JP4305819B2 - Metal film production apparatus and metal film production method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal film manufacturing method and apparatus for manufacturing a metal thin film, and is a useful invention when, for example, a metal material having a high material cost is formed.
[0002]
[Prior art]
At present, in the manufacture of semiconductors and the like, film formation using a plasma CVD (Chemical Vapor Deposition) apparatus is known. A plasma CVD apparatus is a plasma reaction of a gas such as an organometallic complex that becomes a material of a film introduced into a chamber by a high frequency incident from a high frequency antenna, and a chemical reaction on the substrate surface by active excited atoms in the plasma. Is a device for forming a metal thin film or the like by promoting the above.
[0003]
On the other hand, the present inventors installed a member to be etched containing a metal component desired to be formed in a chamber, and etched the member to be etched with a plasma of a halogen gas to thereby obtain a precursor that is a halide of the metal component. And a plasma CVD apparatus and a film forming method for forming only the metal component of the precursor on the substrate have been developed. As an example of the member to be etched, for example, there is a target described in Patent Document 1.
[0004]
[Patent Document 1]
European Patent Application No. 1247872
[0005]
[Problems to be solved by the invention]
In the plasma CVD apparatus and film forming method developed by the present inventors, when a metal material having a high material cost is to be formed, it is necessary to form the member to be etched with a high cost metal material, The problem was occurring. That is, when a member to be etched is formed of a high-cost metal material, the first problem that a high-cost metal material needs to be prepared as a bulk material, and many of the high-cost metal materials have a large specific gravity. The second problem is that the weight of the whole plasma CVD apparatus increases and it is difficult to remove a heavy member to be etched. The present invention has been made in view of the above circumstances, and forms a member to be etched without using a large amount of a high-cost metal material in a bulk state, thereby solving the cost and handling problems of the member to be etched. An object is to provide a manufacturing method and an apparatus.
[0006]
[Means for Solving the Problems]
The member to be etched according to the first invention for solving the above object is as follows: The member to be etched is etched with halogen gas plasma to form a metal component and a halogen precursor, and the metal component of the precursor is formed on the substrate. A member to be etched, which is used in a metal film manufacturing apparatus and serves as a raw material for a metal to be deposited, wherein the carrier is coated with a metal capable of generating a high vapor pressure halide. is there.
[0007]
The member to be etched according to the second invention for solving the above object is
In the member to be etched described in the first invention,
A member to be etched, wherein the carrier is coated with the metal by a sputtering method or a vacuum deposition method.
[0008]
The member to be etched according to the third invention for solving the above object is as follows:
In the member to be etched described in the first invention,
The member to be etched is characterized in that the metal in a ribbon shape is attached to the carrier.
[0009]
The member to be etched according to the fourth invention for solving the above object is as follows:
In the member to be etched described in the first invention,
A member to be etched, wherein the carrier is coated with the metal component of the metal oxide by sintering the metal oxide in the form of a slurry sprayed or coated on the carrier in a reducing atmosphere. It is.
[0010]
The member to be etched according to the fifth invention for solving the above object is as follows:
In the member to be etched described in the first invention,
The carrier has a rod shape, and the metal to be etched is wound around the rod-like carrier.
[0011]
The member to be etched according to the sixth invention for solving the above object is as follows:
In the member to be etched according to any one of the first to fifth inventions,
The member to be etched is characterized in that a metal nitride film is interposed between the carrier and the coated metal.
[0012]
The member to be etched according to the seventh invention for solving the above object is as follows:
In the member to be etched according to the sixth invention,
The metal nitride film is a member to be etched, which is a film made of at least one of tantalum nitride, tungsten nitride, and silicon nitride.
[0013]
The member to be etched according to the eighth invention for solving the above object is
In the member to be etched according to any one of the first to seventh inventions,
The carrier is a member to be etched, which is made of copper.
[0014]
The member to be etched according to the ninth invention for solving the above object is
In the member to be etched according to any one of the first to eighth inventions,
The metal covered is one or more of Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, or Au, and is a member to be etched. .
[0015]
A metal film manufacturing apparatus according to a tenth invention for solving the above-described object is
A chamber containing a substrate;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means for converting the halogen gas into plasma and generating halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
In the metal film manufacturing apparatus, the member to be etched is etched by the halogen gas plasma to generate a precursor of a metal component and a halogen, and the metal component of the precursor is formed on the substrate.
[0016]
A metal film manufacturing apparatus according to an eleventh invention for solving the above object is as follows.
A chamber containing a substrate;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
An external plasma generation chamber communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the external plasma generation chamber;
Plasma generating means for converting the halogen gas into plasma in the external plasma generation chamber and supplying halogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Etching the member to be etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and forming a metal component of the precursor on the substrate Device.
[0019]
The first to solve the above purpose 12 The metal film manufacturing apparatus according to the invention of
A cylindrical chamber in which a grounded substrate is accommodated and one end side is open;
A member to be etched according to any one of the first to ninth inventions, which is provided at a position facing the substrate and sealing the opening of the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
A plasma generating means that includes the member to be etched and a power supply unit that supplies power to the member to be etched, and converts the halogen gas into plasma to generate halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
In the metal film manufacturing apparatus, the member to be etched is etched by the halogen gas plasma to generate a precursor of a metal component and a halogen, and the metal component of the precursor is formed on the substrate.
[0020]
The first to solve the above purpose 13 The metal film manufacturing apparatus according to the invention of
A cylindrical chamber in which a substrate is accommodated and one end side is opened;
A convex ceiling plate curved outwardly of the chamber made of an insulating material that seals the opening of the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means having a conical ring-shaped coil arranged around the outside of the ceiling plate and a power supply unit for supplying power to the coil, and generating halogen gas plasma inside the chamber by converting the halogen gas into plasma When,
A member to be etched according to any one of the first to ninth inventions;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
In the metal film manufacturing apparatus, the member to be etched is etched by the halogen gas plasma to generate a precursor of a metal component and a halogen, and the metal component of the precursor is formed on the substrate.
[0021]
The first to solve the above purpose 14 The metal film manufacturing apparatus according to the invention of
First 13 In the metal film manufacturing apparatus described in the invention,
The member to be etched is the member to be etched according to any one of the first to ninth inventions,
And while being extended in the radial direction of the chamber between the substrate and the ceiling plate, a plurality of circumferentially arranged so as to be discontinuous with respect to the flow direction of the current flowing through the conical ring-shaped coil This is a metal film manufacturing apparatus.
[0022]
The first to solve the above purpose 15 The metal film manufacturing apparatus according to the invention of
First 13 In the metal film manufacturing apparatus described in the invention,
The member to be etched is the member to be etched according to any one of the first to ninth inventions,
And while extending along the curved shape inside the ceiling plate, it extends in the radial direction of the chamber between the substrate and the ceiling plate, and is discontinuous with respect to the flow direction of the current flowing in the conical ring-shaped coil The metal film manufacturing apparatus is characterized in that a plurality of them are arranged in the circumferential direction.
[0023]
The first to solve the above purpose 16 The metal film manufacturing apparatus according to the invention of
A cylindrical chamber in which a substrate is accommodated and one end side is opened;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
A cylindrical passage communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the cylindrical passage;
A coil wound around the cylindrical passage, and a power supply unit for supplying power to the coil, and converts the halogen gas into plasma in the cylindrical passage and supplies the halogen gas plasma into the chamber. Plasma generating means;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Etching the member to be etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and forming a metal component of the precursor on the substrate Device.
[0024]
The first to solve the above purpose 17 The metal film production method according to the invention of
Halogen gas is supplied into the chamber in which the substrate is accommodated, and the halogen gas is turned into plasma to generate halogen gas plasma.
Etching the member to be etched according to any one of the first to ninth inventions with the halogen gas plasma to form a precursor of a metal component and a halogen;
The temperature of the substrate is lower than the temperature of the member to be etched,
In this method, the metal component of the precursor is formed on the substrate.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
<First Embodiment>
A metal film manufacturing method and a metal film manufacturing apparatus according to the first embodiment will be described with reference to FIG. FIG. 1 is a schematic perspective cross-sectional view of a metal film production apparatus for performing the metal film production method according to the first embodiment of the present invention.
[0032]
As shown in FIG. 1, a support base 2 is provided in the vicinity of the bottom of a chamber 1 made of, for example, ceramics (made of an insulating material), and a substrate 3 is placed on the support base 2. . The support base 2 is provided with a temperature control means 6 including a heater 4 and a refrigerant flow means 5, and the support base 2 is set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.) by the temperature control means 6. ) Is controlled.
[0033]
The upper surface of the chamber 1 is an opening, and the opening is closed by the member 7 to be etched. The inside of the chamber 1 closed by the member 7 to be etched is maintained at a predetermined pressure by the vacuum device 8.
[0034]
A coiled plasma antenna 9 is provided around the cylindrical portion of the chamber 1, and a matching unit 10 and a power source 11 are connected to the plasma antenna 9 to supply a high-frequency current. Plasma generating means is constituted by the plasma antenna 9, the matching unit 10 and the power source 11.
[0035]
In the cylindrical portion of the chamber 1 at almost the same height as the support 2, a source gas 18 containing chlorine gas as a halogen gas inside the chamber 1 (He, Ar, etc., the chlorine concentration is ≦ 50%, preferably 10 Nozzle 12 for supplying chlorine gas diluted to about%) is connected. The nozzle 12 opens toward the member 7 to be etched, and the raw material gas 18 is sent to the nozzle 12 via the flow rate controller 13. The source gas 18 is sent from the substrate 3 side to the etched member 7 side in the chamber 1 during film formation. Gases that are not involved in film formation are exhausted from the exhaust port 17. The nozzle 12 and the flow rate controller 13 constitute a halogen gas supply means.
[0036]
Furthermore, in this embodiment, one surface of the copper plate 50 which is a plate-shaped carrier formed of copper is coated with tantalum metal (tantalum coating 51) to form the member 7 to be etched, and the surface coated with tantalum is the chamber. The member to be etched 7 was placed in the upper surface opening of the chamber 1 so as to be inside of the chamber 1. As a method for tantalum coating on the copper plate 50, tantalum metal was coated by sputtering or vacuum deposition.
[0037]
In the metal film manufacturing apparatus described above, the metal thin film 16 is formed by the method described in detail below.
[0038]
First, the raw material gas 18 is supplied from the nozzle 12 into the chamber 1 and electromagnetic waves are incident from the plasma antenna 9 into the chamber 1 to ionize the chlorine gas in the raw material gas 18 to generate chlorine gas plasma. Let The plasma is generated in the region shown by the gas plasma 14. The reaction at this time can be expressed by the following formula.
Cl ₂ → 2Cl ^* (1)
Where Cl ^* Represents a chlorine gas radical.
[0039]
When this gas plasma 14 acts on the tantalum coating 51 of the member 7 to be etched, the member 7 to be etched is heated and an etching reaction occurs in the tantalum metal coated on the copper plate 50. The reaction at this time is represented by the following formula, for example.
Ta (s) + 5Cl ^* → TaCl _Five (G) (2)
Here, s represents a solid state and g represents a gas state. Expression (2) represents a state in which the tantalum coating 51 is etched and gasified by the gas plasma 14. The precursor 15 is gasified TaCl. _Five And substances having a different composition ratio (Ta _X1 Cl _Y1 ).
[0040]
The member 7 to be etched is heated by generating the gas plasma 14, and the temperature control means 6 sets the temperature of the substrate 3 to be lower than the temperature of the member 7 to be etched. As a result, the precursor 15 is adsorbed on the substrate 3. The reaction at this time is represented by the following formula, for example.
TaCl _Five (G) → TaCl _Five (Ad) (3)
Here, ad represents an adsorption state.
[0041]
The tantalum chloride adsorbed on the substrate 3 is reduced by chlorine gas radicals to become a Ta component, thereby forming a part of the metal thin film 16 (Ta thin film). The reaction at this time is represented by the following formula, for example.
TaCl _Five (Ad) + 5Cl ^* → Ta (s) + 5Cl ₂ ↑ ・ ・ （４）
[0042]
Furthermore, a part of the gasified tantalum chloride generated in the above formula (2) is reduced by chlorine gas radicals to become tantalum in a gas state before adsorbing to the substrate 3 (see the above formula (3)). The reaction at this time is represented by the following formula, for example.
TaCl _Five (G) + 5Cl ^* → Ta (g) + 5Cl ₂ ↑ ・ ・ （５）
Thereafter, tantalum in a gas state is formed on the substrate 3 and becomes a part of forming the metal thin film 16.
[0043]
In the present embodiment, the following problems that may occur when a high-cost metal film is formed can be solved. That is, when a member to be etched is formed of a high-cost metal material, the first problem that a high-cost metal material needs to be prepared as a bulk material, and many of the high-cost metal materials have a large specific gravity. The second problem is that the overall weight of the metal film manufacturing apparatus is increased and it is difficult to remove a heavy member to be etched. In the present embodiment, the above-described problem can be solved by configuring the member to be etched 7 from the relatively inexpensive and light copper plate 50 and the tantalum coating 51 that is a metal material desired to be formed.
[0044]
2 to 5 are schematic perspective sectional views of a metal film production apparatus for performing the metal film production methods according to the second to fifth embodiments of the present invention, respectively. In addition, the same code | symbol is attached | subjected to the same kind member as the metal film production apparatus shown in FIG. 1, and the overlapping description is abbreviate | omitted.
[0045]
<Second Embodiment>
In the metal film manufacturing apparatus according to the second embodiment shown in FIG. 2, the upper surface of the chamber 1 is an opening, and the opening is closed by a plate-like ceiling plate 25 made of an insulating material (for example, ceramic). It is. A plasma antenna 27 for converting the inside of the chamber 1 into plasma is provided above the ceiling plate 25, and the plasma antenna 27 is formed in a planar ring shape parallel to the surface of the ceiling plate 25. The plasma antenna 27 is connected to the matching unit 10 and the power source 11 and supplied with a high frequency current.
[0046]
A member 20 to be etched is sandwiched between the opening on the upper surface of the chamber 1 and the ceiling plate 25. The member to be etched 20 includes a protrusion 21 and a ring 22, and the protrusion 21 is formed by coating the surface of a copper rod 52, which is a rod-shaped carrier formed of copper, with tantalum metal (tantalum coating 51). The ring portion 22 is formed by coating a copper ring with tantalum. As a method for coating tantalum, tantalum metal was coated by sputtering or vacuum deposition.
[0047]
FIG. 6 is a schematic plan view of the member 20 to be etched. As shown in the figure, the member 20 to be etched includes a ring-shaped ring portion 22 sandwiched along the side wall portion of the chamber 1, and the center of the ring portion 22 from the ring portion 22 (corresponding to the center of the chamber 1). A plurality of (in the drawing, twelve) protrusions 21 heading toward each other, and a notch 23 is formed between the protrusions 22. The surface of the member to be etched 20 is coated with tantalum metal throughout, and the inside is a carrier made of copper.
[0048]
As shown in FIG. 2, the member to be etched 20 is installed at a position facing the substrate 3 in the chamber 1. In this state, the protrusion 21 is divided into a plurality of portions along the circumferential direction of the side wall of the chamber 1 and protrudes toward the center from the ring portion 22 installed along the cylindrical chamber 1. That is, the protrusion 21 is disposed between the substrate 3 and the ceiling plate 25 so as to be discontinuous with respect to the flow direction of the current flowing through the plasma antenna 27.
[0049]
Also in the second embodiment, it is possible to solve the problem that may occur when the high-cost metal described in the first embodiment is formed. In the second embodiment, the member 20 to be etched is composed of a copper carrier that is relatively inexpensive and has a low specific gravity and a tantalum coating 51 that is a metal material desired to be formed, so that the above problem can be solved. It was.
[0050]
Note that the generation of the gas plasma 14 in the present embodiment is slightly different from that in the first embodiment, and thus will be described below.
[0051]
In the metal film manufacturing apparatus according to the present embodiment, a raw material gas 18 containing chlorine gas as a halogen gas is supplied into the chamber 1 from the nozzle 12, and electromagnetic waves are incident from the plasma antenna 27 into the chamber 1. Chlorine gas is ionized to generate chlorine gas plasma. This plasma is generated in a region shown by the gas plasma 14.
[0052]
The member to be etched 20 that is a conductor is present below the plasma antenna 27. However, as described above, the protrusion 21 of the member to be etched 20 is discontinuous with respect to the flow direction of the current flowing through the plasma antenna 27. Therefore, the gas plasma 14 is stably generated not only in the vicinity of the member to be etched 20 but also between the member to be etched 20 and the substrate 3, that is, below the member to be etched 20. It has become.
[0053]
When the gas plasma 14 acts on the tantalum coating 51 of the member to be etched 20, an etching reaction occurs in the tantalum coating 51, and a metal thin film 16 (tantalum thin film) is formed by the same action as in the first embodiment.
[0054]
<Third Embodiment>
In the metal film manufacturing apparatus according to the third embodiment shown in FIG. 3, the plasma antenna 9 is not provided around the cylindrical portion of the chamber 1 as compared with the metal film manufacturing apparatus shown in FIG. The matching unit 10 and the power source 11 are connected to the member 7 to be etched, and a high frequency current is supplied to the member 7 to be etched. Further, the support base 2 (substrate 3) is grounded. The member to be etched 7 is the member to be etched in the first embodiment.
[0055]
Also in the third embodiment, it is possible to solve the problem that may occur when the high-cost metal described in the first embodiment is formed. In the third embodiment, since the member 7 to be etched is composed of a relatively inexpensive and light copper support and a tantalum coating 51 which is a metal material desired to be formed, the above problem can be solved. It was.
[0056]
Note that the generation of the gas plasma 14 in the present embodiment is slightly different from that in the first embodiment, and thus will be described below.
[0057]
In the metal film manufacturing apparatus according to the present embodiment, a raw material gas 18 containing chlorine gas as a halogen gas is supplied into the chamber 1 from the nozzle 12 and is supplied from the power source 11 to the chamber 1 from the member 7 to be etched. By applying an electrostatic field to the inside, chlorine gas is ionized and chlorine gas plasma is generated. This plasma is generated in a region shown by the gas plasma 14.
[0058]
When the gas plasma 14 acts on the tantalum coating 51 of the member 7 to be etched, an etching reaction occurs in the tantalum coating 51, and the metal thin film 16 (tantalum thin film) is formed by the same action as in the first embodiment.
[0059]
<Fourth Embodiment>
In the metal film manufacturing apparatus according to the fourth embodiment shown in FIG. 4, the upper surface of the chamber 1 is an opening, and the opening is closed by a ceiling plate 25 made of, for example, ceramics (made of an insulating material). Yes. A member to be etched 30 is provided on the lower surface of the ceiling plate 25, and the member to be etched 30 has a conical shape (a convex shape on the substrate 3 side).
[0060]
A slit-shaped opening 31 is formed around the cylindrical portion of the chamber 1 at substantially the same height as the member to be etched 30, and one end of the cylindrical passage 32 is fixed to the opening 31. A cylindrical excitation chamber 33 made of an insulator is provided in the middle of the passage 32, and a coiled plasma antenna 34 is provided around the excitation chamber 33. The plasma antenna 34 is connected to the matching unit 10 and the power source 11. Then, a high frequency current is supplied. A flow rate controller 13 is connected to the other end side of the passage 32, and a raw material gas 18 containing chlorine gas as a halogen gas is supplied into the passage 32 through the flow rate controller 13. In the present embodiment, the plasma generating means is composed of the passage 32, the excitation chamber 33, the plasma antenna 34, the matching unit 10 and the power source 11, and is installed outside the chamber 1, so that it is called “external plasma generation chamber”. .
[0061]
Furthermore, in this embodiment, the conical surface of the copper plate 53, which is a conical carrier formed of copper, is coated with tantalum metal (tantalum coating 51) to form the member 30 to be etched, and is coated with tantalum. The member to be etched 30 was placed on the lower surface of the ceiling plate 25 so that the conical surface was inside the chamber 1 (projected toward the substrate 3). As a method for coating tantalum on the copper plate 53, tantalum metal was coated by sputtering or vacuum deposition.
[0062]
Also in the fourth embodiment, it is possible to solve the problem that may occur when the high-cost metal described in the first embodiment is formed. In the fourth embodiment, the above-described problem can be solved by configuring the member to be etched 30 with a relatively inexpensive and light copper support and a tantalum coating 51 which is a metal material desired to be formed. It was.
[0063]
In addition, since generation | occurrence | production and the etching effect | action of the gas plasma 35 in this embodiment differ a little from 1st Embodiment, description is added below.
[0064]
In the present embodiment, the source gas 18 supplied into the passage 32 via the flow rate controller 13 is sent into the excitation chamber 33. Next, electromagnetic waves are incident on the inside of the excitation chamber 33 from the plasma antenna 34, whereby chlorine gas is ionized to generate gas plasma 35.
[0065]
Since a predetermined differential pressure is set between the pressure in the chamber 1 and the pressure in the excitation chamber 33 by the vacuum device 8, chlorine radicals in the gas plasma 35 in the excitation chamber 33 are etched from the opening 31 in the chamber 1. Sent to member 30. The chlorine radicals act on the tantalum coating 51 of the member to be etched 30, thereby causing an etching reaction in the tantalum coating 51. As a result, a metal thin film 16 (tantalum thin film) is formed on the substrate 3 by a film formation reaction similar to that of the first embodiment.
[0066]
In the metal film manufacturing apparatus according to the present embodiment, the gas plasma 35 is generated in the excitation chamber 33 that is isolated from the chamber 1 (provided outside the chamber 1), so that the substrate 3 may be exposed to the plasma. The substrate 3 is not damaged by the plasma. For example, when another metal film is formed on the substrate 3 on which the metal film is formed, another metal film can be formed without damaging the already formed metal film. As a means for generating the gas plasma 35 in the excitation chamber 33, it is also possible to use a microwave, a laser, an electron beam, emitted light, or the like.
[0067]
<Fifth Embodiment>
In the metal film manufacturing apparatus according to the fifth embodiment shown in FIG. 5, the shapes of the ceiling plate and the plasma antenna are different from those of the metal film manufacturing apparatus shown in FIG. That is, a convex (dome-shaped) ceiling plate 43 that is curved outward from the chamber is fixed to the upper opening of the chamber 1. The ceiling plate 43 is made of an insulating material (ceramics or the like). On the other hand, a plasma antenna 44 for converting the inside of the chamber 1 into plasma is provided around the outside of the ceiling plate 43. The plasma antenna 44 is formed in a conical ring shape along the convex shape of the ceiling plate 43. A matching unit 10 and a power source 11 are connected to the plasma antenna 44 so that high-frequency power is supplied. Plasma generating means is constituted by the plasma antenna 44, the matching unit 10 and the power source 11. The member to be etched 20 is the member to be etched in the second embodiment.
[0068]
In the present embodiment, the ceiling plate 43 is formed in a convex shape, and the plasma antenna 44 is formed in a conical ring shape along the convex shape of the ceiling plate 43, thereby generating a gas plasma as compared with the second embodiment. 45 can be made uniform and stable.
[0069]
Also in the fifth embodiment, it is possible to solve the problem that may occur when the high-cost metal described in the first embodiment is formed. In the fifth embodiment, the above-described problem can be solved by configuring the member to be etched 7 by a relatively inexpensive and low specific gravity copper carrier and a tantalum coating 51 which is a metal material desired to be formed. It was.
[0070]
Note that generation of the gas plasma 45 in the present embodiment is slightly different from that in the first embodiment, and thus will be described below.
[0071]
In the metal film manufacturing apparatus according to the present embodiment, a raw material gas 18 containing chlorine gas as a halogen gas is supplied from the nozzle 12 to the inside of the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 44. Chlorine gas is ionized to generate chlorine gas plasma. This plasma is generated in the region shown by the gas plasma 45.
[0072]
When the gas plasma 45 acts on the tantalum coating 51 of the member to be etched 20, an etching reaction occurs in the tantalum coating 51, and the metal thin film 16 (tantalum thin film) is formed by the same action as in the first embodiment.
[0073]
In the present embodiment, the member to be etched 20 described in the second embodiment is applied as the member to be etched, but the present invention is not limited to this. For example, it extends in the radial direction of the chamber 1 between the substrate 3 and the ceiling plate 43 along the curved shape inside the ceiling plate 43, and is discontinuous with respect to the flow direction of the current flowing in the plasma antenna 44 having a conical ring shape. It is good also as the to-be-etched member arrange | positioned in the side wall peripheral direction of the chamber 1 so that it may be in a state.
[0074]
Next, a member to be etched according to another embodiment will be described with reference to FIGS. 7 to 9 are schematic external views of the protrusions of the member to be etched according to other embodiments. In the member to be etched 20 shown in FIG. 6, a tantalum metal is coated on the copper rod as a carrier by a sputtering method or a vacuum evaporation method to form a protrusion 21.
[0075]
On the other hand, the protrusion 21 of the member to be etched shown in FIG. 7 is configured by sticking a tantalum ribbon 54, which is a tantalum metal in a ribbon shape, around a copper rod 52, which is a carrier, so as to be wound. Further, the protruding portion 21 of the member to be etched shown in FIG. 8 is configured by winding a tantalum wire 55, which is a tantalum metal in a wire shape, around a copper rod 52, which is a carrier, several times.
[0076]
Further, the protrusion 21 of the member to be etched shown in FIG. 9 is configured by sintering a tantalum metal on a copper rod 52 as a carrier. As a method for producing the sintered tantalum 56, powdery tantalum oxide is mixed with a material to form a slurry, and then the slurry tantalum oxide is sprayed or coated on the copper rod 52 and heated in a reducing atmosphere such as hydrogen gas. Thus, a sintered film of only tantalum metal (sintered tantalum 56) was obtained.
[0077]
7 and 9 show examples applied to the member to be etched of the type shown in FIG. 6, but the present invention can also be applied to the plate-like member to be etched shown in FIG. 1, FIG. 3, or FIG. That is, the tantalum ribbon 54 may be attached to the plate-like copper plate 50 or the conical plate-like copper plate 53 as a carrier, or may be covered with the sintered tantalum 56.
[0078]
In each of the above embodiments, the source gas is Cl diluted with He. ₂ The gas has been described as an example, but Cl ₂ It is also possible to use the gas alone or to apply HCl gas. When HCl gas is applied, HCl gas plasma is generated as the source gas plasma, but the precursor generated by etching the tantalum metal of the member to be etched is Ta. _x Cl _y It is. Therefore, the source gas may be any gas containing chlorine, and HCl gas and Cl ₂ It is also possible to use a mixed gas with the gas. Furthermore, in general, not only chlorine but any halogen gas can be used as the raw material gas of the present invention. As the halogen, fluorine, bromine, iodine and the like can be applied.
[0079]
Further, the metal to be coated on the carrier in the member to be etched is not limited to tantalum, and any one of Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, or Au, for example. That's all. Further, as the material for the carrier, a metal such as copper, which is relatively inexpensive, has a small specific gravity and high thermal conductivity is preferable. The reason why the carrier having high thermal conductivity is preferable is that accurate control is possible when the temperature of the member to be etched is controlled. The reason for controlling the temperature is that the metal thin film is formed by adjusting the temperature relationship between the member to be etched and the substrate.
[0080]
In addition, when silicon oxide, metal nitride, or the like is interposed between the support and the coated metal, it is easy to accurately determine the replenishment time of the coated metal. Since silicon oxide and metal nitride have high thermal conductivity like the carrier material and are difficult to etch, it is possible to prevent the coating metal from being etched into the carrier material after being consumed by etching. Here, examples of the metal nitride include tantalum nitride, tungsten nitride, silicon nitride, and titanium nitride.
[0081]
【The invention's effect】
According to the member to be etched according to the first invention,
The member to be etched is etched with halogen gas plasma to form a metal component and a halogen precursor, and the metal component of the precursor is formed on the substrate. The member to be etched, which is used in the metal film production apparatus and serves as the raw material of the metal to be deposited, is configured by covering the carrier with a metal capable of generating a high vapor pressure halide. In the case where the member to be etched is formed of a high-cost metal material that may occur in the first step, the first problem that it is necessary to prepare a high-cost metal material as a bulk material, and many of the high-cost metal materials Since the specific gravity is large, it is possible to solve the second problem that the weight of the entire metal film manufacturing apparatus is increased and it is difficult to remove the heavy member to be etched.
[0082]
According to the member to be etched according to the second invention,
In the member to be etched described in the first invention,
Since the metal is coated on the carrier by sputtering or vacuum evaporation,
The metal can be uniformly coated on the surface of the carrier.
[0083]
According to the member to be etched according to the third invention,
In the member to be etched described in the first invention,
Since the ribbon-shaped metal is attached to the carrier,
The surface of the carrier can be coated with a metal by an inexpensive method.
[0084]
According to the member to be etched according to the fourth invention,
In the member to be etched described in the first invention,
Since the metal oxide of the metal oxide is coated on the support by sintering the metal oxide in a slurry state sprayed or coated on the support in a reducing atmosphere,
The surface of the carrier can be coated with a metal uniformly and inexpensively.
[0085]
According to the member to be etched according to the fifth invention,
In the member to be etched described in the first invention,
Since the carrier is rod-shaped, and the wire-shaped metal is wound around the rod-shaped carrier,
The surface of the support can be coated with a metal by a simple method.
[0086]
According to the member to be etched according to the sixth invention,
In the member to be etched according to any one of the first to fifth inventions,
Since a metal nitride film is interposed between the carrier and the coated metal,
It is possible to accurately determine the replenishment time of the coated metal. Further, since the metal nitride has high thermal conductivity like the carrier material and is difficult to etch, the metal nitride can be prevented from being etched up to the carrier material after being consumed by the etching.
[0087]
According to the member to be etched according to the seventh invention,
In the member to be etched according to the sixth invention,
Since the metal nitride film is a film made of at least one of tantalum nitride, tungsten nitride, or silicon nitride,
It is possible to more accurately determine the replenishment time of the coated metal and further prevent the carrier material from being etched.
[0088]
According to the member to be etched according to the eighth invention,
In the member to be etched according to any one of the first to seventh inventions,
Since the carrier is made of copper,
The member to be etched can be made relatively inexpensive and lightweight, and the temperature of the member to be etched can be accurately controlled.
[0089]
According to the member to be etched according to the ninth invention,
In the member to be etched according to any one of the first to eighth inventions,
Since the coated metal is one or more of Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt or Au,
A high-cost metal can be formed by a relatively easy film formation operation while suppressing the film formation cost.
[0090]
According to the metal film manufacturing apparatus of the tenth invention,
A chamber containing a substrate;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means for converting the halogen gas into plasma and generating halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since the halogen gas plasma is used to etch the member to be etched to generate a metal component and a halogen precursor, and the metal component of the precursor is deposited on the substrate.
When forming a member to be etched with a high-cost metal material, the first problem is that it is necessary to prepare a high-cost metal material as a bulk material, and many of the high-cost metal materials have a high specific gravity. Solves the second problem that the overall weight of the film manufacturing apparatus increases and it is difficult to remove a heavy member to be etched. A film can be formed.
[0091]
According to the metal film manufacturing apparatus of the eleventh invention,
A chamber containing a substrate;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
An external plasma generation chamber communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the external plasma generation chamber; plasma generation means for converting the halogen gas into plasma in the external plasma generation chamber and supplying halogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
The to-be-etched member is etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and the metal component of the precursor is formed on the substrate. So
When forming a member to be etched with a high-cost metal material, the first problem is that it is necessary to prepare a high-cost metal material as a bulk material, and many of the high-cost metal materials have a high specific gravity. Solves the second problem that the overall weight of the film manufacturing apparatus increases and it is difficult to remove a heavy member to be etched. A film can be formed.
[0094]
First 12 According to the metal film manufacturing apparatus according to the invention,
A cylindrical chamber in which a grounded substrate is accommodated and one end side is open;
A member to be etched according to any one of the first to ninth inventions, which is provided at a position facing the substrate and sealing the opening of the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
A plasma generating means that includes the member to be etched and a power supply unit that supplies power to the member to be etched, and converts the halogen gas into plasma to generate halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since the halogen gas plasma is used to etch the member to be etched to generate a metal component and a halogen precursor, and the metal component of the precursor is deposited on the substrate.
In addition to the effects of the tenth or eleventh invention, the plasma generating antenna can be eliminated, and the degree of freedom around the chamber can be increased.
[0095]
First 13 According to the metal film manufacturing apparatus according to the invention,
A cylindrical chamber in which a substrate is accommodated and one end side is opened;
A convex ceiling plate curved outwardly of the chamber made of an insulating material that seals the opening of the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means having a conical ring-shaped coil arranged around the outside of the ceiling plate and a power supply unit for supplying power to the coil, and generating halogen gas plasma inside the chamber by converting the halogen gas into plasma When,
A member to be etched according to any one of the first to ninth inventions;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since the halogen gas plasma is used to etch the member to be etched to generate a metal component and a halogen precursor, and the metal component of the precursor is deposited on the substrate.
In addition to the effects of the tenth or eleventh invention, plasma can be generated stably.
[0096]
First 14 According to the metal film manufacturing apparatus according to the invention,
First 13 In the metal film manufacturing apparatus described in the invention,
The member to be etched The Since it is arranged in the circumferential direction so as to be discontinuous with respect to the flow direction of the current flowing through the conical ring-shaped coil while extending in the radial direction of the chamber between the substrate and the ceiling plate,
First 13 This invention can be realized by a member to be etched that is easy to process.
[0097]
First 15 According to the metal film manufacturing apparatus according to the invention,
First 13 In the metal film manufacturing apparatus described in the invention,
The member to be etched The While extending along the curved shape inside the ceiling plate, it extends in the radial direction of the chamber between the substrate and the ceiling plate, and is discontinuous with respect to the flow direction of the current flowing through the conical ring-shaped coil. As we arranged in the circumferential direction as
First 13 In this invention, the film formation efficiency can be improved.
[0098]
First 16 According to the metal film manufacturing apparatus according to the invention,
A cylindrical chamber in which a substrate is accommodated and one end side is opened;
A member to be etched according to any one of the first to ninth inventions provided at a position facing the substrate in the chamber;
A cylindrical passage communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the cylindrical passage;
A coil wound around the cylindrical passage, and a power supply unit for supplying power to the coil, and converts the halogen gas into plasma in the cylindrical passage and supplies the halogen gas plasma into the chamber. Plasma generating means;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
The to-be-etched member is etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and the metal component of the precursor is formed on the substrate. So
In addition to the effects of the tenth or eleventh invention, damage to the metal thin film formed on the substrate by plasma can be prevented.
[0099]
First 17 According to the metal film manufacturing method of the invention,
Halogen gas is supplied into the chamber in which the substrate is accommodated, and the halogen gas is turned into plasma to generate halogen gas plasma.
Etching the member to be etched according to any one of the first to ninth inventions with the halogen gas plasma to form a precursor of a metal component and a halogen;
The temperature of the substrate is lower than the temperature of the member to be etched,
Since the metal component of the precursor was deposited on the substrate,
When forming a member to be etched with a high-cost metal material, the first problem is that it is necessary to prepare a high-cost metal material as a bulk material, and many of the high-cost metal materials have a high specific gravity. Solves the second problem that the overall weight of the film manufacturing apparatus increases and it is difficult to remove a heavy member to be etched. A film can be formed.
[Brief description of the drawings]
FIG. 1 is a schematic perspective cross-sectional view of a metal film production apparatus for performing a metal film production method according to a first embodiment.
FIG. 2 is a schematic perspective cross-sectional view of a metal film production apparatus for performing a metal film production method according to a second embodiment.
FIG. 3 is a schematic perspective cross-sectional view of a metal film production apparatus for performing a metal film production method according to a third embodiment.
FIG. 4 is a schematic perspective cross-sectional view of a metal film production apparatus for performing a metal film production method according to a fourth embodiment.
FIG. 5 is a schematic perspective cross-sectional view of a metal film production apparatus for performing a metal film production method according to a fifth embodiment.
FIG. 6 is a schematic external view of a member to be etched of a metal film manufacturing apparatus according to a second embodiment.
FIG. 7 is a schematic external view of a protrusion of an etched member according to another embodiment.
FIG. 8 is a schematic external view of a protrusion of a member to be etched according to another embodiment.
FIG. 9 is a schematic external view of a protrusion of a member to be etched according to another embodiment.
[Explanation of symbols]
1 chamber
2 Support stand
3 Substrate
4 Heater
5 Refrigerant distribution means
6 Temperature control means
7 Member to be etched
8 Vacuum equipment
9 Plasma antenna
10 Matching device
11 Power supply
12 nozzles
13 Flow controller
14 Gas plasma
15 Precursor
16 Tantalum thin film
17 Exhaust port
18 Source gas
20 Member to be etched
21 Protrusion
22 Ring part
23 Notch
25 Ceiling board
27 Plasma antenna
30 Member to be etched
31 opening
32 passage
33 Excitation room
34 Plasma antenna
35 Gas plasma
40 Member to be etched
41 Protrusion
42 Ring part
43 Ceiling board
44 Plasma antenna
45 Gas plasma
50 copper plate
51 Tantalum coating
52 Copper Rod
53 Copper plate
54 Tantalum ribbon
55 Tantalum wire
56 Sintered tantalum

Claims (17)

Metal to be used in a metal film production apparatus for forming a metal component and a halogen precursor by etching a member to be etched with halogen gas plasma and forming a metal component of the precursor on a substrate. A member to be etched, which is a material to be etched, wherein the carrier is coated with a metal capable of generating a high vapor pressure halide. The member to be etched according to claim 1,
A member to be etched, wherein the carrier is coated with the metal by a sputtering method or a vacuum deposition method. The member to be etched according to claim 1,
A member to be etched, wherein the metal in a ribbon shape is stuck to the carrier. The member to be etched according to claim 1,
A member to be etched, wherein the carrier is coated with the metal component of the metal oxide by sintering the metal oxide in the form of a slurry sprayed or coated on the carrier in a reducing atmosphere. . The member to be etched according to claim 1,
The member to be etched is characterized in that the carrier is rod-shaped, and the wire-shaped metal is wound around the rod-shaped carrier. In the member to be etched according to any one of claims 1 to 5,
A member to be etched, wherein a metal nitride film is interposed between the carrier and the coated metal. The member to be etched according to claim 6,
The member to be etched is characterized in that the metal nitride film is a film made of at least one of tantalum nitride, tungsten nitride, and silicon nitride. The member to be etched according to any one of claims 1 to 7,
A member to be etched, wherein the carrier is made of copper. The member to be etched according to any one of claims 1 to 8,
The member to be etched is characterized in that the coated metal is at least one of Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au. A chamber containing a substrate;
The member to be etched according to any one of claims 1 to 9, which is provided at a position facing the substrate in the chamber,
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means for converting the halogen gas into plasma and generating halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal film manufacturing apparatus that forms a precursor of a metal component and a halogen by etching the member to be etched by the halogen gas plasma, and deposits the metal component of the precursor on the substrate. A chamber containing a substrate;
The member to be etched according to any one of claims 1 to 9, which is provided at a position facing the substrate in the chamber,
An external plasma generation chamber communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the external plasma generation chamber; plasma generation means for converting the halogen gas into plasma in the external plasma generation chamber and supplying halogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Etching the member to be etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and forming a metal component of the precursor on the substrate apparatus. A cylindrical chamber in which a grounded substrate is accommodated and one end side is open;
The member to be etched according to any one of claims 1 to 9, wherein the member is sealed at an opening of the chamber and is opposed to the substrate.
Halogen gas supply means for supplying halogen gas into the chamber;
A plasma generating means that includes the member to be etched and a power supply unit that supplies power to the member to be etched, and converts the halogen gas into plasma to generate halogen gas plasma inside the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal film manufacturing apparatus that forms a precursor of a metal component and a halogen by etching the member to be etched by the halogen gas plasma, and deposits the metal component of the precursor on the substrate. A cylindrical chamber in which a substrate is accommodated and one end side is opened;
A convex ceiling plate curved outwardly of the chamber made of an insulating material that seals the opening of the chamber;
Halogen gas supply means for supplying halogen gas into the chamber;
Plasma generating means having a conical ring-shaped coil arranged around the outside of the ceiling plate and a power supply unit for supplying power to the coil, and generating halogen gas plasma inside the chamber by converting the halogen gas into plasma When,
The member to be etched according to any one of claims 1 to 9,
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal film manufacturing apparatus that forms a precursor of a metal component and a halogen by etching the member to be etched by the halogen gas plasma, and deposits the metal component of the precursor on the substrate. In the metal film production apparatus according to claim 13 ,
The etched member may extend in a radial direction of the chamber between the substrate and the ceiling plate, in the circumferential direction so as to be discontinuous with respect to the flow direction of the current flowing through the coil of the conical ring-shaped A metal film manufacturing apparatus, wherein a plurality of metal film manufacturing apparatuses are arranged. In the metal film production apparatus according to claim 13 ,
The etched member may extend in a radial direction of the chamber between the substrate and the ceiling plate while along the inner side of the curved shape of the ceiling board, to the flow direction of the current flowing through the coil of the conical ring-shaped A metal film manufacturing apparatus, wherein a plurality of devices are arranged in the circumferential direction so as to be discontinuous. A cylindrical chamber in which a substrate is accommodated and one end side is opened;
The member to be etched according to any one of claims 1 to 9, which is provided at a position facing the substrate in the chamber,
A cylindrical passage communicating with the interior of the chamber;
Halogen gas supply means for supplying halogen gas to the cylindrical passage;
A coil wound around the cylindrical passage, and a power supply unit for supplying power to the coil, and converts the halogen gas into plasma in the cylindrical passage and supplies the halogen gas plasma into the chamber. Plasma generating means;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Etching the member to be etched by the halogen gas plasma supplied into the chamber to generate a precursor of a metal component and a halogen, and forming a metal component of the precursor on the substrate apparatus. Halogen gas is supplied into the chamber in which the substrate is accommodated, and the halogen gas is converted into plasma to generate halogen gas plasma.
A member to be etched according to claim 1 is etched with the halogen gas plasma to form a precursor of a metal component and a halogen, and the temperature of the substrate is lower than the temperature of the member to be etched. And
A metal film manufacturing method for forming a metal component of the precursor on the substrate.

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