JP2011157571A - Substrate processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate processing apparatus capable of enhancing the quality of a metal thin film even in the case of a high melting point metal, and a method for manufacturing a semi-conductor device. <P>SOLUTION: The substrate processing apparatus includes a processing chamber 1 having a substrate supporting part for supporting a member 18 to be etched and a substrate, a gas supply unit for supplying halogen gas so as to allow the member to be etched in the processing chamber to be exposed therewith, a plasma generation unit for making the supplied gas in a plasma state, and a power source for applying the DC current to a solid metal as the member to be etched. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a substrate processing apparatus for forming a metal thin film on a substrate.

  As a process of manufacturing a semiconductor device such as a DRAM, a halogen-containing gas is supplied into a processing chamber containing a substrate to form a plasma state, and a metal member provided in the processing chamber is etched by the halogen-containing gas in a plasma state. Then, the metal halide (precursor) generated by the etching is adsorbed on the substrate, and the metal halide adsorbed on the substrate reacts with the halogen-containing gas in a plasma state to cause the metal on the substrate. A substrate processing step of depositing and forming a metal thin film on the substrate has been performed (for example, Non-Patent Document 1).

N. Oyama, Y. Ogura, Y. Mitake, Y. Tomita, H. Sakamoto, S. Nagase, M. Watanabe, N. Fujiwara, S. Ohshima, and F. Hirose, Jpn. J. Appl. Phys., 46 (2007) pp.L506-L508

The above-described substrate processing process proceeds as follows. In the following description, chlorine gas (Cl ₂ ) is used as the halogen-containing gas, and copper (Cu) is used as the constituent material of the metal member.

Cl ₂ → 2Cl ^* ·· Formula (1)
Cu + Cl ^* → CuCl (gas) ・ ・ Formula (2)
CuCl (gas) → CuCl (adsorption) ・ ・ Formula (3)
CuCl (adsorption) + Cl ^* → Cu (solid) + Cl ₂ (gas) ↑ ・ ・ Formula (4)

Expression (1) shows that chlorine gas supplied into the processing chamber is in a plasma state, whereby chlorine is decomposed and radicals (Cl ^* ) are generated. In formula (2), a metal member made of copper (Cu) provided in the processing chamber is etched by radicals (Cl ^* ) contained in chlorine gas in a plasma state, and copper chloride (CuCl) as a metal halide is etched. ) The gas is generated in the processing chamber. Formula (3) shows how the copper chloride gas as the metal halide is adsorbed on the substrate. In the formula (4), copper chloride adsorbed on the substrate reacts with radicals in chlorine gas in a plasma state, whereby copper (Cu) is deposited on the substrate and chlorine (Cl) is The state of desorption from the substrate as chlorine gas (Cl ₂ ) is shown.

  However, in the above-described substrate processing step, the chlorine elimination reaction shown in Formula (4) does not proceed sufficiently, chlorine (Cl) as a halogen element remains in the formed metal thin film, and the film quality of the metal thin film is In some cases, it worsened.

  It is an object of the present invention to provide a substrate processing apparatus and a semiconductor device manufacturing method capable of suppressing the residual halogen element in the metal thin film and improving the film quality of the metal thin film.

According to one aspect of the present invention, a processing chamber having a substrate support portion that supports a member to be etched and a substrate, a gas supply unit that supplies a halogen gas to the member to be etched in the processing chamber, and the supply There is provided a substrate processing apparatus having a plasma generation unit that converts the generated gas into a plasma state and a power source that applies a direct current to the solid metal that is the member to be etched.

  According to the substrate processing apparatus and the method for manufacturing a semiconductor device according to the present invention, it is possible to improve the film quality of a metal thin film even in a high melting point metal.

It is side surface sectional drawing of the substrate processing apparatus which concerns on the 1st Embodiment of this invention. It is a figure explaining the gas supply sequence which concerns on the 1st Embodiment of this invention. It is side surface sectional drawing of the substrate processing apparatus which concerns on the 2nd Embodiment of this invention.

<First Embodiment of the Present Invention>
The first embodiment of the present invention will be described below.

(1) Configuration of Substrate Processing Apparatus First, the configuration of a substrate processing apparatus according to the present embodiment will be described with reference to FIG. FIG. 1 is a side sectional view of the substrate processing apparatus according to the present embodiment.

(Processing room)
The substrate processing apparatus 100 according to this embodiment includes a processing chamber 1 that accommodates a wafer 3 as a substrate. The processing chamber 1 is composed of a quartz ceiling plate 7 and a lower container 5 made of a metal material such as SUS. The ceiling plate 7 is sealed and separated from the lower container 5 by an O-ring. The lower container 5 is grounded (earthed). A wafer transfer port (not shown) and a gate valve for opening and closing the wafer transfer port are provided on the side wall of the processing chamber 1. In the processing chamber 1, a wafer support mechanism 2 is provided as a substrate support portion configured to be movable up and down while ensuring airtightness in the processing chamber 1 with a bellows. The wafer 3 is transferred into and out of the processing chamber 1 by the cooperation of the opening / closing operation of the gate valve, the transfer operation of the wafer 3 by a transfer device (not shown), and the raising / lowering operation of the wafer support mechanism 2.

(Plasma generator)
A metal member 18 is provided at a position facing the substrate placement surface of the wafer placement mechanism 2, and a plasma generation antenna 9 is provided outside the ceiling plate 7 of the processing chamber 1. That is, the metal member 18 is provided between the plasma generating antenna 9 and the substrate mounting surface of the wafer mounting mechanism 2. The plasma generating antenna 9 turns the gas supplied into the processing chamber 1 into a plasma state during substrate processing.

  The plasma generating antenna 9 is connected to a high frequency power source 11 as a power supply unit via a matching circuit 10, and the high frequency power source 11 is grounded. The high frequency power supply 11 applies a high frequency of 13.56 MHz to the plasma generating antenna 9.

By supplying high-frequency power from the high-frequency power source 11 to the plasma generating antenna 9 in a state where a mixed gas (halogen-containing gas) of chlorine gas and helium gas is supplied into the processing chamber 1 by a gas supply unit described later, In the vicinity of the metal material 18 to be etched, a mixed gas of chlorine gas and helium gas can be brought into a plasma state.
The plasma generation antenna 9, the matching circuit 10, and the high frequency power source 11 constitute a plasma generation unit according to this embodiment.

(heater)
A heater 4 configured as a resistance heater or the like is provided in the wafer support mechanism 2. By adjusting the energization amount to the heater 4, the temperature of the wafer 3, the metal member 18, and the like placed on the placement surface of the wafer support mechanism 2 can be adjusted.

(Gas supply part)
A gas supply path for supplying gas is connected to the side surface of the processing chamber 1 via a nozzle 12. Gas supply paths 62a, 62b, 62c, and 62d are connected to the nozzle 12.
From the upstream side, the gas supply path 62a is provided with a chlorine (Cl2) gas source 32a, a mass flow controller (MFC) 42a for adjusting the gas flow rate, and an open / close valve 52a for supplying / stopping the gas. Similarly, a helium (He) gas source 32b, a mass flow controller (MFC) 42b, and an open / close valve 52b are provided in the gas supply path 62b from the upstream. The gas supply path 62c is provided with a hydrogen (H2) gas source 32c, a mass flow controller (MFC) 42c, and an opening / closing valve 52c from the upstream. A nitrogen (N2) gas source 32d, a mass flow controller (MFC) 42d, and an open / close valve 52d are provided in the gas supply path 62d from the upstream.

The flow rate is controlled by the mass flow controllers 42a and 42b, and the open / close valves 52a and 52b are opened to supply a mixed gas of chlorine gas and helium gas as a halogen-containing gas into the processing chamber 1. . Further, the mixed gas of hydrogen gas and nitrogen gas is supplied into the processing chamber 1 by opening the on-off valves 52c and 52d while controlling the flow rate by the mass flow controllers 42c and 42d. Further, the flow rate is controlled by the mass flow controller 42d, and the open / close valve 52d is opened to supply nitrogen gas into the processing chamber 1.

  The nozzle 12 and the gas supply paths 62a, 62b, 62c, and 62d mainly constitute the gas supply unit according to this embodiment.

(Metal member)
Between the substrate support mechanism 2 and the ceiling plate 7, a metal member 18 as an etched member is provided. The metal member 18 is made of a metal material that is a raw material for the metal thin film formed on the wafer 3, such as tungsten (W). The metal member 18 has a net-like shape, for example, a tungsten wire net having a diameter of 0.1 mm and a mesh of 30 mesh per 1 cm, and has a width of 30 mm and a length of 100 mm. A DC power source 20 is connected to the metal member 18 and can be directly energized. By energizing, the entire metal member 18 is heated to 500 ° C. or higher, preferably 750 ° C. or higher, and equal to 800 ° C. or higher when the metal is tungsten.

As a method of heating the metal member 18, it is conceivable to provide a sheath heater in the vicinity of the metal member 18 and heat it thereby. However, it is difficult for the entire metal member to be heated uniformly, and there is a risk of contamination by impurity elements from the sheath heater material. Furthermore, when the metal member is set to a floating potential, a tendency to increase from room temperature to, for example, about 500 ° C. over several minutes is seen, and then the temperature of the metal member 18 varies within a range of 500 ° C. to 545 ° C. Even if an attempt is made to control the temperature with a sheath heater from the outside because the temperature is not stable, the temperature followability of the metal member cannot be secured, and a stable metal film, that is, a metal film having a uniform film thickness or quality cannot be formed.
From the above, it is preferable that the metal member 18 is directly energized and heated as described above.

The metal member 18 is grounded, and has the same potential as that of the reaction chamber 1 and the potential is fixed. By setting the same potential, the metal member 18 can be prevented from being charged by ion irradiation when the metal member 18 is exposed to plasma. Thereby, suppression of the plasma amount to the board | substrate 3 by charging can be prevented.
Further, fixing the potential prevents the potential of the metal member 18 from approaching the plasma potential when exposed to plasma. If the potential is not fixed, the metal member 18 is charged, the transport of chlorine ions in the plasma to the metal member is hindered, and there is a possibility that sufficient metal halide cannot be supplied to the wafer.
Here, the reaction chamber 1 and the metal member 18 have the same potential. However, the present invention is not limited to this, and the potential of the metal member 18 may be lower than that of the reaction chamber 1.

The tip of the nozzle 12 that supplies the gas is configured to face the metal member 18. While supplying a mixed gas (halogen-containing gas) of chlorine gas and helium gas into the processing chamber 1 by the nozzle 12 described above, high-frequency power is supplied to the plasma generating antenna 9 by the above-described power supply unit, so that the halogen-containing gas is supplied. Is in a plasma state, the metal member 18 is etched by the halogen-containing gas in the plasma state and radicals (Cl ^* ) contained in the gas, and, for example, tungsten chloride (WCl) gas as a metal halide is contained in the processing chamber 1. It is configured to be generated. The metal halide generated by the etching is configured to be adsorbed and deposited on the wafer 3. At the time of deposition, since the metal member 18 has a net shape, the generated plasma passes through the net uniformly, and as a result, the metal halide compound can be uniformly deposited on the substrate.

(Exhaust part)
An exhaust port 17 is provided below the processing chamber 1. A pressure gauge, an exhaust valve 44 and a vacuum pump 60 (not shown) are connected to the exhaust port 17 in order from the upstream side. The pressure in the processing chamber 1 can be adjusted by operating the vacuum pump 60 and adjusting the opening degree of the exhaust valve 44. The exhaust part according to this embodiment is mainly configured by the exhaust port 17, a pressure gauge (not shown), the exhaust valve 44, and the vacuum pump 60.

(controller)
Wafer support mechanism 2, heater 4, mass flow controllers 42a, 42b, 42c, 42d, open / close valves 52a, 52b, 52c, 52d, matching unit 10, high frequency power supply 11, pressure gauge (not shown), exhaust valve 44, gate valve ( (Not shown) is connected to a controller 70 as a control unit. The controller 70 controls the flow rate of the mass flow controllers 42a, 42b, 42c, and 42d, opens and closes the opening and closing valves 52a, 52b, 52c, and 52d, energizes the heater 4 and the metal member 18, adjusts the impedance of the matching unit 10, and performs high frequency. The power supply 11 and the DC power supply 20 are configured to control the power supply operation, the exhaust valve 44 opening adjustment operation, the gate valve opening / closing operation, and the wafer support mechanism 2 lifting / lowering operation.

(2) Substrate Processing Step Next, a substrate processing step according to the present embodiment performed by the above-described substrate processing apparatus will be described with reference to FIGS. In the substrate processing step according to the present embodiment, as shown in FIG. 2, the film forming step (S30) as one step for forming a metal thin film on the substrate and the residual gas of the processing gas used in S30 are exhausted. A vacuuming step (S31) as a second step, a reducing step (S32) as a third step of reducing the halogen element contained in the metal thin film by supplying hydrogen gas in a plasma state to the formed metal thin film ) And the purge step (S33) as the fourth step for exhausting the gas supplied in S32, this cycle is repeated. In the following description, the operation of each part of the substrate processing apparatus described above is controlled by the controller 70.

(Wafer carry-in process (S10))
First, the gate valve is opened while the wafer support mechanism 2 is raised, and the wafer 3 is loaded into the processing chamber 1 by a transfer device (not shown) and placed on the wafer support mechanism 2. Then, the gate valve 20 is closed.

(Evacuation step (S20))
Next, the vacuum pump 60 is operated, the opening degree of the exhaust valve 44 is adjusted, and the processing chamber 1 is controlled so as to have a desired pressure (film forming pressure) within 1 to 10,000 Pa. In addition, the heater 4, the metal member 18, and the wafer 3 in the substrate support mechanism 2 are controlled so as to have a predetermined temperature (film formation temperature).
The heater 4 is set to a desired temperature within a range of room temperature to 1000 ° C., and the metal member 18 is set to a desired temperature within 800 ° C. or more.

(Film formation process (S30))
Next, the flow rate is controlled by the mass flow controllers 42a and 42b, and the open / close valves 52a and 52b are opened to supply a mixed gas of chlorine gas as a halogen-containing gas and helium gas for plasma excitation into the processing chamber 1. To start. A mixed gas of chlorine gas and helium gas supplied from the gas supply unit into the processing chamber 1 is supplied via the nozzle 12 into the processing chamber, particularly around the metal member 18.
Note that neon (Ne), argon (Ar), and nitrogen (N2) may be used as the plasma excitation gas.

While supplying a mixed gas of chlorine gas and helium gas into the processing chamber 1, high-frequency power is supplied from the high-frequency power source 11 to the plasma generating antenna, and DC power is supplied from the DC power source 20 to the metal member 18. The mixed gas is brought into a plasma state while maintaining the member 18 at a desired temperature. As a result, the mixed gas in the plasma state and radicals contained in the gas (Cl ^* , see formula (5) to be described later) etch the metal member 18 to form a metal halide (reaction product, precursor). For example, tungsten chloride (WCl) gas is generated (see formula (6) described later). The tungsten chloride (WCl) gas generated by the etching is adsorbed and deposited on the wafer 3. At this time, the temperature of the metal member 18 is set to 800 ° C or higher. By setting the temperature to 800 ° C. or higher, etching of tungsten (W) can be promoted.

Tungsten (W) is deposited on the wafer 3 to form a metal thin film containing W as a main component (see formula (7) described later). Note that chlorine (Cl) is dissociated from the metal thin film as chlorine gas (Cl ₂ ) (see formula (8) described later).
Depending on the desired film thickness, the plasma state is maintained and the temperature of the metal material 18 is maintained for 3 to 40 minutes.

The above process is expressed as follows.
Cl ₂
+
e * → 2Cl * + e
..Formula (5)
M
+
Cl * → MCl (gas) ・ ・ Formula (6)
MCl (gas) → MCl (adsorption)
..Formula (7)
MCl
+
Cl * → M (solid) + Cl ₂ (gas) ↑ ・ ・ Formula (8)
Here, M represents a metal atom. Expressions (6) to (8) are phenomena that occur simultaneously in the same process.

Although description has been made using tungsten as an example of the metal film to be formed, the present invention is not limited to this, and other metal members are also possible. For example, ruthenium (Ru), nickel (Ni), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), aluminum (Al), gallium (Ga) ) And indium (In).

Among the above, in the case of nickel (Ni) and copper (Cu), the melting point of Ni is 1455 ° C., and Cu has a relatively low melting point of 1083 ° C. Comparing the temperatures at which the vapor pressure is 10 ^-2 Torr, Ni is 1510 ° C and Cu is 1273 ° C. When etching with chlorine radicals, the temperature of the metal member 18 can be in the range of 500 ° C. or more and 600 ° C. or less.
On the other hand, for a material having a high melting point such as tungsten W (3382 ° C. in the case of W), a metal film cannot be successfully formed at a low temperature such as nickel or copper. In order for Equation (6) to proceed, the temperature of the member to be etched needs to be raised to some extent, but the temperature at which the vapor pressure becomes 10 ⁻² Torr is 3309 ° C. for W and is etched with chlorine radicals. When the metal member 18 is tungsten, it is necessary to set the temperature in the range of 800 ° C. or higher and 1000 ° C. or lower.

  When a metal thin film having a desired film thickness is formed after a predetermined time has elapsed, power supply to the high-frequency power supply 11 is stopped and the open / close valves 52a and 52b are closed.

In addition, as conditions in the film-forming process (S30) which concerns on this embodiment, for example,
Flow rate of mixed gas of chlorine gas and helium gas: 2 slm,
Pressure in the processing chamber 1: 133 Pa,
Wafer 3 temperature: 280 ° C.
Metal member 18 temperature: 800 ° C.
Is exemplified.

(Evacuation step (S31))
As described above, the on-off valves 52a and 52b are closed, and supply of chlorine (Cl2) and helium (He) is stopped. Further, the opening / closing valve 52d is opened, and nitrogen (N 2), which is a carrier gas, whose flow rate is adjusted by the mass flow controller 42c, is supplied into the processing chamber 1. At this time, the exhaust valve 44 of the gas exhaust pipe 17 is kept open, and the residual gas is exhausted by the vacuum pump 60 so that the inside of the processing chamber 1 becomes 20 Pa or less.
Thereby, the processing chamber 1 is replaced with nitrogen (N 2).

(Reduction process (S32))
Supply of a mixed gas of hydrogen gas and nitrogen gas into the processing chamber 1 is started by opening the open / close valves 52c and 52d while controlling the flow rate by the mass flow controllers 42c and 42d. A mixed gas of hydrogen gas and helium gas supplied from the gas supply unit into the processing chamber 1 is supplied from the nozzle 12 toward the wafer 3.
At this time, the ratio of hydrogen to nitrogen is 2% for hydrogen and 98% for nitrogen.

While supplying a mixed gas of hydrogen gas and nitrogen gas into the processing chamber 1, high frequency power is supplied from the high frequency power supply 11 to the plasma generating antenna 9, and the mixed gas is brought into a plasma state. As a result, radicals (H ^* ) contained in the mixed gas in the plasma state reduce Cl contained in the metal thin film.

When the reduction of Cl of the metal thin film is completed after a predetermined time has elapsed, the power supply to the plasma generating antenna 9 is stopped, and the open / close valve 52c is closed to supply the mixed gas with hydrogen gas into the processing chamber 1. To stop.
Here, the predetermined time is, for example, between 3 and 40 minutes.

In addition, as conditions in the reduction | restoration process (S31) which concerns on this embodiment, for example,
Flow rate of mixed gas of hydrogen gas and helium gas: 1 slm,
Pressure in the processing chamber 1: 133 Pa,
Wafer 3 temperature: 280 ° C.
Is exemplified.

(Evacuation step (S33))
As described above, the on-off valve 52c is closed and the supply of hydrogen is stopped. The on-off valve 52d is kept open, and nitrogen (N2), which is a carrier gas, whose flow rate is adjusted by the mass flow controller 42d, is supplied into the processing chamber 1. At this time, the exhaust valve 44 of the gas exhaust pipe 17 is kept open, and the residual gas is exhausted by the vacuum pump 60 so that the inside of the processing chamber 1 becomes 20 Pa or less.
Thereby, the processing chamber 1 is replaced with nitrogen (N 2).

(Repeated process)
Thereafter, the film forming step (S30) to the reducing step (S33) are set as one cycle, and this cycle is repeated a predetermined number of times to form a metal thin film having a desired film thickness.

(Wafer unloading step (S40))
The on-off valve 52d is kept open, and nitrogen (N2) as an inert gas, whose flow rate is adjusted by the mass flow controller 42d, is supplied into the processing chamber 1. The opening degree of the exhaust valve 44 is adjusted to return the inside of the processing chamber 1 to atmospheric pressure. Then, the film-formed wafer 3 is unloaded from the processing chamber 1 by the reverse process of the above process.

(3) Effects according to the present embodiment According to the present embodiment, the following one or more effects are achieved.

  According to this embodiment, since the metal member can be uniformly heated in the above-described film forming step (S30), it is possible to promote etching by plasma.

  In addition, according to the present embodiment, the metal member can be heated to a high temperature in the above-described film forming step (S30), so that etching can be promoted even for a metal that needs to be in a high temperature state such as tungsten. Can do.

  In addition, since the metal member 18 has the same potential as or lower than that of the reaction chamber 1, charging of the metal member can be prevented, and halide can be generated efficiently.

  In addition, since the charging of the metal member is prevented, it is possible to continue the generation of halide, that is, the film formation.

  In the reduction step (S31) for reducing the halogen element according to this embodiment, high-frequency power is supplied to the lower electrode 35 instead of the upper electrode 34, and the mixed gas of hydrogen gas and helium gas is brought into a plasma state. In this way, damage to the metal member 18 can be reduced by supplying high-frequency power not to the upper electrode 34 but to the lower electrode 35 that is relatively far from the metal member 18.

Further, in the reduction step (S31) for reducing the halogen element according to the present embodiment, a plasma state is generated by supplying a mixed gas of hydrogen gas and nitrogen gas instead of supplying hydrogen gas into the processing chamber 1 alone. It is said. Thus, by adding nitrogen gas to hydrogen gas, the lifetime of radical (H ^* ) can be increased, the efficiency of reduction treatment can be improved, and the film quality of the metal thin film can be further improved.

Further, according to the present embodiment, the chlorine gas is not supplied into the processing chamber 1 alone, but a mixed gas of chlorine gas and helium gas is supplied to form a plasma state. Thus, by adding helium gas to chlorine gas, the lifetime of the radical (Cl ^* ) can be increased, the efficiency of the film forming process can be improved, and the film quality of the metal thin film can be improved.

<Second Embodiment of the Present Invention>
The substrate processing apparatus according to this embodiment is different from the above-described embodiment in that a DC power source 21 that is a second DC power source is provided in order to control the potential of the metal member 18.

FIG. 3 is a side sectional view of the substrate processing apparatus according to the present embodiment.
In the description of FIG. 3, the description of the same numbered configuration as in FIG. 1 is omitted.
In the configuration of FIG. 1, the metal member 7 is at ground potential, whereas in FIG. 3, the potential of the metal member 7 can be arbitrarily changed by the DC power source 21. When the metal member is set to a floating potential, part of the chlorine gas is ionized and collects around the metal member to be charged. For this reason, the ionized chlorine gas cannot approach the metal member and the etching is hindered. When the DC power supply 21 is provided, the etching of ions can be promoted by changing the potential of the metal member.

According to the present embodiment, since the potential of the metal member 18 can be controlled to be lower than the potential of the processing chamber 1, the metal member 18 is prevented from being charged by ion irradiation when the metal member 18 is exposed to plasma. It becomes possible. Thereby, suppression of the plasma amount to the board | substrate 3 by charging can be prevented.

<Still another embodiment of the present invention>
As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, Various changes are possible in the range which does not deviate from the summary.

  For example, in the above-described embodiment, the substrate processing apparatus including the plasma generation unit having the plasma generation antenna has been described. However, the present invention is not limited to such a form. That is, the present invention can be suitably applied to a substrate processing apparatus including a plasma generation unit such as a parallel plate type or an ECR plasma type, without being limited to the inductive coupling type.

Here, description has been made using tungsten as an example of the metal member, but the present invention is not limited to this, and other metal members are also possible. For example, ruthenium (Ru),
Nickel (Ni), Titanium (Ti), Zirconium (Zr), Hafnium (Hf), Niobium (Nb), Tantalum (Ta), Molybdenum (Mo), Aluminum (Al), Gallium (Ga), Indium (In) is there.
However, in the case of a metal member having a high melting point temperature such as tungsten, it is necessary to make the temperature of the entire member uniform and high.

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

<Appendix 1>
A processing chamber having a substrate support portion for supporting a member to be etched and a substrate, a gas supply portion for supplying a halogen gas to the member to be etched in the processing chamber, and a plasma in which the supplied gas is in a plasma state A substrate processing apparatus comprising: a generation unit; and a power source that applies a direct current to the solid metal that is the member to be etched.

<Appendix 2>
The substrate processing apparatus according to appendix 1, wherein the solid metal has at least one component of Ru, Ni, Ti, Zr, Hf, Nb, Ta, Mo, W, Al, Ga, and In.

<Appendix 3>
The substrate processing apparatus according to appendix 1, wherein the solid metal is tungsten, and the solid metal is 800 ° C. or higher and 1000 ° C. or lower in the film forming step.

<Appendix 4>
The substrate processing apparatus according to claim 1, wherein the solid metal has the same potential as the processing chamber or lower than the potential of the processing chamber.

<Appendix 5>
A halogen gas (in this case, chlorine gas) and a rare gas are supplied into a chamber containing a substrate, and plasma is generated in the chamber by a high frequency applied from the outside, so that a precursor of a metal component and a halogen contained in the member to be etched is generated. A body is generated and carried to the substrate, and only a metal component is generated from the precursor by a reduction reaction between halogens in the precursor, and a film is formed on the substrate. At this time, a metal film forming method and apparatus characterized in that a direct current is directly applied to a solid metal that is a member to be etched to control the temperature of the solid metal material to deposit the metal film.

<Appendix 6>
A step of carrying at least one substrate into the processing chamber, a step of supplying halogen gas into the processing chamber, reacting a halogen gas plasma excited at a high frequency with a solid metal, and supplying a metal chloride onto the substrate; 6. The method and apparatus for forming a metal film according to appendix 5, which includes a step of depositing a metal film by a reduction reaction of the metal chloride precursor and the halogen gas radical, and a step of unloading the substrate from the processing chamber.

<Appendix 7>
The metal film deposition method according to appendix 5 to 6, wherein the solid metal material is a metal material containing Ru, Ni, Ti, Zr, Hf, Nb, Ta, Mo, W, Al, Ga, In, or the like. And equipment.

<Appendix 8>
The method and apparatus for forming a metal film according to appendices 5 to 7, wherein the halogen gas for plasma etching the solid metal material is a halogen gas containing chlorine (Cl ₂ ) and hydrogen chloride (HCl).

<Appendix 9>
The method for forming a metal film according to appendices 5 to 8, wherein a gas radical such as hydrogen (H ₂ ), a hydrogen radical, and a chlorine radical is used as a reducing gas for removing impurities contained in the metal film, and apparatus.

<Appendix 10>
The metal film deposition method and apparatus according to appendices 5 to 9, wherein helium (He), neon (Ne), argon (Ar), and nitrogen (N ₂ ) are used as the excitation gas.

<Appendix 11>
The method and apparatus for forming a metal film according to appendices 5 to 10, wherein the temperature of the solid metal is 500 ° C. or higher and 1000 ° C. or lower.

<Appendix 12>
The metal film deposition method and apparatus according to appendices 5 to 11, wherein the processing chamber pressure in the deposition step is 1 Pa or more and 10,000 Pa or less.

<Appendix 13>
13. The method and apparatus for forming a metal film according to appendices 5 to 12, wherein the potential of the member to be etched is set equal to or lower than the chamber potential.

DESCRIPTION OF SYMBOLS 1 Processing chamber 2 Wafer support mechanism 3 Wafer 4 Heater 5 Lower container 7 Ceiling board 9 Plasma generating antenna 10 Matching device 11 Power supply 12 Nozzle 17 Exhaust port 18 Metal member (etched member)
19 ring unit 20 first DC power source 21 second DC power source 32, 32a, 32b, 32c 32d gas source 42a, 42b, 42c, 42d mass flow controller 44 exhaust valve 52a, 52b, 52c, 52d raw material gas valve 60 pump 62a, 62b, 62c, 62d Gas supply path 70 Controller

Claims (4)

A processing chamber having a member to be etched and a substrate supporting portion for supporting the substrate;
A gas supply section for supplying a halogen gas to the member to be etched in the processing chamber;
A plasma generating unit for bringing the supplied gas into a plasma state;
A power source for applying a direct current to the solid metal as the member to be etched;
A substrate processing apparatus.   2. The substrate processing apparatus according to claim 1, wherein the solid metal has at least one component of Ru, Ni, Ti, Zr, Hf, Nb, Ta, Mo, W, Al, Ga, and In.   The substrate processing apparatus according to claim 1, wherein the solid metal is tungsten, and the solid metal is set to 800 ° C. or more and 1000 ° C. or less in the film forming step.   The substrate processing apparatus according to claim 1, wherein the solid metal has the same potential as the processing chamber or lower than the potential of the processing chamber.