Ni _x Si _y , or Ni _x O _y (wherein x and y are integers or fractions). 2. A method for manufacturing a semiconductor device according to 1. The method for manufacturing a semiconductor device according to claim 1, wherein the nickel compound is Ni (C ₅ H ₅ ) ₂ or Ni (C ₅ H ₄ CH ₃ ) ₂ .   The method for manufacturing a semiconductor device according to claim 1, wherein the halogen-based gas is a gas containing chlorine, fluorine, or bromine. 2. The halogen-based gas is at least one gas selected from the group consisting of ClF ₃ , Cl ₂ , HCl, NF ₃ , F ₂ , BCl ₃ , BBr ₃ , and HBr. 4. A method for manufacturing a semiconductor device according to any one of items 1 to 3.   6. The method of manufacturing a semiconductor device according to claim 1, wherein the gas containing a cyclopenta group is cyclopentadiene, dicyclopentadiene, or methylcyclopentadiene. A processing vessel for processing a substrate;
A raw material supply system for supplying a raw material containing nickel into the processing vessel;
A halogen-based gas supply system for supplying a halogen-based gas into the processing vessel;
A cyclopenta group-containing gas supply system for supplying a gas containing a cyclopenta group into the processing vessel;
An exhaust system for exhausting the inside of the processing vessel;
A heater for heating the inside of the processing container;
After performing the process of supplying the raw material into the processing container and forming a film containing nickel on the substrate, the halogenated gas is supplied into the processing container without the substrate in the processing container. A nickel halide is produced by reacting with a deposit containing nickel adhering to the inside of the processing vessel, and then a gas containing a cyclopenta group is supplied into the processing vessel to react with the nickel halide to produce a nickel compound. The raw material supply system, the halogen-based gas supply system so as to remove the deposits containing nickel adhering to the processing container by heating and vaporizing the nickel compound and discharging it from the processing container. A control unit for controlling the cyclopenta group-containing gas supply system, the exhaust system, and the heater;
A substrate processing apparatus comprising: