JP2003147530A - Device and method for forming metallic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a high quality Cu thin film 19 at a high film formation rate without exposing a substrate to plasma while remarkably reducing cost. SOLUTION: An electromagnetic wave is entered from a plasma antenna 11 into an excitation chamber 15, which is separated from a substrate storing chamber 1 to form Cl2 gas plasma 16 and etch a member 8 by excited chlorine, thereby forming a precursor (CuxCly) 18 in the chamber 1. The precursor (CuxCly) 18 is carried to the substrate 3 controlled at a temperature lower than that of the member 8 to be etched, and is turned to Cu ion only through a reducing reaction, then the Cu ion is applied to the substrate 3 to form a Cu thin film 19 on the surface of the substrate 3. Thus, in the state that the substrate is not exposed to plasma, the high quality Cu thin film 19 is formed at a high film formation rate while remarkably reducing cost.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal film production apparatus and a metal film production method for producing a metal film on a surface of a substrate by a vapor phase growth method.

[0002]

2. Description of the Related Art Conventionally, when a metal film, for example, a copper thin film, is produced by a vapor phase growth method, for example, a liquid organometallic complex such as copper / hexafluoroacetylacetonato / trimethylvinylsilane is used as a raw material. The raw material is dissolved in a solvent and vaporized using a thermal reaction to form a film on the substrate.

[0003]

In the conventional technique, it is difficult to improve the film forming rate because the film is formed by utilizing a thermal reaction. Further, the metal complex as a raw material is expensive, and since hexafluoroacetylacetonate and trimethylvinylsilane accompanying copper remain as impurities in the copper thin film, it is difficult to improve the film quality. It was

The present invention has been made in view of the above circumstances, and it is possible to use a low-priced raw material having a high film-forming rate.
An object of the present invention is to provide a metal film production apparatus and a metal film production method in which impurities do not remain in the film.

[0005]

In order to achieve the above object, the structure of the metal film forming apparatus of the present invention excites the chamber in which the substrate is housed and the source gas containing halogen which is isolated from the chamber. Exciting means, producing means for producing a precursor of a metal and a raw material in the chamber by the raw material excited by the exciting means, and the temperature of the substrate side is lower than the temperature of the producing means side, and the metal component of the precursor And a temperature control means for forming a film on the substrate.

Further, in the structure of the metal film forming apparatus of the present invention for achieving the above-mentioned object, the source gas containing halogen is plasma-excited and excited in the chamber in which the substrate is accommodated and the site separated from the chamber. Generating means for generating a precursor of a metal component and a raw material contained in the member to be etched inside the chamber by etching the member to be etched made of metal with the raw material, and the temperature of the substrate side from the temperature of the member to be etched side And a temperature control means for forming a film of the metal component of the precursor on the substrate.

Further, the structure of the metal film forming apparatus of the present invention for achieving the above object is provided in a cylindrical chamber in which a substrate is accommodated on one end face side and a chamber on the other end face side facing the substrate. A metal member to be etched, an excitation chamber in which one end is opened in the cylindrical portion of the chamber and a source gas containing halogen is supplied from the other end, and the inside of the excitation chamber is turned into plasma to generate source gas plasma to generate an excitation source. Is introduced into the chamber to etch the member to be etched in the chamber to generate a precursor of the metal component and the source gas contained in the member to be etched, and the temperature on the substrate side of the member to be etched And a temperature control means for forming a film of the metal component of the precursor on the substrate at a temperature lower than the temperature.

Further, the structure of the metal film forming apparatus of the present invention for achieving the above object is provided in a cylindrical chamber in which a substrate is accommodated on one end face side and a chamber on the other end face side facing the substrate. Porous disk-shaped member to be etched made of metal, excitation chamber provided on the opposite side of the substrate with the member to be etched being supplied, and a source gas containing halogen is supplied, and source gas plasma is generated by converting the inside of the excitation chamber into plasma. A plasma generating means for generating a precursor of a metal component contained in the member to be etched and a source gas inside the chamber by etching the member to be etched by passing the excited raw material through the member to be etched having a porous disk shape. And a temperature control unit for lowering the temperature of the substrate side to be lower than the temperature of the member to be etched to deposit the metal component of the precursor on the substrate.

Further, the structure of the metal film forming apparatus of the present invention for achieving the above object is provided in a cylindrical chamber in which a substrate is accommodated on one end face side and a chamber on the other end face side facing the substrate. A perforated disk-shaped ceiling plate made of an insulating material, a tubular member provided on the opposite side of the chamber with the ceiling plate sandwiched therebetween, a metal-etched member for sealing a portion of the tubular member facing the ceiling plate, and a ceiling plate A raw material gas supply means for supplying a raw material gas containing halogen to the inside of a tubular member surrounded by a member to be etched, and a raw material gas plasma generated by turning the inside of the tubular member into a plasma to generate a raw material gas plasma. By etching the member to be etched with gas plasma, a precursor of the metal component contained in the member to be etched and the source gas is generated, and the precursor is supplied into the chamber from the hole in the ceiling plate. A plasma generating means, characterized in that the to metal component of the precursor below the temperature of the temperature of the substrate side etched member side and a temperature control means for depositing on the substrate.

In order to achieve the above object, the metal film forming apparatus of the present invention comprises a chamber in which a substrate is accommodated and an upper part thereof is opened, and a porous plate made of an insulating material for sealing the upper opening of the chamber. Ceiling plate, a second chamber provided outside the ceiling member, an antenna member for plasmaizing the inside of the second chamber by power supply, and a raw material for supplying a raw material gas containing halogen into the second chamber A gas supply means, a plurality of metallic members to be etched that are arranged in the second chamber in a discontinuous state with respect to the electric current flow direction of the antenna member, and power is supplied to the antenna member to the ceiling plate side of the member to be etched. By generating an electric flow in the same direction as the electric flow direction of the antenna member, the inside of the second chamber is turned into a plasma to generate a source gas plasma, which is then covered with the source gas plasma. A plasma generating means for generating a precursor of a metal component and a source gas contained in the member to be etched by etching the etching member to supply the precursor into the chamber from the hole of the ceiling plate, and the temperature on the substrate side. And a temperature control means for lowering the temperature of the member to be etched to form a metal component of the precursor on the substrate.

The source gas containing halogen is
It is characterized by being a raw material gas containing chlorine. In addition, when the member to be etched is made of copper, CuxCly is generated as a precursor. In addition, the temperature control means is a means that is provided in the member to be etched and holds the member to be etched at a temperature higher than the temperature on the substrate side, and the member to be etched is tantalum or a chloride-forming metal. It is characterized by being tungsten or titanium.

In the method for producing a metal film of the present invention to achieve the above object, a halogen-containing source gas is excited separately from the chamber in which the substrate is accommodated, and the metal and the source are excited by the excited source. Generate a precursor inside the chamber,
It is characterized in that the temperature of the substrate side is made lower than the temperature of the generating means side to deposit the metal component of the precursor on the substrate.

Further, in the method for producing a metal film of the present invention for achieving the above object, a halogen-containing source gas is made into plasma at a site separated from a chamber in which a substrate is accommodated, and a metal source is excited by the excited source. By etching the member to be etched, a precursor of the metal component and the raw material contained in the member to be etched is generated inside the chamber,
The temperature of the substrate side is lower than the temperature of the member to be etched, and the metal component of the precursor is deposited on the substrate.

The source gas containing halogen is
It is characterized by being a raw material gas containing chlorine. It is also characterized in that CuxCly is produced as a precursor.
Further, the metal component of the precursor is characterized by being tantalum, tungsten, or titanium which is a chloride-forming metal.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A first embodiment of a metal film production apparatus and a metal film production method according to the present invention will be described with reference to FIGS. FIG. 1 is a schematic side view of the metal film forming apparatus according to the first embodiment of the present invention, and FIG. 2 is a view taken along the line II-II in FIG.

As shown in FIG. 1, it is formed in a cylindrical shape,
For example, a support base 2 is provided in the vicinity of the bottom of a chamber 1 made of ceramics (made of an insulating material), and a substrate 3 is provided on the support base 2.
Is placed. The support base 2 is provided with a temperature control means 6 provided with a heater 4 and a coolant circulation means 5, and the support base 2 is controlled by the temperature control means 6 to a predetermined temperature (for example, the substrate 3 is 100 ° C.).
To a temperature of 200 ° C.). The upper surface of the chamber 1 is an opening, and the opening is, for example, a ceiling plate 7 made of ceramics (insulating material).
Is blocked by. A metal (copper: Cu) member 8 to be etched is provided on the lower surface of the ceiling plate 7, and the member 8 to be etched has a quadrangular pyramid shape.

As shown in FIGS. 1 and 2, slit-shaped openings 9 are formed at four locations around the cylindrical portion of the chamber 1, and one end of a cylindrical passage 10 is formed in each opening 9. It is fixed. A tubular excitation chamber 15 made of an insulator is provided in the middle of the passage 10, and a coil-shaped plasma antenna 11 is provided around the excitation chamber 15.
1 is connected to a matching unit 12 and a power supply 13 to supply power. Plasma antenna 11, matching device 12 and power supply 13
The plasma generating means is constituted by.

A flow rate controller 14 is connected to the other end of the passage 10, and a raw material gas containing chlorine as halogen (He, Ar, etc., having a chlorine concentration of ≦ 50 is connected to the inside of the passage 10 via the flow rate controller 14. Cl ₂ gas diluted to about 10%, preferably about 10%)
Is supplied. By injecting an electromagnetic wave into the excitation chamber 15 from the plasma antenna 11, Cl ₂ gas is ionized and Cl ₂ gas plasma (raw material gas plasma) 16 is generated. That is, the excitation means for exciting the source gas containing chlorine in the excitation chamber 15 isolated from the chamber 1 is configured. Excited chlorine is sent from the opening 9 into the chamber 1 by the generation of the Cl ₂ gas plasma 16, and the member 8 to be etched is etched by the excited chlorine. The halogen contained in the raw material gas includes fluorine (F) and bromine (Br).
And iodine (I) can be applied.

In the above-mentioned metal film forming apparatus, the flow rate controller
The source gas is supplied into the passage 10 via the excitation chamber 1
Feed the raw material gas into 5. Power from the plasma antenna 11
By injecting a magnetic wave into the excitation chamber 15, Cl₂Gas
Ionized Cl₂Gas plasma (raw material gas plasma)
16 occurs. The pressure in the chamber 1 is adjusted by the vacuum device 17.
A predetermined differential pressure is set between the force and the pressure in the excitation chamber 15.
Therefore, Cl in the excitation chamber 15 ₂Excited chlorine of gas plasma 16
Send from the opening 9 to the member 8 to be etched in the chamber 1.
Be done. Etching the etched member 8 with excited chlorine
A reaction occurs, and inside the chamber 1, a precursor (CuxCly) 18
Is generated (generation means). At this time, the part to be etched
The material 8 is a heater 21 (temperature control hand) provided on the ceiling plate 7.
A predetermined temperature higher than the temperature of the substrate 3 (for example,
200 to 400 ° C.).

Precursor (Cu
The xCly) 18 is carried to the substrate 3 whose temperature is controlled to be lower than that of the member 8 to be etched. The precursor (CuxCly) 18 carried to the substrate 3 is reduced to Cu ions only and applied to the substrate 3, and a Cu thin film 19 is formed on the surface of the substrate 3.

The reaction at this time can be represented by the following equation. 2Cu + Cl ₂ → 2CuCl → 2Cu ↓ + Cl ₂ ↑ Exhaust port 2 for gases and etching products not involved in the reaction
Exhausted from 0.

Although Cl ₂ gas diluted with He, Ar or the like has been described as an example of the raw material gas, Cl ₂ gas may be used alone or HCl gas may be applied. HCl
When a gas is applied, HCl gas plasma is generated as the source gas plasma, but the precursor generated by the etching of the member 8 to be etched is CuxCly. Therefore, the source gas may be any gas containing chlorine, such as HCl gas and Cl gas.
It is also possible to use a mixed gas with _two gases. Also,
The material of the member to be etched 8 is not limited to copper (Cu), but a halide-forming metal, preferably a chloride-forming metal A
It is possible to use g, Au, Pt, Ta, Ti, W or the like. In this case, the precursor is a halide (chloride) of Ag, Au, Pt, Ta, Ti, W, etc., and the thin film formed on the surface of the substrate 3 is Ag, Au,
Pt, Ta, Ti, W, etc.

Since the metal film forming apparatus having the above structure uses the Cl ₂ gas plasma (source gas plasma) 16, the reaction efficiency is greatly improved and the film forming speed is increased. Further, since Cl ₂ gas is used as the source gas, the cost can be significantly reduced. Further, since the temperature of the substrate 3 is controlled to be lower than that of the copper plate member 7 by using the temperature control means 6, it is possible to reduce the amount of impurities such as chlorine remaining in the Cu thin film 19 and to improve the quality of the Cu thin film 19. Can be generated.

In the excitation chamber 15 which is isolated from the chamber 1,
Since the Cl ₂ gas plasma 16 is generated, the substrate 3 is not exposed to the plasma, and the substrate 3 is not damaged by the plasma. For example,
In the substrate 3 on which the film of another material is formed in the previous step, the film of the material formed in the previous step is not damaged.

The means for generating the Cl ₂ gas plasma 16 in the excitation chamber 15, that is, the means for exciting the raw material gas to generate the excited raw material (excitation means) includes a microwave, a laser,
It is also possible to use an electron beam, synchrotron radiation or the like.

In addition, a copper filament is provided inside the excitation chamber 15, the copper filament is connected to a DC power source, and a precursor gas (CuxCly) is brought into contact with the copper filament heated to 300 ° C. to 800 ° C. by the DC power source. )
It is also possible to generate and send it into the chamber 1 (generation means). Further, a copper plate with a hole is provided inside the excitation chamber 15, the copper plate is connected to a DC power source, and a precursor gas (CuxCly) is caused by flowing a source gas through the hole of the copper plate heated to 300 ° C. to 800 ° C. by the DC power source. It is also possible to generate and send it into the chamber 1 (generation means). In these cases, the member to be etched 8 becomes unnecessary, restrictions on the shape of the chamber 1 are lessened, and the size of the apparatus can be reduced.

A metal film production apparatus and a metal film production method according to the second embodiment of the present invention will be described with reference to FIG. FIG. 3 shows a schematic side view of a metal film forming apparatus according to a second embodiment of the invention. The same members as those shown in FIG. 1 are designated by the same reference numerals, and duplicate description is omitted.

As shown in the figure, the upper surface (the other end surface side) of the chamber 1 is an opening, and the opening is made of metal (made of copper: Cu
It is closed by a member 22 to be etched having a porous disk shape having a large number of holes 22a. Member to be etched 22
A ceiling chamber 23 is provided on the upper side of the above, that is, on the side opposite to the substrate 3 with the member to be etched 22 interposed therebetween, and the lower end of a cylindrical passage 24 is fixed to the top of the ceiling chamber 23. An insulating tubular excitation chamber 25 is provided in the middle of the passage 24, a coil-shaped plasma antenna 11 is provided around the excitation chamber 25, and the plasma antenna 11 includes a matching unit 12 and a power supply 13. It is connected and power is supplied. It is also possible to arrange the plasma antenna 11 to the outside of the ceiling chamber 23.

A flow rate controller 14 is connected to the upper end side of the passage 24, and a source gas containing chlorine as halogen (He, Ar, etc., having a chlorine concentration of ≦ 50%) is fed into the passage 24 via the flow rate controller 14. , Preferably Cl ₂ gas diluted to about 10%)
Is supplied. By injecting electromagnetic waves from the plasma antenna 11 into the excitation chamber 25, Cl ₂ gas is ionized and Cl ₂ gas plasma (raw material gas plasma) 16 is generated. That is, the excitation means for exciting the source gas containing chlorine in the excitation chamber 25 isolated from the chamber 1 is configured. Due to the generation of Cl ₂ gas plasma 16, excited chlorine is sent to the member to be etched 22 and passes through the hole 22a, and the member to be etched 22 is etched by the excited chlorine to generate a precursor (CuxCly) 18 inside the chamber 1. .

In the above-described metal film forming apparatus, Cl ₂ gas plasma 16 is generated in the excitation chamber 25, and the member 22 to be etched is etched by the excited chlorine to generate the precursor (CuxCly) 18 inside the chamber 1. . Due to the etching action of the excited chlorine, the member 22 to be etched has a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3.
The precursor (CuxCly) 18 generated inside the chamber 1 is carried to the substrate 3 whose temperature is controlled to be lower than that of the member 22 to be etched. The precursor (CuxCly) 18 carried to the substrate 3 is converted into only Cu ions by a reduction reaction and applied to the substrate 3, and a Cu thin film 16 is formed on the surface of the substrate 3.

In the above-described metal film forming apparatus, the Cl ₂ gas plasma 16 is generated in the excitation chamber 25 which is isolated from the chamber 1. Therefore, the substrate 3 is not exposed to the plasma and the substrate 3 is exposed to the plasma. No damage will occur. In addition, isolation from the chamber 1 is prevented by a large number of holes 22a.
Since the perforated plate-shaped member to be etched 22 having the above is used, the member for isolation can be used also as the member to be etched, and the number of parts of the apparatus can be reduced.

A metal film production apparatus and a metal film production method according to the third embodiment of the present invention will be described with reference to FIG. FIG. 4 shows a schematic side view of the metal film production apparatus according to the third embodiment of the present invention. The same members as those shown in FIG. 1 are designated by the same reference numerals, and duplicate description is omitted.

As shown in the figure, the upper surface (the other end surface side) of the chamber 1 is an opening, and the opening is closed by a perforated disk-shaped ceiling plate 28 having a large number of holes 28a made of an insulating material. There is. Upper part of the chamber 1 (opposite end side) with the ceiling plate 28 interposed
A tubular member 29 is provided in the container, and an upper opening (a portion facing the ceiling plate 28) of the tubular member 29 is sealed by an etched member 30 made of metal (made of copper: Cu). A plasma chamber 31 is formed inside the cylindrical member 29 surrounded by the ceiling plate 28 and the member 30 to be etched.

A coil-shaped plasma antenna 34 is provided around the cylindrical member 29 of the plasma chamber 31, and a matching device 35 and a power source 36 are connected to the plasma antenna 34 to supply power. The plasma antenna 34, the matching device 35, and the power supply 36 constitute plasma generating means.

The tubular member 29 above the plasma chamber 31 has
A source gas containing chlorine as a halogen in the plasma chamber 31 (He, Ar, etc., having a chlorine concentration of ≦ 50%, preferably
Nozzle 32 for supplying Cl ₂ gas diluted to about 10%
Are connected. The nozzle 32 is opened in the horizontal direction, and the raw material gas is sent to the nozzle 32 via the flow rate controller 33 (raw material gas supply means). As the halogen contained in the source gas, it is possible to apply fluorine (F), bromine (Br), iodine (I), or the like.

A ceiling plate made of an insulating material is provided in place of the member to be etched 30, and a perforated disk-shaped member to be etched having a large number of holes a made of metal is provided in place of the ceiling plate 28. It is also possible to arrange the planar coil-shaped plasma antenna above the ceiling plate.

In the above-described metal film forming apparatus, the raw material gas is supplied from the nozzle 32 into the plasma chamber 31, and the electromagnetic wave is incident from the plasma antenna 34 into the plasma chamber 31, whereby the Cl ₂ gas is ionized. Cl ₂ gas plasma (source gas plasma) 37 is generated. The Cl ₂ gas plasma 37 causes an etching reaction in the member to be etched 30, and a precursor (CuxCly) 18 is generated, and the precursor (CuxCly) 18 is supplied to the inside of the chamber 1 through the hole 28 a of the ceiling plate 28. It

At this time, the member to be etched 30 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the Cl ₂ gas plasma 37, and the precursor supplied to the inside of the chamber 1. The (CuxCly) 18 is the substrate 3 whose temperature is controlled to be lower than that of the member to be etched 30.
Be carried to. The precursor (CuxCly) 18 carried to the substrate 3 is reduced to Cu ions only and applied to the substrate 3, and a Cu thin film 19 is formed on the surface of the substrate 3.

In the above-mentioned metal film forming apparatus, the Cl ₂ gas plasma 37 is generated in the plasma chamber 31 which is isolated from the chamber 1. Therefore, the substrate 3 is not exposed to the plasma, and the substrate 3 is exposed to the plasma. No damage will occur. Further, since the member 30 to be etched closes the upper part of the plasma chamber 31, the member 30 to be etched can be easily replaced even if the member 30 to be etched is consumed by etching.

A metal film production apparatus and a metal film production method according to the fourth embodiment of the present invention will be described with reference to FIG. FIG. 5 shows a schematic side view of a metal film forming apparatus according to a fourth embodiment of the present invention. The same members as those shown in FIGS. 1 and 4 are designated by the same reference numerals, and duplicate description is omitted.

As shown in the figure, the upper surface (the other end surface side) of the chamber 1 is an opening, and the opening is closed by a perforated disk-shaped ceiling plate 28 having a large number of holes 28a made of an insulating material. There is. A second chamber 41 is provided above the ceiling plate 28. The second chamber 41 includes a tubular portion 42 provided on the upper portion of the chamber 1 and a second ceiling plate 43 that seals an upper opening of the tubular portion 42. Second chamber 41
A planar coil-shaped plasma antenna 44 as an antenna member is provided on the upper surface of the second ceiling plate 43, and a matching device 45 and a power supply 46 are connected to the plasma antenna 44 to supply power. The matching device 45 and the power supply 46 constitute a plasma generating means.

A metal (Cu) member to be etched 47 is sandwiched between the opening on the upper surface of the second chamber 41 and the second ceiling plate 43. The member to be etched 47 is the second
A ring portion 48 that is sandwiched between the openings on the upper surface of the chamber 41.
And the ring portion 48 has a short tubular shape with the same diameter as the second chamber 41. Second on the inner circumference side of the ring portion 48
A plurality of protrusions 49 extending in the vicinity of the center of the chamber 41 in the radial direction are provided in the circumferential direction with the same width, and the lower surface is inclined upward and the thickness is gradually reduced. The ring portion 48 is grounded, and the plurality of protrusions 49 are electrically connected to each other and maintained at the same potential. Then, there is a notch (space) between the protrusions 49. That is, the plurality of ring portions 48 of the member to be etched 47 are arranged inside the second chamber 41 in a discontinuous state with respect to the flow direction of electricity of the plasma antenna 44.

It is also possible to provide a sheath heater or a sensor member on the protrusion 49 to control the temperature of the protrusion 49 to a predetermined temperature higher than the temperature of the substrate 3 (temperature control means). At this time, the sheath heater and the sensor member may be provided on all the projections 49, or may be provided on the projections 49 alternately arranged. Further, the sheath heater and the sensor member can be provided on the ring portion 48.

The member to be etched 47 of the second chamber 41
In the lower part of the second chamber 41, a source gas containing chlorine as halogen (He, Ar, etc., having a chlorine concentration of ≦ 50
A nozzle 32 for supplying Cl ₂ gas diluted to about 10%, preferably about 10% is connected. The nozzle 32 opens obliquely upward, and a raw material gas is sent to the nozzle 32 via a flow rate controller 33 (raw material gas supply means). As the halogen contained in the source gas, it is possible to apply fluorine (F), bromine (Br), iodine (I), or the like.

In the above-described metal film forming apparatus, the raw material gas is supplied from the nozzle 32 into the second chamber 41, and the electromagnetic wave is introduced into the second chamber 41 from the plasma antenna 44, whereby the Cl ₂ gas is ionized. As a result, Cl ₂ gas plasma (source gas plasma) 37 is generated. The member to be etched 47, which is a conductor, exists under the plasma antenna 44, but since there is a notch (space) between the protrusions 49, even if an induced current flows, the protrusion 4 does not move.
When a current flows around 9 and the member 47 to be etched is viewed from the substrate 3 side, there is no flow in the direction canceling the flow of electricity of the plasma antenna 44, and
The ring portion 48 is grounded and the protrusion 49 is maintained at the same potential. As a result, the member to be etched 4 which is a conductor
Even if 7 is present, the electromagnetic wave from the plasma antenna 44 surely enters the second chamber 41, and the Cl ₂ gas plasma 37 is stably generated below the member to be etched 47.

The Cl ₂ gas plasma 37 causes an etching reaction on the member to be etched 47 made of copper, and the precursor (Cu
xCly) 18 is generated and the precursor (CuxCly) 18 is supplied to the inside of the chamber 1 through the hole 28 a of the ceiling plate 28. At this time, the member to be etched 47 is maintained at a predetermined temperature (eg, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the Cl ₂ gas plasma 37, and the chamber 1
The precursor (CuxCly) 18 supplied to the inside of the substrate is carried to the substrate 3 whose temperature is controlled to be lower than that of the member to be etched 47. The precursor (CuxCly) 18 carried to the substrate 3 is reduced to Cu ions only and applied to the substrate 3, and a Cu thin film 19 is formed on the surface of the substrate 3.

In the above-described metal film forming apparatus, the Cl ₂ gas plasma 37 is generated in the second chamber 41 which is separated from the chamber 1. Therefore, the substrate 3 is not exposed to the plasma and the plasma is applied to the substrate 3. Will not cause damage. Further, since the member to be etched 47 is composed of the ring portion 48 and the protruding portion 49, the second chamber 4
It becomes possible to dispose the member to be etched 47 made of copper, which is a conductor, in the inside of 1. Further, since the ring portion 47 side of the protrusion 49 is thick, it is possible to effectively use the Cl ₂ gas plasma 37 in the lower portion to efficiently carry out the etching reaction.

A large number of grooves, depressions, etc. are formed on the lower side of the member to be etched 47 (protrusions 49) to make the surface discontinuous on the concave side, which is etched by the Cl ₂ gas plasma 37. Even if copper grows from the formed precursor 18 to the lower side of the protrusion 49, it does not grow directly below. It is also possible to extend the second ceiling plate 43 to the outer periphery of the tubular portion 42 and to provide a coil-shaped plasma antenna on the outside of the extended second ceiling plate 43 (outer periphery of the tubular portion 42). Is.

A metal film production apparatus and a metal film production method according to the fifth embodiment of the present invention will be described with reference to FIG. FIG. 6 shows a schematic side view of a metal film forming apparatus according to a fifth embodiment of the present invention. The same members as those shown in FIGS. 1 and 5 are designated by the same reference numerals, and duplicate explanations are omitted.

As shown in the figure, the upper surface (the other end surface side) of the chamber 1 is an opening, and the opening is closed by a perforated disk-shaped ceiling plate 28 having a large number of holes 28a made of an insulating material. There is. A second chamber 51 is provided above the ceiling plate 28. The second chamber 51 is configured such that a bowl-shaped (dome-shaped) ceiling member 52 that is convex outward of an insulating material (ceramics or the like) is fixed to the opening of the chamber 1.

The opening on the upper surface of the chamber 1 and the ceiling member 52
An etching target member 53 made of metal (Cu) is sandwiched between and. The member to be etched 53 has a chamber 1
Is provided with a ring portion 54 that is clamped in an opening on the upper surface of
On the inner peripheral side of the ring portion 54, a plurality of projections 55 are provided in the circumferential direction that extend to the vicinity of the radial center of the chamber 1 and extend along the bowl shape inside the ceiling member 52. The ring portion 54 is grounded, and the plurality of protrusions 55 are electrically connected to maintain the same potential.

On the other hand, a plasma antenna 56, which serves as an antenna member for plasmaizing the inside of the second chamber 51, is provided above the ceiling member 52, and the plasma antenna 56 follows the bowl shape of the ceiling member 52. It is formed in the shape of a conical ring. A matching device 45 as a plasma generating means and a power source 46 are connected to the plasma antenna 56 to supply power. In the member to be etched 53, a plurality of protrusions 55 are provided on the inner peripheral side of the ring portion 54 in the circumferential direction along the bowl shape of the ceiling member 52, and the notches (spaces) formed between the protrusions 55. Exists. Therefore, a plurality of plasma antennas 56 are arranged inside the second chamber 41 in a discontinuous state with respect to the direction of electricity flow.

At the top of the ceiling member 52 of the second chamber 51, a source gas containing chlorine as a halogen inside the second chamber 51 (a chlorine concentration of ≦ 50%, preferably about 10% for He, Ar, etc.) is provided. A nozzle 57 for supplying Cl ₂ gas diluted to the above is connected. The nozzle 57 is opened downward, and the raw material gas is sent to the nozzle 57 via the flow rate controller 58 (raw material gas supply means). As the halogen contained in the source gas, it is possible to apply fluorine (F), bromine (Br), iodine (I), or the like.

In the above-described metal film forming apparatus, the raw material gas is supplied from the nozzle 57 into the second chamber 51, and the electromagnetic wave is incident from the plasma antenna 56 into the second chamber 51, whereby the Cl ₂ gas is ionized. As a result, Cl ₂ gas plasma (source gas plasma) 37 is generated. The member to be etched 53, which is a conductor, exists under the plasma antenna 56, but since there is a notch (space) between the protrusions 55, the protrusion 5 does not flow even if an induced current flows.
When a current flows around 5 and the member to be etched 53 is viewed from the substrate 3 side, there is no flow in the direction canceling the flow of electricity of the plasma antenna 56, and
The ring portion 54 is grounded and the protrusion 55 is maintained at the same potential. As a result, the member to be etched 5 which is a conductor
Even if 3 exists, the electromagnetic wave from the plasma antenna 56 surely enters the second chamber 51, and the Cl ₂ gas plasma 37 is stably generated below the member 53 to be etched.

The Cl ₂ gas plasma 37 causes an etching reaction on the member to be etched 53 made of copper, and the precursor (Cu
xCly) 18 is generated and the precursor (CuxCly) 18 is supplied to the inside of the chamber 1 through the hole 28 a of the ceiling plate 28. At this time, the member to be etched 53 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the Cl ₂ gas plasma 37, and the chamber 1 is
The precursor (CuxCly) 18 supplied to the inside of the substrate is carried to the substrate 3 whose temperature is controlled to be lower than that of the member to be etched 53. The precursor (CuxCly) 18 carried to the substrate 3 is reduced to Cu ions only and applied to the substrate 3, and a Cu thin film 19 is formed on the surface of the substrate 3.

In the above-described metal film forming apparatus, the Cl ₂ gas plasma 37 is generated in the second chamber 51 which is separated from the chamber 1. Therefore, the substrate 3 is not exposed to the plasma, and the plasma is applied to the substrate 3. Will not cause damage. Further, since the member to be etched 53 is composed of the ring portion 54 and the protruding portion 55, the second chamber 5
It becomes possible to dispose the member to be etched 47 made of copper, which is a conductor, in the inside of 1. Further, since the ceiling member 52 is formed in a bowl shape and the plasma antenna 56 is formed in a conical ring shape along the bowl shape of the ceiling member 52, an electromagnetic wave is incident from around the ceiling member 52 and Cl ₂ gas is emitted. Plasma 37 can be generated, and Cl inside the ceiling member 52 can be generated.
It becomes possible to stabilize the _two- gas plasma 37. Therefore, the Cl ₂ gas plasma 37 inside the second chamber 51 can be made uniform by one power supply 46.

A large number of grooves, depressions, etc. are formed on the lower side of the member 53 to be etched (protruding portion 55) to make the surface discontinuous on the concave side, which is etched by the Cl ₂ gas plasma 37 and generated. Even if copper grows from the formed precursor 18 to the lower side of the protrusion 55, it does not grow directly below.

In the above-mentioned embodiment, the precursor (CuxCly) is supplied from the ceiling side of the chamber, but the setting of the precursor (CuxCly) supply direction may be reversed. Well, in some cases, it is also possible to set the supply direction of the precursor (CuxCly) in the left-right direction.

[0059]

According to the metal film forming apparatus of the present invention, a chamber for accommodating a substrate, an exciting means for exciting a source gas containing halogen from the chamber and exciting the source gas, and a metal source is excited by the exciting means. And a temperature control means for forming a precursor metal component on the substrate by making the temperature of the substrate side lower than the temperature of the generation means side. Therefore, the film formation speed is fast and an inexpensive raw material can be used without exposing the substrate to the excitation source so that damage due to the excitation source does not occur, and a metal film in which no impurities remain in the film is formed. It is possible to provide an apparatus for producing a metal film.

Further, the apparatus for producing a metal film of the present invention includes a chamber for accommodating a substrate and a source material gas containing halogen which is plasma-excited at a site separated from the chamber to form a metal member to be etched by the excited source material. A means for generating a precursor of a metal component and a raw material contained in the member to be etched by etching inside the chamber, and a metal component of the precursor by setting the temperature on the substrate side lower than the temperature on the member to be etched. Since it is provided with a temperature control means for forming a film on the substrate, the film formation speed is fast and an inexpensive raw material can be used in a state where there is no risk of plasma damage without exposing the substrate to the plasma. It is possible to provide a metal film forming apparatus capable of forming a metal film in which no impurities remain in the film.

Further, the metal film forming apparatus of the present invention includes a cylindrical chamber in which the substrate is accommodated on one end surface side, a metal member to be etched provided in the chamber on the other end surface side facing the substrate, and the chamber. The inside of the chamber is formed by introducing an excitation source into the chamber by turning the inside of the excitation chamber into a plasma and generating the source gas plasma by exciting the inside of the excitation chamber into the excitation chamber to which the source gas containing halogen is supplied from the other end. The plasma generating means for etching the member to be etched to generate a precursor of the metal component and the source gas contained in the member to be etched, and the temperature of the substrate side lower than the temperature of the member to be etched side of the precursor Since the temperature control means for forming the metal component on the substrate is provided, the plasma is separated from the substrate by generating the plasma in the excitation chamber, and the substrate is exposed to the plasma. A metal film forming apparatus capable of forming a metal film that has a high film formation rate, can use an inexpensive raw material, and has no impurities remaining in the film, without the possibility of plasma damage You can

In addition, the apparatus for producing a metal film of the present invention includes a cylindrical chamber for accommodating a substrate on one end surface side and a metal porous disk-shaped object to be etched provided in the chamber on the other end surface side facing the substrate. Member, the excitation chamber provided on the opposite side of the substrate across the member to be etched, to which the source gas containing halogen is supplied, and the inside of the excitation chamber is plasmatized to generate the source gas plasma, and the excitation source is a porous disk. Of the member to be etched by passing through the member to be etched to generate a precursor of a metal component and a source gas contained in the member to be etched inside the chamber; Since the temperature control means for lowering the temperature of the substrate side to deposit the metal component of the precursor on the substrate is provided, the plasma is generated in the excitation chamber and the substrate Zuma is isolated by the member to be etched itself, there is no risk of plasma damage without exposing the substrate to plasma, the film formation rate is fast, inexpensive raw materials can be used, and impurities do not remain in the film A metal film manufacturing apparatus capable of forming a metal film can be provided.

Further, the metal film forming apparatus of the present invention has a cylindrical chamber in which a substrate is housed on one end surface side and a porous disk-shaped ceiling made of an insulating material provided in the chamber on the other end surface side facing the substrate. Plate, a tubular member provided on the opposite side of the chamber with the ceiling plate sandwiched therebetween, a metal-etched member for sealing a portion of the tubular member facing the ceiling plate, and a tube surrounded by the ceiling plate and the etched member. A raw material gas supply means for supplying a raw material gas containing halogen to the inside of the member, and a plasma of the inside of the cylindrical member which is provided around the cylindrical member to generate the raw material gas plasma, and the material to be etched is etched with the raw material gas plasma As a result, plasma generating means for generating a precursor of the metal component and the source gas contained in the member to be etched and supplying the precursor into the chamber from the hole of the ceiling plate, and the temperature of the substrate side. Since the temperature control means for forming a metal component of the precursor on the substrate by lowering the temperature lower than the temperature of the member to be etched is provided, the substrate and the plasma are separated by generating plasma inside the tubular member, Without exposing the substrate to plasma, there is no risk of damage due to plasma, and in addition, the member to be etched can be easily replaced.
It is possible to provide a metal film manufacturing apparatus that can form a metal film in which an inexpensive raw material can be used, which has a high film formation speed, and impurities do not remain in the film.

Further, the metal film production apparatus of the present invention includes a chamber in which a substrate is accommodated and an upper portion thereof is opened, a perforated ceiling plate made of an insulating material for sealing the upper opening of the chamber, and an outer portion of the ceiling member. A second chamber provided on one side, an antenna member for turning the inside of the second chamber into a plasma by power supply, a source gas supply means for supplying a source gas containing halogen into the second chamber, and an electric power of the antenna member. A plurality of metallic members to be etched arranged in the second chamber in a discontinuous state with respect to the flow direction of the antenna, and the antenna member is fed to the ceiling plate side of the member to be etched to have the same electric flow direction of the antenna member. By generating a flow of electricity in the direction, the inside of the second chamber is turned into plasma to generate source gas plasma, and the member to be etched is etched by the source gas plasma. By means of a plasma generating means for generating a precursor of a metal component and a source gas contained in the member to be etched and supplying the precursor into the chamber from the hole of the ceiling plate, and the temperature of the substrate side of the member to be etched side Since the temperature control means for lowering the temperature to deposit the metal component of the precursor on the substrate is provided, the substrate and the plasma are generated by generating the plasma in the state where the member to be etched is arranged inside the second chamber. To form a metal film that is isolated and does not expose the substrate to plasma and is not damaged by plasma. It is possible to provide a metal film production apparatus capable of

In the method for producing a metal film of the present invention, a source gas containing halogen is excited by being isolated from the chamber in which the substrate is housed, and the metal and the precursor of the source are introduced into the chamber by the excited source. Since the temperature of the substrate is generated and the temperature of the substrate is made lower than the temperature of the generator to deposit the metal component of the precursor on the substrate, damage by the excitation source may occur without exposing the substrate to the excitation source. It is possible to provide a method for producing a metal film, in which a metal film having a high film formation rate and an inexpensive raw material can be used in the absence of impurities, and a metal film in which impurities do not remain in the film can be formed.

Further, in the method for producing a metal film of the present invention, the halogen-containing source gas is made into plasma at a site separated from the chamber in which the substrate is accommodated, and the metal-to-be-etched member is etched by the excited source. As a result, a precursor of the metal component and the raw material contained in the member to be etched is generated inside the chamber, the temperature on the substrate side is made lower than the temperature on the member to be etched, and the metal component of the precursor is deposited on the substrate. Since the substrate is not exposed to plasma, there is no risk of damage due to plasma, the deposition rate is fast, inexpensive raw materials can be used, and a metal film that does not leave impurities in the film is formed. A method for producing a metal film capable of forming a film can be used.

[Brief description of drawings]

FIG. 1 is a schematic side view of a metal film manufacturing apparatus according to a first embodiment of the present invention.

FIG. 2 is a view taken along the line II-II in FIG.

FIG. 3 is a schematic side view of a metal film production apparatus according to a second embodiment of the present invention.

FIG. 4 is a schematic side view of a metal film production apparatus according to a third embodiment of the present invention.

FIG. 5 is a schematic side view of a metal film production apparatus according to a fourth embodiment of the present invention.

FIG. 6 is a schematic side view of a metal film forming apparatus according to a fifth embodiment of the present invention.

[Explanation of symbols]

1 Chamber 2 Support 3 Substrate 4 Heater 5 Refrigerant Flow Means 6 Temperature Control Means 7 Copper Plate Members 8, 22, 47, 53 Etched Member 9 Openings 10, 24 Passages 11, 34, 44, 56 Plasma Antennas 12, 35, 45 Matching device 13, 36, 46 Power supply 14, 33, 58 Flow controller 15, 25 Excitation chamber 16, 37 Cl ₂ gas plasma (source gas plasma) 17 Vacuum device 18 Precursor (CuxCly) 19 Cu thin film 20 Exhaust port 21 Heater 23 Ceiling chamber 31 Plasma chamber 32,57 Nozzle 41,51 Second chamber 42 Cylindrical part 43 Second ceiling plate 48,54 Ring part 49,55 Projection part 52 Ceiling member

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hitoshi Sakamoto             1-8 Koura, Kanazawa-ku, Yokohama-shi, Kanagawa               Mitsubishi Heavy Industries, Ltd. Basic Technology Research Center F-term (reference) 4K030 AA02 AA03 BA01 BA17 BA18                       BA20 EA01

Claims (15)

[Claims] 1. A chamber for accommodating a substrate, an excitation means for exciting a source gas containing halogen from the chamber and exciting the source gas, and a precursor of a metal and a source for the chamber by the source excited by the excitation means. An apparatus for producing a metal film, comprising: a generating unit that is generated inside, and a temperature control unit that makes the temperature of the substrate lower than the temperature of the generating unit to form a metal component of the precursor on the substrate. . 2. A chamber for accommodating a substrate and a source gas containing halogen are plasma-converted at a site separated from the chamber, and the metal-to-be-etched member is etched by the excited raw material to be included in the member to be etched. Generating means for generating a precursor of the metal component and the raw material inside the chamber, and a temperature control means for forming the precursor metal component on the substrate by making the temperature of the substrate side lower than the temperature of the member to be etched. An apparatus for producing a metal film, comprising: 3. A cylindrical chamber in which a substrate is accommodated on one end face side, a metal member to be etched which is provided in the chamber on the other end face side facing the substrate, and one end of which is opened in the cylindrical portion of the chamber. The excitation chamber to which the source gas containing halogen is supplied from the end and the inside of the excitation chamber are turned into plasma to generate source gas plasma, and the excited source is introduced into the chamber to etch the member to be etched in the chamber. Plasma generating means for generating a precursor of a metal component and a source gas contained in the etching member, and a temperature for forming a metal component of the precursor on the substrate by lowering the temperature of the substrate side than the temperature of the member to be etched side A metal film production apparatus comprising: a control means. 4. A cylindrical chamber in which a substrate is housed on one end surface side, and a metal porous disk-shaped member to be etched provided in the chamber on the other end surface side facing the substrate,
An excitation chamber, which is provided on the opposite side of the substrate across the member to be etched and to which a source gas containing halogen is supplied, and the inside of the excitation chamber is turned into plasma to generate source gas plasma, and the excitation source is etched into a porous disk shape. A plasma generating means for etching a member to be etched by passing the member to generate a precursor of a metal component and a raw material gas contained in the member to be etched inside the chamber, and a temperature of the substrate side to a temperature of the member to be etched side. And a temperature control means for forming a metal component of the precursor on the substrate at a temperature lower than that of the metal film forming apparatus. 5. A cylindrical chamber in which a substrate is accommodated on one end face side, a perforated disk-shaped ceiling plate made of an insulating material provided in the chamber on the other end face side facing the substrate, and a chamber sandwiching the ceiling plate. , A metal member to be etched which seals a portion of the tubular member facing the ceiling plate of the tubular member, and a raw material containing halogen inside the tubular member surrounded by the ceiling plate and the member to be etched. A metal contained in the member to be etched by supplying a source gas supplying means for supplying a gas and a plasma provided inside the cylindrical member provided around the cylindrical member to generate a source gas plasma and etching the member to be etched with the source gas plasma. Plasma generating means for generating a precursor of the component and the source gas to supply the precursor into the chamber from the hole of the ceiling plate, and the temperature of the substrate side from the temperature of the etched member side. And a temperature control means for film-forming the metal component of the precursor on the substrate. 6. A chamber in which a substrate is accommodated and whose upper portion is opened, a perforated ceiling plate made of an insulating material for sealing the upper opening of the chamber, and a second chamber provided outside the ceiling member. An antenna member for turning the inside of the second chamber into plasma by power supply, a source gas supply means for supplying a source gas containing halogen into the second chamber, and a discontinuous state with respect to the electric flow direction of the antenna member. In the second chamber, a plurality of metallic members to be etched and the antenna member are supplied with electric power to generate electric current in the same direction as the electric current flowing through the antenna member on the ceiling plate side of the member to be etched. Included in the member to be etched by converting the inside of the second chamber into plasma to generate a source gas plasma and etching the member to be etched with the source gas plasma. Plasma generating means for generating a precursor of a metal component and a source gas to supply the precursor to the inside of the chamber from the hole in the ceiling plate, and the precursor on the side of the substrate lower than the temperature of the member to be etched. An apparatus for producing a metal film, comprising: a temperature control means for forming a metal component of a body on a substrate. 7. The metal film forming apparatus according to claim 1, wherein the halogen-containing source gas is a chlorine-containing source gas. 8. The metal film forming apparatus according to claim 8, wherein the member to be etched is made of copper to generate CuxCly as a precursor. 9. The temperature control unit according to claim 2, wherein the temperature control unit is a unit that is provided on the member to be etched and that keeps the member to be etched at a temperature higher than the temperature on the substrate side. An apparatus for producing a metal film. 10. The metal film forming apparatus according to claim 2, wherein the member to be etched is tantalum, tungsten or titanium which is a halide forming metal. . 11. A substrate gas is isolated from a chamber in which a substrate is housed, a halogen-containing source gas is excited, a precursor of a metal and a source is generated inside the chamber by the excited source, and the temperature of the substrate side is increased. Is lower than the temperature on the side of the generating means to form the metal component of the precursor on the substrate. 12. A source gas containing halogen is converted into plasma at a site separated from the chamber in which the substrate is accommodated,
The precursor of the metal component and the raw material contained in the member to be etched is generated inside the chamber by etching the member to be etched made of metal with the excited raw material, and the temperature of the substrate side is lower than the temperature of the member to be etched side. A method for producing a metal film, characterized in that the metal component of the precursor is formed into a film on the substrate by lowering 13. The method for producing a metal film according to claim 11 or 12, wherein the halogen-containing source gas is a chlorine-containing source gas. 14. The Cu as a precursor according to claim 13,
A method for producing a metal film, which comprises producing xCly. 15. The method according to any one of claims 11 to 13,
The metal film forming method, wherein the metal component of the precursor is tantalum, tungsten or titanium which is a halide forming metal.