JP2004197196A - Apparatus and method for treating multilayer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer film producing apparatus which prevents oxidation, and deterioration in film properties. <P>SOLUTION: A substrate 12 having a barrier metal coated on its surface is transported to a metal film production apparatus 3 in a state where oxidation is prevented by using a transport chamber 4 in a vacuum state. The member to be etched is subjected to etching in gaseous starting material plasma, so that the precursor of a metal component(s) included in the member to be etched and the gaseous starting material is produced inside a chamber 11. The temperature of the substrate 12 is made lower than that of the member to be etched, so that the metallic component(s) in the precursor is film-deposited on the substrate. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a multilayer film forming apparatus and a multilayer film forming method for forming a multilayer metal film, a metal oxide film, and a metal nitride film (hereinafter collectively referred to as a metal film) on a surface of a substrate.
[0002]
[Prior art]
In a semiconductor provided with electrical wiring, copper has been used as a material for the wiring due to a reduction in switching speed, transmission loss, high density, and the like. In the case of providing copper wiring, a copper thin film is formed on the surface including the concave portion by a vapor phase growth method or the like on a substrate having a concave portion for wiring on the surface.
[0003]
When producing a copper thin film, for example, a liquid organometallic complex such as copper, hexafluoroacetylacetonato, or trimethylvinylsilane is used as a raw material, a solid raw material is dissolved in a solvent, and a gas is formed by utilizing a thermal reaction. And forming a film on the substrate.
[0004]
When a copper thin film is formed on the surface of the substrate, a barrier metal film (for example, tantalum, titanium, silicon, etc.) is previously formed on the surface of the substrate in order to eliminate the diffusion of copper to the substrate and maintain the density of copper. Nitride) has been produced.
[0005]
[Problems to be solved by the invention]
In the conventional technology, it is difficult to improve the film forming speed because the film is formed using a thermal reaction. In addition, the metal complex as a raw material is expensive, and hexafluoroacetylacetonato and trimethylvinylsilane attached to copper remain as impurities in the copper thin film, so that it is difficult to improve the film quality. Was.
[0006]
Since the barrier metal film and the copper thin film are manufactured using different devices, it is necessary to transport the substrate on which the barrier metal film has been manufactured to the device for manufacturing the copper thin film. There was a risk of doing so. For this reason, various devices have conventionally been proposed as devices for producing a copper thin film from a substrate on which a barrier metal film has been produced while being shielded from the atmosphere (for example, see Patent Document 1).
[0007]
[Patent Document 1]
Japanese Patent No. 3064268
[0008]
However, oxidation during transportation or film formation cannot be eliminated, and it has been desired to suppress oxidation and improve film quality.
[0009]
The present invention has been made in view of the above circumstances, and has a high film-forming rate, can use inexpensive raw materials, can suppress oxidation, and can produce a multilayer film in which impurities do not remain in the film. It is an object to provide a processing apparatus and a multilayer film processing method.
[0010]
[Means for Solving the Problems]
The multilayer film processing apparatus of the present invention for achieving the above object,
A chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, a source gas supply unit for supplying a source gas containing halogen into the chamber, and a plasma in the chamber. Means for generating a precursor of a metal component contained in the member to be etched and a source gas by generating a source gas plasma and etching the member to be etched with the source gas plasma; Temperature control means for forming a film of at least a metal component of the precursor on the substrate by lowering the temperature on the side, comprising a metal film production apparatus,
Further, a transfer chamber system provided with natural oxidation suppressing means,
A substrate processing apparatus that performs processing on the surface of the substrate,
The substrate processed by the substrate processing apparatus is sent from the transfer chamber system to the metal film forming apparatus.
[0011]
And in the multilayer processing apparatus according to claim 1,
The natural oxidation suppressing means in the transfer chamber system is a vacuum device for evacuating the inside of the transfer chamber system.
[0012]
Further, in the multilayer processing apparatus according to claim 1,
The natural oxidation suppressing means in the transfer chamber system is characterized by comprising a rare gas introduction means for introducing a rare gas into the transfer chamber.
[0013]
Further, in the multilayer processing apparatus according to claim 1,
The natural oxidation suppressing means in the transfer chamber system is characterized by comprising a rare gas introduction means for introducing a gas containing halogen into the transfer chamber.
[0014]
Further, in the multilayer processing apparatus according to claim 1,
The natural oxidation suppressing means in the transfer chamber system is characterized by comprising a rare gas introduction means for introducing a rare gas into the transfer chamber and a rare gas introduction means for introducing a gas containing halogen.
[0015]
Further, in the multilayer film processing apparatus according to any one of claims 1 to 3,
Backflow preventing means for preventing backflow of the halogen gas in the chamber of the metal film forming apparatus into the transfer chamber is provided.
[0016]
Further, in the multilayer processing apparatus according to claim 6,
The backflow prevention means is a concentration reducing means for reducing the concentration of the residual halogen gas in the chamber of the metal film forming apparatus.
[0017]
Further, in the multilayer processing apparatus according to any one of claims 1 to 5,
The apparatus is characterized in that a pressure adjusting means for maintaining the pressure in the transfer chamber higher than the pressure in the chamber of the metal film manufacturing apparatus and preventing the gas in the chamber from flowing into the transfer chamber is provided.
[0018]
Further, in the multilayer processing apparatus according to any one of claims 1 to 8,
The substrate processing apparatus is a barrier layer manufacturing apparatus for forming a barrier metal film on a surface of a substrate.
[0019]
Further, in the multilayer film processing apparatus according to claim 9,
The transfer chamber system is provided with an accommodation chamber system for a substrate, and is provided with two metal film production apparatuses. Between the accommodation chamber system and the barrier layer production apparatus, and between the barrier layer production apparatus and the two equipment metal film production apparatus. A transport device for transporting the substrate between them.
[0020]
In order to achieve the above object, a metal film manufacturing apparatus according to the present invention includes a chamber in which a substrate is housed, a metal member to be etched provided in the chamber at a position facing the substrate, and a raw material containing halogen in the chamber. A raw material gas supply unit for supplying a gas, a precursor of a metal component and a raw material gas contained in the member to be etched by generating a raw material gas plasma by converting the inside of the chamber into a plasma, and etching the member to be etched with the raw material gas plasma; And temperature control means for lowering the temperature of the substrate side from the temperature of the plasma generation means to deposit at least the metal component of the precursor on the substrate. The substrate is transferred from a transfer chamber system provided with a suppressing unit.
[0021]
In order to achieve the above object, the transfer chamber of the present invention includes a chamber in which a substrate is housed, a metal member to be etched provided in the chamber at a position facing the substrate, and a source gas containing halogen in the chamber. A source gas supply unit for supplying, and a source of the metal component and the source gas contained in the member to be etched by generating a source gas plasma by converting the inside of the chamber into a plasma to generate the source gas plasma and etching the member to be etched with the source gas plasma The substrate is transported to a metal film forming apparatus comprising: a plasma generating means for performing the heat treatment; and a temperature control means for lowering the temperature on the substrate side to a temperature lower than the temperature on the plasma generating means side and forming at least the precursor metal component on the substrate. And a natural oxidation suppressing means.
[0022]
A transfer chamber according to the present invention for achieving the above object is a transfer chamber for transferring a substrate from a substrate processing apparatus that performs processing on a surface of a substrate, and includes a natural oxidation suppressing unit.
[0023]
And in the transfer chamber according to claim 13,
A substrate from a substrate processing apparatus that performs processing on the surface of the substrate is transported to a metal film forming apparatus.
[0024]
A substrate processing apparatus of the present invention for achieving the above object is a substrate processing apparatus that performs processing on a surface of a substrate, and transports a substrate that has been subjected to surface processing in a transport chamber provided with natural oxidation suppressing means. It is characterized by.
[0025]
In order to achieve the above object, the method for producing a multilayer film according to the present invention comprises: transporting a substrate having a surface treated into a metal film production apparatus chamber in a transport chamber in a state where natural oxidation is suppressed; A precursor of a metal component and a source gas contained in the member to be etched is generated in the chamber by etching the member to be etched with the plasma, and the temperature of the substrate side is made lower than the temperature of the member to be etched to at least the precursor. The metal component of the body is formed on the substrate.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
According to the present invention, a metal film (in a state where natural oxidation is suppressed (for example, a vacuum state or a state where a rare gas or the like is filled)) is applied to a substrate whose surface is treated (for example, a barrier metal film is formed) in a transfer chamber. For example, a copper film, an alloy film, a metal oxide film, a metal nitride film, and the like are transported into a chamber for producing a metal film (hereinafter simply referred to as a metal film), and are etched by a source gas plasma (for example, a gas containing halogen). By etching a member (for example, a copper member, a copper halide member, an alloy member, etc.), a precursor of a metal component and a source gas contained in the member to be etched is generated in the chamber, and the temperature of the substrate side is etched. At least the metal component of the precursor is formed on the substrate by lowering the temperature on the member side.
[0027]
This makes it possible to suppress the natural oxidation of the substrate whose surface has been treated, and to manufacture a metal film in which no impurities remain in the oxide film or the like by using an inexpensive material having a high film forming rate. For example, when copper is manufactured as a wiring member of a semiconductor, oxidation after forming a barrier metal film is prevented, and an organic metal containing oxygen is not used even when a copper film is formed. Deterioration of film characteristics such as no residual and high electric resistance can be prevented, and the film performance of the multilayer film is dramatically improved.
[0028]
An embodiment of the present invention will be described with reference to FIGS. FIG. 1 shows a schematic configuration of a multilayer film manufacturing apparatus according to the first embodiment of the present invention, and FIG. 2 shows a schematic configuration of a multilayer film manufacturing apparatus according to the second embodiment of the present invention.
[0029]
<First Embodiment>
As shown in FIG. 1, the multilayer film processing apparatus includes a substrate cassette 1 for holding a large number of substrates, a barrier layer forming apparatus 2 as a substrate processing apparatus for performing processing (for example, forming a barrier metal film) on the surface of the substrate. A metal film forming apparatus 3 for forming a metal film (for example, a copper film) on the surface of a substrate on which a barrier metal film has been formed, and between the substrate cassette 1 and the barrier layer forming apparatus 2 and between the barrier layer forming apparatus 2 and the metal film. A transfer chamber device 4 as a transfer chamber system for transferring a substrate between the manufacturing apparatuses 3.
[0030]
The substrate cassette 1 holds a large number of substrates 12. The barrier layer manufacturing apparatus 2 includes a chamber 6 in which a substrate is accommodated. In the chamber 6, a substrate 12 is accommodated. For example, the introduction of the processing gas from the processing gas nozzle 7 and the temperature control control the temperature of the processing gas onto the surface of the substrate 12. A barrier layer of the component is made.
[0031]
The metal film forming apparatus 3 includes a chamber 11 in which a substrate is accommodated. The chamber 11 is provided with a metal (for example, copper) member to be etched 13 at a position facing the substrate 12. A source gas nozzle 14 is provided in the chamber 11 above the substrate 12 as source gas supply means for supplying a source gas containing chlorine (a gas containing chlorine) into the chamber 11.
[0032]
A plasma antenna 13 is provided on the ceiling of the chamber 11 as a flat ring-shaped plasma generating means, and the inside of the chamber 11 is turned into plasma by the plasma antenna 13 to generate source gas plasma.
[0033]
In the metal film forming apparatus 3, a precursor of the metal component (copper component) contained in the member to be etched 13 and the source gas is generated by etching the member to be etched 13 with the source gas plasma, and the metal component of the precursor is A film is formed on the substrate 12.
[0034]
The material of the member to be etched 13 can be set arbitrarily (for example, made of an alloy, a metal halide, or the like). When the member to be etched 13 made of an alloy is used, an alloy film can be formed. It is possible. In addition, the type of the source gas can be appropriately set, and a film of a metal oxide, a metal nitride, or the like can be formed.
[0035]
The transfer chamber device 4 includes a transfer chamber 15 having transfer means and the like, and the inside of the transfer chamber 15 is evacuated by a vacuum device 16 as a natural oxidation suppressing means.
[0036]
Further, the pressure in the chamber 11 of the metal film forming apparatus 3 is detected by the pressure detecting means 17, and the vacuum device 16 is controlled so that the pressure in the transfer chamber 15 becomes higher than the pressure in the chamber 11. means).
[0037]
As a result, the inside of the transfer chamber 15 is evacuated and the source gas (chlorine-containing gas) remaining in the chamber 11 of the metal film forming apparatus 3 does not flow into the transfer chamber 15, and the chlorine-containing gas is removed. The gas does not damage the transfer chamber 15 and the substrate 12 on which the film is formed.
[0038]
Instead of providing the pressure detecting means 17 to generate a pressure difference, a means for positively discharging the raw material gas remaining in the chamber 11 of the metal film forming apparatus 3 is provided, and the residual raw material gas in the chamber 11 is provided. It is also possible to prevent the inflow of the source gas into the transfer chamber 15 by positively discharging the gas.
[0039]
In the multilayer processing apparatus of the embodiment described above, the barrier layer is formed on the surface of the substrate 12 by the barrier layer manufacturing apparatus 2, and the substrate 12 on which the barrier layer is manufactured is transferred from the transfer chamber apparatus 4 to the metal film forming apparatus 3. Then, a metal film such as copper is formed on the surface of the substrate 12 on which the barrier layer has been formed, thereby forming a multilayer film.
[0040]
Since the inside of the transfer chamber 15 of the transfer chamber device 4 is evacuated by the vacuum device 16, natural oxidation does not occur on the substrate 12 on which the barrier layer has been formed, and oxidation of the surface is reliably suppressed. Therefore, when a metal film is produced, the interface is not affected by oxidation.
[0041]
Further, since the pressure in the transfer chamber 15 is controlled to be higher than the pressure in the chamber 11, the source gas (chlorine-containing gas) of the metal film forming apparatus 3 flows into the transfer chamber 15 of the transfer chamber apparatus 4. The transfer chamber 15 and the substrate 12 on which the film is formed are not damaged by the chlorine-containing gas.
[0042]
Therefore, it is possible to use a low-cost raw material with a high film-forming rate, and to provide a multilayer processing apparatus capable of manufacturing a multilayer film in which oxidation is reliably suppressed and impurities are not left in the film. .
[0043]
<Example of Second Embodiment>
As shown in FIG. 2, the multilayer film processing apparatus includes a substrate cassette 1 for holding a large number of substrates, a barrier layer manufacturing apparatus 2 as a substrate processing apparatus for performing processing (for example, manufacturing of a barrier metal film) on the surface of the substrate. A metal film forming apparatus 3 for forming a metal film (for example, a copper film) on the surface of a substrate on which a barrier metal film has been formed, and between the substrate cassette 1 and the barrier layer forming apparatus 2 and between the barrier layer forming apparatus 2 and the metal film. A transfer chamber device 4 as a transfer chamber system for transferring a substrate between the manufacturing apparatuses 3.
[0044]
In the second embodiment, the natural oxidation suppressing means provided in the transfer chamber device 4 is different from the first embodiment. For this reason, the same members as those of the first embodiment are denoted by the same reference numerals, and duplicate description is omitted.
[0045]
The transfer chamber device 4 is provided with a transfer chamber 15 having transfer means and the like, and the inside of the transfer chamber 15 is provided with a rare gas introducing means 19 as a natural oxidation suppressing means. A rare gas such as argon or helium is introduced.
[0046]
Further, the pressure in the chamber 11 of the metal film forming apparatus 3 is detected by the pressure detecting means 20, and the rare gas introducing means 19 is controlled so that the pressure in the transfer chamber 15 becomes higher than the pressure in the chamber 11 ( Backflow prevention means).
[0047]
As a result, the inside of the transfer chamber 15 is filled with a rare gas, and the source gas (chlorine-containing gas) remaining in the chamber 11 of the metal film forming apparatus 3 is prevented from flowing into the transfer chamber 15. The transport gas 15 and the substrate 12 on which the film is formed are not damaged by the contained gas.
[0048]
Instead of providing the pressure detecting means 20 to generate a pressure difference, a means for positively discharging the raw material gas remaining inside the chamber 11 of the metal film forming apparatus 3 is provided, and the residual raw material gas in the chamber 11 is provided. It is also possible to prevent the inflow of the source gas into the transfer chamber 15 by positively discharging the gas.
[0049]
In the multilayer processing apparatus of the embodiment described above, similarly to the first embodiment, the barrier layer is formed on the surface of the substrate 12 by the barrier layer manufacturing apparatus 2, and the substrate 12 on which the barrier layer is manufactured is transferred to the transfer chamber apparatus. 4 to a metal film forming apparatus 3, where a metal film such as copper is formed on the surface of the substrate 12 on which the barrier layer has been formed, thereby forming a multilayer film.
[0050]
Since the inside of the transfer chamber 15 of the transfer chamber device 4 is filled with the rare gas from the rare gas introducing means 19, the substrate 12 on which the barrier layer has been formed is not exposed to the atmosphere, and natural oxidation may occur. And oxidation of the surface is suppressed. Therefore, when a metal film is produced, the interface is not affected by oxidation. By blocking the substrate 12 from the atmosphere by filling a rare gas, natural oxidation can be prevented without providing an expensive device.
[0051]
Further, since the pressure in the transfer chamber 15 is controlled to be higher than the pressure in the chamber 11, the source gas (chlorine-containing gas) of the metal film forming apparatus 3 flows into the transfer chamber 15 of the transfer chamber apparatus 4. The transfer chamber 15 and the substrate 12 on which the film is formed are not damaged by the chlorine-containing gas.
[0052]
Therefore, a multi-layer processing apparatus capable of forming a multi-layer film in which film formation speed is high, inexpensive raw materials can be used, and oxidation is suppressed without adding expensive equipment and impurities are not left in the film. It becomes possible to do.
[0053]
In the first embodiment and the second embodiment, an example is described in which the substrate cassette 1, the barrier layer manufacturing apparatus 2, and the metal film manufacturing apparatus 3 are provided one by one. As long as the apparatus is provided with one facility, the substrate processing apparatus for treating the surface is limited to the embodiment example as long as it is a facility for producing a multilayer film such as the metal film producing apparatus 3 or another etching apparatus. It will not be done. It is also possible to equip each facility with a plurality of facilities. For example, it is also possible to provide a plurality of metal film manufacturing apparatuses 3 and manufacture a multilayer film in which an amorphous layer and a crystalline metal layer are stacked.
[0054]
For example, the production of a barrier layer by the barrier layer production apparatus 2 is a short process because of the small thickness, and the production of a metal film by the metal film production apparatus 3 requires a predetermined thickness. It takes a longer time than the production of the layer. For this reason, by providing one apparatus for forming the barrier layer 2 and two apparatuses for preparing the metal film 3, while one metal film forming apparatus 3 is manufacturing a metal film, the other metal film forming apparatus 3 is provided with the other apparatus. A barrier layer can be formed on the substrate 12 to be transported by the barrier layer forming apparatus 2, and a multilayer film forming apparatus with high productivity can be obtained.
[0055]
Hereinafter, specific examples of the multilayer film manufacturing apparatus and the barrier layer manufacturing apparatus 2 and the metal film manufacturing apparatus 3 which are constituent equipment of the multilayer film manufacturing apparatus will be described with reference to the drawings. 3 is a schematic plan view of a multilayer film manufacturing apparatus according to one embodiment of the present invention, FIG. 4 is a schematic cross section of a barrier layer manufacturing apparatus according to one embodiment of the present invention, and FIG. 1 shows a schematic cross section of a metal film manufacturing apparatus according to the first embodiment. The configuration shown in FIGS. 3 to 5 is a specific example of the first embodiment shown in FIG.
[0056]
<Example of multilayer film manufacturing apparatus>
As shown in FIG. 3, the transfer chamber 15 of the transfer chamber device 4 is configured in a hexagonal column state, and around the transfer chamber 15, a substrate cassette 1 and a barrier layer manufacturing device 2 are provided, one each. Around the transfer chamber 15, two metal film forming apparatuses 3 are provided. Then, the inside of the transfer chamber 15 is evacuated by the vacuum device 16, and the vacuum device 16 is controlled by the pressure detecting means 17 so that the pressure in the transfer chamber 15 is higher than the pressure in the chamber 11 of the metal film forming apparatus 3. Have been.
[0057]
<Example of barrier layer manufacturing apparatus>
An example of the barrier layer manufacturing apparatus will be described based on FIG. The device shown below is an example, and the production of the barrier layer can be applied to devices other than the device shown below.
[0058]
As shown in FIG. 4, a support 21 is provided near the bottom of a cylindrical chamber 6 (made of an insulating material) made of, for example, ceramics (made of an insulating material). Is placed. The support table 21 is provided with a temperature control means 24 including a heater 22 and a coolant circulation means 23. The support table 21 is controlled by the temperature control means 24 to a predetermined temperature (for example, a temperature at which the substrate 12 is maintained at 100 to 200 ° C.). ) Is controlled.
[0059]
The upper surface of the chamber 6 is an opening, and the opening is closed by a metal member 25 (for example, W, Ti, Ta, TiSi, or the like). The inside of the chamber 6 closed by the metal member 25 is maintained at a predetermined pressure by the vacuum device 26. A plasma antenna 27 is provided around the cylindrical portion of the chamber 6, and a matching device 28 and a power supply 29 are connected to the plasma antenna 27 to supply power.
[0060]
In the cylindrical portion of the chamber 6 below the metal member 25, a raw material gas containing chlorine as a halogen (such as He, Ar, etc., having a chlorine concentration of ≤50%, preferably about 10%) is provided inside the chamber 6. Cl _Two Nozzle 30 for supplying gas). A source gas is sent to the nozzle 30 via a flow controller 31. Note that as the halogen contained in the source gas, fluorine (F), bromine (Br), iodine (I), or the like can be used.
[0061]
On the other hand, slit-shaped openings 32 are formed in a plurality of places (for example, four places) below the cylindrical portion of the chamber 6, and one ends of the cylindrical passages 33 are fixed to the openings 32, respectively. I have. A cylindrical excitation chamber 34 made of an insulator is provided in the middle of the passage 33, and a coil-shaped plasma antenna 35 is provided around the excitation chamber 34, and the plasma antenna 35 is connected to a matching unit 36 and a power supply 37. Then, power is supplied. A flow controller 38 is connected to the other end of the passage 33, and an ammonia gas (NH) as a nitrogen-containing gas is supplied into the passage 33 through the flow controller 38. _Three Gas) is supplied.
[0062]
In the barrier layer manufacturing apparatus 2 described above, the source gas is supplied from the nozzle 30 into the chamber 6, and an electromagnetic wave is incident from the plasma antenna 27 into the chamber 6, whereby Cl _Two Gas is ionized and Cl _Two Gas plasma (source gas plasma) 39 is generated. Cl _Two The gas plasma 39 causes an etching reaction in the metal member 25 to generate a precursor (MxCly: M is a metal such as W, Ti, Ta, TiSi) 40.
[0063]
Further, NH 3 is introduced into the passage 33 through the flow controller 31. _Three Supply gas and supply NH to excitation chamber 34 _Three Send gas. When an electromagnetic wave enters the inside of the excitation chamber 34 from the plasma antenna 35, NH 3 _Three The gas is ionized and NH _Three Gas plasma 41 is generated. Since a predetermined pressure difference between the pressure in the chamber 6 and the pressure in the excitation chamber 34 is set by the vacuum device 26, the NH in the excitation chamber 34 _Three Excited ammonia of the gas plasma 41 is sent from the opening 32 to the precursor (MxCly) 40 in the chamber 6.
[0064]
As a result, the metal component of the precursor (MxCly) 40 reacts with ammonia to form metal nitride (MN). At this time, the metal member 25 and the excitation chamber 34 are maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 12 by the plasma.
[0065]
The metal nitride (MN) generated inside the chamber 6 is carried to the substrate 12 controlled at a low temperature, and an MN thin film 42 is generated on the surface of the substrate 12. After the MN thin film 42 is formed, NH 3 _Three By stopping the power supply to the gas and the power supply 37, the precursor (MxCly) 40 is transferred to the substrate 12 controlled to a lower temperature than the metal member 25. The precursor (MxCly) 40 carried to the substrate 12 is reduced to only metal (M) ions by the reduction reaction and applied to the substrate 12, and an M thin film 43 is formed on the MN thin film 42 of the substrate 12. The MN thin film 42 and the M thin film 43 form a barrier metal film 44 (barrier layer).
[0066]
The reaction when the MN thin film 42 is generated can be expressed by the following equation.
2MCl + 2NH _Three → 2MN ↓ + HCl ↑ + 2H _Two ↑
The reaction when the M thin film 43 is generated can be represented by the following equation.
2MCl → 2M ↓ + Cl _Two ↑
Gases not involved in the reaction and etching products are exhausted from the exhaust port 45.
[0067]
As a source gas, Cl diluted with He, Ar, etc. _Two Although explained using gas as an example, Cl _Two It is also possible to use the gas alone or to use HCl gas. When HCl gas is applied, the source gas plasma is generated as HCl gas plasma. Therefore, the source gas may be any gas containing chlorine, and may be HCl gas and Cl gas. _Two It is also possible to use a mixed gas with a gas. Further, as the material of the metal member 7, an industrially applicable metal such as Ag, Au, Pt, or Si can be used.
[0068]
On the substrate 12 on which the barrier metal film 44 is formed, a copper (Cu) thin film or the like (other metal thin film, alloy thin film, metal oxide thin film, metal nitride thin film, etc.) is formed on the barrier metal film 44 by a film forming apparatus. Is done. By the presence of the barrier metal film 44, for example, the diffusion of Cu into the substrate 12 is prevented by the MN thin film 42, and the adhesion of Cu is ensured by the M thin film 43.
[0069]
The M thin film 43 may be omitted as the barrier metal film 44 depending on the case where the material to be formed is a material having no problem in adhesion (for example, Al) or the case where the nitride is a metal capable of maintaining the adhesion. It is also possible. Although the reduction reaction is caused by the temperature difference, a reduction gas plasma may be separately generated to cause the reduction reaction.
[0070]
In the barrier layer manufacturing apparatus 2 having the above-described configuration, the metal is generated by the plasma to manufacture the barrier metal film 44. Therefore, the barrier metal film 44 can be formed uniformly and in a thin film. For this reason, the barrier metal film 44 is formed with high accuracy even in a small concave portion having a width of several hundreds of nm provided on the substrate 12, has excellent embedding properties, and is formed in a very thin state at a high speed. It becomes possible to do.
[0071]
The configuration of the barrier layer manufacturing apparatus 2 is an example. For example, the ceiling is formed of an insulator, the metal member 25 is disposed in the chamber 6, and the planar coil-shaped plasma antenna is provided on the ceiling. It is also possible. It is also possible to supply power directly to the metal member 25 constituting the ceiling part to form a capacitively coupled structure also serving as a plasma antenna. _Two NH3 gas plasma 39 _Three Like the gas plasma 41, it can be formed separately in an excitation chamber.
[0072]
<Example of metal film production apparatus>
An example of the metal film manufacturing apparatus will be described based on FIG. The apparatus shown below is an example, and the production of the metal film can be applied to apparatuses other than the apparatus shown below.
[0073]
As shown in FIG. 5, a support 51 is provided near the bottom of a chamber 11 made of, for example, a ceramic (made of an insulating material), and a barrier metal film 44 is formed on the support 51. The mounted substrate 12 is placed. The support table 51 is provided with a temperature control means 54 including a heater 52 and a coolant circulation means 53. The support table 51 is controlled by the temperature control means 54 to a predetermined temperature (for example, a temperature at which the substrate 12 is maintained at 100 ° C. to 200 ° C.). ) Is controlled.
[0074]
The upper surface of the chamber 11 is an opening, and the opening is closed by a plate-shaped ceiling plate 55 made of an insulating material (for example, made of ceramics). The inside of the chamber 11 closed by the ceiling plate 55 is maintained at a predetermined pressure by the vacuum device 50. A plasma antenna 56 for converting the inside of the chamber 11 into plasma is provided above the ceiling plate 55, and the plasma antenna 56 is formed in a planar ring shape parallel to the surface of the ceiling plate 55. A matching device 57 and a power supply 58 are connected to the plasma antenna 56 to supply a high-frequency current.
[0075]
A member to be etched 59 formed of a metal (copper in the present embodiment) capable of forming a high vapor pressure halide is sandwiched in the cylindrical portion of the chamber 11. The member to be etched 59 includes a projection 60 and a ring 61, and is installed at a position facing the substrate 12 in the chamber 11, and the projection 60 is divided into a plurality in the circumferential direction of the chamber 11, and is disposed. It has a structure that protrudes toward the center side from a ring portion 61 installed in the cylindrical chamber 1.
[0076]
That is, a plurality of the protrusions 60 are provided in the circumferential direction from the inner wall of the chamber 11 toward the center in the radial direction, and a space exists between the protrusions 60. For this reason, the protrusion 60 is arranged 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.
[0077]
The material of the member to be etched 59 is not limited to copper (Cu) but may be a halide-forming metal, preferably a chloride-forming metal such as Ag, Au, Pt, Ir, Ta, Ti, W, or the like. .
[0078]
A nozzle 62 is connected to the cylindrical portion of the chamber 11 substantially corresponding to the support table 51. From the nozzle 62, a raw material gas containing chlorine gas as a halogen gas (He, Ar, or the like, having a chlorine concentration of ≦ 50%, preferably Chlorine gas diluted to about 10%) is supplied into the chamber 1. The nozzle 62 opens toward the member to be etched 59, and a raw material gas is sent to the nozzle 62 via a flow rate controller 63.
[0079]
In the above-described metal film manufacturing apparatus 3, the metal thin film 64 is formed by a method described in detail below.
[0080]
First, a raw material gas is supplied from the nozzle 62 into the chamber 1 and an electromagnetic wave is incident on the inside of the chamber 11 from the plasma antenna 56, thereby ionizing chlorine gas in the raw material gas to generate chlorine gas plasma. The plasma is generated in a region shown by a gas plasma 65. The reaction at this time can be represented by the following equation.
Cl _Two → 2Cl ^* ・ ・ (1)
Where Cl ^* Represents a chlorine gas radical.
[0081]
When the gas plasma 65 acts on the member to be etched 59, the member to be etched 59 is heated and an etching reaction occurs in the member to be etched 59. The reaction at this time is represented by the following equation.
Cu (s) + 2Cl ^* → CuCl _Two (G) ・ ・ (2)
Here, s represents a solid state, and g represents a gas state. The above equation (2) represents a state where the Cu component of the member to be etched 55 is etched by the gas plasma 65 and gasified. The precursor 66 is gasified CuCl _Two And substances having different composition ratios (Cu _X1 Cl _Y1 ).
[0082]
The member to be etched 59 is heated by generating gas plasma 65, and the temperature of the substrate 12 is controlled by the temperature control means 54, so that the temperature of the substrate 12 becomes lower than the temperature of the member to be etched 59. As a result, the precursor 66 is adsorbed on the substrate 12. The reaction at this time is represented by the following equation.
CuCl _Two (G) → CuCl _Two (Ad) ・ ・ (3)
Here, “ad” represents an adsorption state.
[0083]
CuCl adsorbed on substrate 3 _Two Forms a part of the metal thin film 64 (Cu thin film) by being reduced by a chlorine gas radical to become a Cu component. The reaction at this time is represented by the following equation.
CuCl _Two (Ad) + 2Cl ^* → Cu (s) + Cl _Two ↑ ・ ・ （４）
[0084]
Further, the gasified CuCl generated in the above equation (2) _Two Before being adsorbed on the substrate 12 (see the above equation (3)), a part of is reduced by chlorine gas radicals to become gaseous Cu. The reaction at this time is represented by the following equation.
CuCl _Two (G) + 2Cl ^* → Cu (g) + 2Cl _Two ↑ ・ ・ (5)
Thereafter, the gaseous copper (Cu) is deposited on the substrate 12 and becomes a part of forming the metal thin film 64.
[0085]
Gases and etching products not involved in the reaction are exhausted from the exhaust port 67.
[0086]
The member to be etched 59, which is a conductor, exists below the plasma antenna 56. As described above, the member to be etched 59 is arranged in a discontinuous state with respect to the flow direction of the current flowing through the plasma antenna 56. Therefore, the gas plasma 65 is stably generated between the member to be etched 59 and the substrate 12, that is, under the member to be etched 59. Further, the precursor 66 is also uniformly adsorbed on the substrate 12.
[0087]
In the metal film manufacturing apparatus 3 having the above-described configuration, the gas plasma 65 is used, so that the reaction efficiency is greatly improved and the film forming speed is increased. Further, Cl is used as a source gas. _Two Since gas is used, the cost can be significantly reduced. Further, since oxygen is not contained in the raw material, an oxidizing atmosphere does not occur during film formation, oxidation is suppressed, impurities can be reduced, and a high-quality metal thin film 64 can be manufactured. Become.
[0088]
The configuration of the metal film manufacturing apparatus 3 is merely an example. For example, a configuration in which the ceiling portion is formed of a metal member to be etched and a coil-shaped plasma antenna is disposed in the cylindrical portion of the chamber 11 is also possible. Further, it is also possible to configure the ceiling portion with a metal member to be etched and to supply power directly to the member to be etched, thereby forming a capacitively coupled structure that also serves as a plasma antenna. Furthermore, it is also possible to adopt a configuration in which gas plasma is separately formed in an excitation chamber and excited chlorine is supplied into the chamber.
[0089]
【The invention's effect】
A multilayer film processing apparatus according to the present invention includes a chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, and a source gas supply for supplying a source gas containing halogen into the chamber. Means for generating a precursor of a metal component and a source gas contained in the member to be etched by generating a source gas plasma by converting the inside of the chamber into a plasma to generate a source gas plasma and etching the member to be etched with the source gas plasma; A temperature control means for lowering the temperature of the substrate side than the temperature of the member to be etched side and forming at least a metal component of the precursor on the substrate, and further comprising a natural oxidation suppressing means. And a substrate processing apparatus for performing processing on the surface of the substrate. Since it is sent from a metal system to a metal film forming apparatus, a film forming speed is high, an inexpensive raw material can be used, and a multilayer film processing capable of suppressing oxidation and producing a multilayer film in which no impurities remain in the film can be manufactured. It becomes possible to be a device.
[0090]
Further, in the multilayer film processing apparatus according to the first aspect, the natural oxidation suppressing means in the transfer chamber system is a vacuum device that evacuates the inside of the transfer chamber system, so that oxidation can be reliably suppressed.
[0091]
Further, in the multilayer film processing apparatus according to the first aspect, since the natural oxidation suppressing means in the transfer chamber system is constituted by a rare gas introduction means for introducing a rare gas into the transfer chamber, special expensive equipment is additionally provided. Oxidation can be suppressed without performing.
[0092]
Further, in the multilayer film processing apparatus according to the first aspect, the natural oxidation suppressing means in the transfer chamber system is constituted by a rare gas introducing means for introducing a gas containing halogen into the transfer chamber, so that it is particularly expensive. Oxidation can be suppressed without any additional equipment.
[0093]
Further, in the multilayer film processing apparatus according to claim 1, the natural oxidation suppressing means in the transfer chamber system includes a rare gas introduction means for introducing a rare gas into the transfer chamber and a rare gas introduction means for introducing a gas containing halogen. Therefore, oxidation can be suppressed without providing special expensive equipment.
[0094]
The multilayer film processing apparatus according to any one of claims 1 to 3, further comprising backflow prevention means for preventing backflow of the halogen gas in the chamber of the metal film forming apparatus into the transfer chamber. In addition, the halogen gas does not flow back into the transfer chamber.
[0095]
Further, in the multilayer film processing apparatus according to the present invention, the backflow preventing means is a concentration reducing means for reducing the concentration of residual halogen gas in the chamber of the metal film forming apparatus. Can be prevented.
[0096]
Further, in the multilayer film processing apparatus according to any one of claims 1 to 5, the pressure in the transfer chamber is maintained higher than the pressure in the chamber of the metal film forming apparatus, and the transfer of the gas in the chamber is performed. Since the pressure adjusting means for preventing the inflow into the chamber is provided, the backflow of the halogen gas can be reliably prevented.
[0097]
Further, in the multilayer film processing apparatus according to any one of claims 1 to 8, since the substrate processing apparatus is a barrier layer manufacturing apparatus for manufacturing a barrier metal film on a surface of a substrate, oxidation is suppressed. A multilayer film having a barrier layer can be manufactured.
[0098]
Further, in the multilayer film processing apparatus according to the ninth aspect, the transfer chamber system is provided with an accommodation chamber system for the substrate, and two metal film production apparatuses are provided. Since the transfer device for transferring the substrate between the barrier metal film forming apparatus and the two metal film forming apparatuses is provided, it is possible to efficiently manufacture a multilayer film in which oxidation is suppressed.
[0099]
A metal film manufacturing apparatus according to the present invention includes a chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, and a source gas supply for supplying a source gas containing halogen into the chamber. Means for generating a precursor of a metal component and a source gas contained in the member to be etched by generating a source gas plasma by converting the inside of the chamber into a plasma to generate a source gas plasma and etching the member to be etched with the source gas plasma; A temperature control means for lowering the temperature of the substrate side than the temperature of the plasma generation means side to form at least a metal component of the precursor on the substrate, and a transfer chamber provided with a natural oxidation suppressing means in the chamber. Since the substrate is transported from the system, the film forming speed is high, and inexpensive raw materials can be used. Things it is possible to a metal film production apparatus capable of producing a multi-layer film does not remain.
[0100]
The transfer chamber of the present invention includes a chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, and a source gas supply unit for supplying a source gas containing halogen into the chamber. Plasma generating means for generating a precursor of a metal component and a source gas contained in a member to be etched by generating a source gas plasma by converting the inside of the chamber into a plasma to generate a source gas plasma and etching the member to be etched with the source gas plasma; A temperature control means for lowering the temperature on the side than the temperature on the plasma generation means side and forming a metal component of at least a precursor on the substrate, and a transfer chamber for transferring the substrate to a metal film production apparatus, Since natural oxidation suppressing means is provided, the film forming speed is high and inexpensive raw materials can be used. Pure things makes it possible to transfer chamber capable of producing a multi-layer film does not remain.
[0101]
The transfer chamber of the present invention for achieving the above object is a transfer chamber for transferring a substrate from a substrate processing apparatus for performing a process on the surface of the substrate, and is provided with a natural oxidation suppressing means. A transfer chamber that prevents oxidation of the substrate that has been formed can be provided.
[0102]
Further, in the transfer chamber according to claim 13, since the substrate from the substrate processing apparatus for performing the processing on the surface of the substrate is transferred to the metal film forming apparatus, the substrate without oxidation can be transferred to the metal film forming apparatus. become.
[0103]
The substrate processing apparatus of the present invention is a substrate processing apparatus that performs processing on the surface of a substrate, and transports the substrate that has been subjected to the surface processing in a transport chamber provided with a natural oxidation suppressing unit. Oxidation of the substrate is prevented.
[0104]
In the method for producing a multilayer film according to the present invention, a substrate whose surface has been treated is transported into a chamber of a metal film production apparatus in a transport chamber in a state where natural oxidation is suppressed, while a member to be etched is etched with a source gas plasma. By generating a precursor of the metal component and the source gas contained in the member to be etched in the chamber, the temperature of the substrate is made lower than the temperature of the member to be etched, and at least the metal component of the precursor is formed on the substrate. Since a film is formed, a film forming rate is high, an inexpensive raw material can be used, and a multilayer film processing method capable of suppressing oxidation and producing a multilayer film in which impurities do not remain in the film can be formed. Becomes possible.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a multilayer film manufacturing apparatus according to a first embodiment of the present invention.
FIG. 2 is a schematic configuration diagram of a multilayer film manufacturing apparatus according to a second embodiment of the present invention.
FIG. 3 is a schematic plan view of a multilayer film manufacturing apparatus according to one embodiment of the present invention.
FIG. 4 is a schematic sectional view of an apparatus for producing a barrier layer according to one embodiment of the present invention.
FIG. 5 is a schematic sectional view of a metal film manufacturing apparatus according to one embodiment of the present invention.
[Explanation of symbols]
1 Board cassette
2 Barrier layer production equipment
3 Metal film production equipment
4 Transfer chamber device
6,11 chamber
7 Processing gas nozzle
12 Substrate
13,27,35,56 Plasma antenna
14 Raw material gas nozzle
15 transfer chamber
16,26,50 Vacuum equipment
17,20 Pressure detecting means
19 Noble gas introduction means
21,51 support base
22, 52 heater
23, 53 refrigerant distribution means
24,54 Temperature control means
25 metal members
28, 36, 57 Matching device
29, 37, 58 Power supply
30 nozzles
31, 38, 63 Flow controller
32 opening
33 passage
34 Excitation Chamber
39 Cl _Two Gas plasma
40,66 precursor
41 NH _Three Gas plasma
42 MN film
43 M film
44 Barrier metal film
50 vacuum equipment
55 ceiling board
59 Member to be etched
60 protrusion
61 Ring section
62 nozzle
64 metal thin film
65 Gas plasma

Claims (16)

A chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, a source gas supply unit for supplying a source gas containing halogen into the chamber, and a plasma in the chamber. Means for generating a precursor of a metal component contained in the member to be etched and a source gas by generating a source gas plasma and etching the member to be etched with the source gas plasma; Temperature control means for forming a film of at least a metal component of the precursor on the substrate by lowering the temperature on the side, comprising a metal film production apparatus,
Further, a transfer chamber system provided with natural oxidation suppressing means,
A substrate processing apparatus that performs processing on the surface of the substrate,
A multilayer film processing apparatus, wherein a substrate processed by the substrate processing apparatus is sent from a transfer chamber system to a metal film forming apparatus. The multilayer processing apparatus according to claim 1,
The multi-layer processing apparatus, wherein the natural oxidation suppressing means in the transfer chamber system is a vacuum device for evacuating the inside of the transfer chamber system. The multilayer processing apparatus according to claim 1,
A multilayer film processing apparatus, wherein the natural oxidation suppressing means in the transfer chamber system comprises a rare gas introduction means for introducing a rare gas into the transfer chamber. The multilayer processing apparatus according to claim 1,
The multilayer film processing apparatus, wherein the natural oxidation suppressing means in the transfer chamber system is constituted by a rare gas introducing means for introducing a gas containing halogen into the transfer chamber. The multilayer processing apparatus according to claim 1,
A multi-layer processing apparatus characterized in that the natural oxidation suppressing means in the transfer chamber system comprises a rare gas introduction means for introducing a rare gas into the transfer chamber and a rare gas introduction means for introducing a gas containing halogen. apparatus. The multilayer processing apparatus according to any one of claims 1 to 3,
A multilayer film processing apparatus comprising a backflow preventing means for preventing backflow of a halogen gas in a chamber of a metal film manufacturing apparatus into a transfer chamber. The multilayer processing apparatus according to claim 6,
The multilayer film processing apparatus, wherein the backflow preventing means is a concentration reducing means for reducing the concentration of a residual halogen gas in a chamber of the metal film forming apparatus. The multilayer processing apparatus according to any one of claims 1 to 5,
A multi-layer processing apparatus comprising: a pressure adjusting means for maintaining a pressure in the transfer chamber higher than a pressure in the chamber of the metal film forming apparatus to prevent a gas in the chamber from flowing into the transfer chamber. . The multilayer processing apparatus according to any one of claims 1 to 8,
The substrate processing apparatus is a barrier layer manufacturing apparatus for manufacturing a barrier metal film on a surface of a substrate. The multilayer processing apparatus according to claim 9,
The transfer chamber system is provided with an accommodation chamber system for a substrate, and is provided with two metal film production apparatuses. Between the accommodation chamber system and the barrier layer production apparatus, and between the barrier layer production apparatus and the two equipment metal film production apparatus. A multilayer film processing apparatus comprising a transfer device for transferring a substrate between them. A chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, a source gas supply unit for supplying a source gas containing halogen into the chamber, and a plasma in the chamber. Generating means for generating a precursor of the metal component contained in the member to be etched and the source gas by generating the source gas plasma by etching the member to be etched with the source gas plasma, and controlling the temperature of the substrate side to the plasma generating means. Temperature control means for lowering the temperature of the side and forming at least the metal component of the precursor on the substrate.
A metal film manufacturing apparatus, wherein a substrate is transferred into a chamber from a transfer chamber system having a natural oxidation suppressing means. A chamber for accommodating a substrate, a metal member to be etched provided in the chamber at a position facing the substrate, a source gas supply unit for supplying a source gas containing halogen into the chamber, and a plasma in the chamber. Generating means for generating a precursor of the metal component contained in the member to be etched and the source gas by generating the source gas plasma by etching the member to be etched with the source gas plasma, and controlling the temperature of the substrate side to the plasma generating means. Temperature control means for lowering the temperature of the precursor metal component on the substrate by lowering the temperature on the side, and a transfer chamber for transferring the substrate to a metal film forming apparatus,
A transfer chamber comprising natural oxidation suppressing means. A transfer chamber for transferring a substrate from a substrate processing apparatus that performs processing on the surface of the substrate,
A transfer chamber comprising natural oxidation suppressing means. The transfer chamber according to claim 13,
A transfer chamber for transferring a substrate from a substrate processing apparatus that performs processing on a surface of the substrate to a metal film forming apparatus. What is claimed is: 1. A substrate processing apparatus for processing a surface of a substrate, wherein the substrate having been subjected to the surface processing is transferred in a transfer chamber provided with a natural oxidation suppressing unit. The substrate whose surface has been treated is transferred into the chamber of the metal film forming apparatus in a transfer chamber in a state where natural oxidation is suppressed, and is included in the member to be etched by etching the member to be etched with source gas plasma. A multilayer comprising generating a precursor of a metal component and a source gas in a chamber, lowering the temperature of the substrate side from the temperature of the member to be etched, and forming at least the metal component of the precursor on the substrate. Film preparation method.

Images