JPH11312653A - Method of forming barrier metal layer - Google Patents

Abstract

(57) Abstract: A method for forming a barrier metal layer by a plasma CVD method, which has excellent characteristics under accurate temperature control in a formation process and can minimize residual halogens. provide. In a method of forming a barrier metal layer, a composite material including a base material in which the structure of a ceramic member is filled with an aluminum-based material and a ceramic layer provided on a surface of the base material. In a state where the substrate is mounted on the substrate mounting stage 10 having an electrostatic chuck function and having a temperature control means, a barrier metal layer made of a high melting point metal or a compound thereof is plasma-coated on the substrate. It is formed by a CVD method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a barrier metal layer required for forming a contact hole, a via hole, a trench wiring and the like.

[0002]

2. Description of the Related Art The miniaturization and high integration of LSI have not stopped, and the mass production of devices of the 0.13 μm rule is imminent. In such an LSI manufacturing process of the next generation and thereafter, it is necessary to form a barrier metal layer before forming a contact hole, a via hole, a trench wiring and the like. Attention has been paid to a technique of forming a barrier metal layer formed at the bottom of a contact hole or a via hole or in a trench wiring by a CVD method instead of a conventional sputtering method. This is because the aspect ratio is increasing in contact holes, via holes, trench wiring in a damascene process, and combinations of via holes and trench wiring in a dual damascene process (these may be collectively referred to as contact holes, etc.). This is because it is becoming difficult to secure sufficient coverage of the barrier metal layer in the conventional sputtering method. When the coverage of the barrier metal layer is insufficient, for example, when spikes occur in the silicon semiconductor substrate or when a contact hole or the like is buried in tungsten, the nucleus of tungsten does not grow at the bottom of the contact hole or the like, and the contact with tungsten It becomes difficult to fill holes and the like.

The barrier metal layer is usually made of a high melting point metal or a compound thereof, and can be formed by a plasma CVD method or a thermal CVD method. In the plasma CVD method, a metal halide is reduced with hydrogen to form a barrier metal layer. On the other hand, heat C
In the VD method, a metal complex is used as a source gas.

[0004]

The thermal CVD method using a metal complex as a source gas has a problem that the resistance of the barrier metal layer increases because carbon remains in the formed barrier metal layer. In particular, in the damascene process or the dual damascene process, since the side wall and the bottom surface of the trench wiring are covered with the barrier metal layer, it is a very serious problem that the resistance of the barrier metal layer is high. Further, in the thermal CVD method, the film formation temperature is as high as about 650 ° C., so that the barrier metal layer may not be formed depending on the base material in some cases.

On the other hand, film formation by the plasma CVD method can be performed at a lower temperature than the thermal CVD method, so that film formation can be performed with any base material. However, since a metal halide, for example, a metal chloride is used as a source gas, halogen remains in the barrier metal layer, and as a result, there is a problem that, for example, the wiring made of an aluminum-based material is corroded. There is a problem with reliability. That is, since the formation of the barrier metal layer by the plasma CVD method is based on the reduction reaction of the metal halide by the hydrogen plasma, it is important to accurately maintain the temperature of the base which is the base when forming the barrier metal layer. is there.
When the temperature of the substrate changes during the formation of the barrier metal layer, there arises a problem that characteristics change in the thickness direction of the barrier metal layer, and in particular, a residual amount of halogen in the barrier metal layer changes. That is, if the temperature of the substrate at the time of forming the barrier metal layer is low, the amount of halogen remaining in the barrier metal layer increases, and the amount of halogen finally remaining in the barrier metal layer increases.

Incidentally, in the plasma CVD method,
Large heat input from the plasma to the substrate occurs due to irradiation of the substrate (for example, a semiconductor substrate) with high-density plasma.
As a result, for example, the temperature of the base may increase by about 40 ° C. to 100 ° C. or more compared to before the generation of plasma. Therefore, when the substrate is heated by a substrate mounting stage (for example, a wafer stage) for holding the substrate and formed by a plasma CVD method at a high temperature, the effect of heat input from the plasma to the substrate is suppressed, and the substrate is precisely formed. Despite the importance of the technique of controlling the temperature to the set temperature, a sufficiently satisfactory method has not yet been obtained.

For accurate temperature control in the formation process, for example, it is necessary to bring the semiconductor substrate into close contact with the substrate mounting stage. A simple means for that purpose is a clamp. However, when a clamp is used, a barrier metal layer cannot be formed on a portion of the semiconductor substrate in contact with the clamp. Also, since the semiconductor substrate is pressed against the substrate mounting stage only at the peripheral portion of the semiconductor substrate, uniform contact between the central portion and the peripheral portion of the semiconductor substrate at the substrate mounting stage is required as the diameter of the semiconductor substrate increases. There is a problem that it is difficult.

As another means for bringing a semiconductor substrate into close contact with a substrate mounting stage, there is an electrostatic chuck. This electrostatic chuck is, as it is, an apparatus for adsorbing a semiconductor substrate to a substrate mounting stage by electrostatic attraction. That is, the electrostatic chuck usually includes a dielectric member provided on the surface of the substrate mounting stage, and generates an electrostatic attraction force on the dielectric member by applying a DC voltage to the dielectric member. When the electrostatic chuck is used, unlike the case where a clamp is used, the entire surface of the semiconductor substrate can be securely brought into close contact with the base mounting stage.

By the way, when a conventional substrate mounting stage provided with an electrostatic chuck is heated to a high temperature, the difference between the linear expansion coefficient of the substrate mounting stage and the linear expansion coefficient of the dielectric member causes the dielectric member to move. Cracks occur, and the function as an electrostatic chuck is lost. Means for solving such a problem is disclosed in, for example, JP-A-10-32239. The electrostatic chuck stage disclosed in this patent publication is formed by joining a ceramic sintered body plate for an electrostatic chuck and a composite plate of ceramic and aluminum. By using this electrostatic chuck stage, the semiconductor substrate can be securely brought into close contact with the base mounting stage even at a high temperature. However, this patent publication does not describe nor suggest formation of a specific barrier metal layer by a plasma CVD method.

Accordingly, it is an object of the present invention to form a barrier metal layer by a plasma CVD method which has excellent characteristics under accurate temperature control in a forming process and can minimize the residual halogen. It is to provide a method.

[0011]

An object of the present invention is to provide a composite material comprising a base material in which the structure of a ceramic member is filled with an aluminum-based material, and a ceramic layer provided on the surface of the base material. Has an electrostatic chuck function,
The present invention is characterized in that a barrier metal layer made of a high melting point metal or a compound thereof is formed on a substrate by a plasma CVD method while the substrate is mounted on a substrate mounting stage provided with a temperature control means. Can be achieved by the method of forming a barrier metal layer described above.

The substrate temperature when forming the barrier metal layer by the plasma CVD method is preferably 300 ° C. to 500 ° C. Examples of the base include a substrate, an insulating layer provided on the substrate, and wiring formed on the substrate and the insulating layer. Examples of the substrate forming the base include a compound semiconductor such as a silicon semiconductor substrate and a GaAs substrate or a semi-insulating substrate, a semiconductor substrate having an SOI structure, and an insulating substrate. The insulating layer constituting the base may be SiO ₂ , BPSG, PSG, BSG, AsS
G, PbSG, SbSG, NSG, SOG, LTO (Lo
w TemperatureOxide, low-temperature CVD-SiO _2), Si
Known materials such as N, SiON, and a fluorocarbon film (—CF ₂ ) _n , or a laminate of these materials can be exemplified.

A specific structure of the base is exemplified below. In the case of forming a contact hole: The base is, for example, a semiconductor substrate and an insulating layer (interlayer insulating layer) formed on the semiconductor substrate, and an opening is formed in the insulating layer (interlayer insulating layer). When forming: The base is a lower wiring formed on the base insulating layer and an insulating layer (interlayer insulating layer) formed on the entire surface including the lower wiring, and an opening is formed in the insulating layer (interlayer insulating layer). In the case of forming trench wiring based on a damascene process: a structure in which a base is an insulating layer, and a groove in which wiring is to be formed is formed in this insulating layer, a combination of a via hole and a trench wiring based on a dual damascene process is used. When forming: The base is a lower wiring formed on the base insulating layer and an insulating layer (interlayer insulating layer) formed on the entire surface including the lower wiring. Configuration mouth and grooves communicating with the opening portions are provided

In the method for forming a barrier metal layer according to the present invention, the high melting point metal or its compound constituting the barrier metal layer may be made of Ti, TiN, Ta, TaN, W, WN,
At least one selected from the group consisting of Mo and MoN
Preferably, it is a seed material. Specifically, as a high melting point metal or a compound thereof constituting a barrier metal layer, a single layer structure of Ti, TiN, Ta, TaN, W, WN, Mo or MoN, Ti / TiN, Ta / TaN, W /
A lamination structure of WN, Ti / WN, and Mo / MoN can be exemplified. In the laminated structure, the material before “/” indicates the lower layer, and the material after “/” indicates the upper layer. The same applies to the following.

In the method of forming a barrier metal layer according to the present invention, it is preferable that the substrate mounting stage is used as an electrode, and the ceramic layer exhibits a function as an electrostatic chuck. In addition, it is preferable that a temperature control means is provided on the substrate mounting stage, and the temperature control means is constituted by a heater. The heater may be disposed outside the composite material, or may be disposed inside the base material. In the latter case,
Assuming that the linear expansion coefficient of the base material is α ₁ [unit: 10 ⁻⁶ / K], the linear expansion coefficient α _{H of} the material constituting the heater [unit: 10]
⁻⁶ / K] preferably satisfies the relationship of (α ₁ -3) ≦ α _H ≦ (α ₁ +3). Here, the material forming the heater means a material forming a portion of the heater (for example, a sheath tube) in contact with the base material. The same applies to the following. Alternatively, a temperature control means is provided on the substrate mounting stage, and the temperature control means may be constituted by a pipe for flowing a temperature control heat medium provided inside the base material. In this case, When the linear expansion coefficient of the base material is α ₁ [unit: 10 ⁻⁶ / K], the linear expansion coefficient α _P [unit: 10 ⁻⁶ / K] of the pipe is (α ₁ -3) ≦ α _P ≦ ( It is preferable to satisfy the relationship of α ₁ +3). In general, the linear expansion coefficient α can be expressed as α = (dL / dθ) / L ₀ where L is the length of the object, L _{0 is} the length of the object at 0 ° C., and θ is the temperature. The unit is K ^-1 (1 / K), but in the present specification, 10 ^-6 /
The coefficient of linear expansion is expressed in units of K. Hereinafter, when the linear expansion coefficient is described, a unit may be omitted in some cases.

When the linear expansion coefficient α _{1 of the} base material and the linear expansion coefficients α _H and α _{P of} the material and the pipe constituting the heater satisfy these relationships, it is possible to effectively prevent the ceramic layer from being damaged. Can be prevented.

The coefficient of linear expansion of the base material is α ₁ [unit: 10
⁻⁶ / K], the coefficient of linear expansion α of the ceramic layer
₂ [unit: 10 ⁻⁶ / K] is (α ₁ −3) ≦ α ₂ ≦ (α ₁ +
It is preferable that the relationship of 3) is satisfied. by this,
For example be used at a high temperature of about 500 ° C, it can be almost certainly prevent damage occurrence of the ceramic layer due to the difference in linear expansion coefficient alpha ₂ of the linear expansion coefficient alpha ₁ and the ceramic layer of the base material Becomes

Such a base material is prepared by, for example, (A) filling a structure of a ceramic member with an aluminum-based material and thereby forming a base material having a structure of the ceramic member filled with an aluminum-based material. And a step of (B) providing a ceramic layer on the surface of the base material.

In this case, the composition of the ceramic member forming the base material is cordierite ceramics, and the composition of the aluminum-based material forming the base material is aluminum (A
1) and silicon (Si), and the material constituting the ceramic layer can be Al ₂ O ₃ or AlN. The material constituting the ceramic layer includes, for example, TiO ₂ in order to adjust the coefficient of linear expansion and the electrical characteristics of the ceramic layer.
May be added. It is desirable to determine the volume ratio between the cordierite ceramics and the aluminum-based material so as to satisfy the relationship of (α ₁ -3) ≦ α ₂ ≦ (α ₁ +3). Alternatively, the volume ratio of cordierite ceramics / aluminum-based material is 25/75 to 75/25,
Preferably, it is set to 25/75 to 50/50. With such a volume ratio, not only the control of the coefficient of linear expansion of the base material, but also the base material has a value closer to the metal than the electrical conductivity or thermal conductivity of pure ceramics. As a result, not only a voltage but also a bias can be applied to such a base material. Furthermore, based on the aluminum-based material, the aluminum-based material contains 12 to 35% by volume of silicon, preferably 16 to 35% by volume, and more preferably 20 to 35% by volume. α ₁ -3) ≦ α ₂ ≦ (α ₁ +
It is desirable to satisfy the relationship of 3). Actually, the structure of a ceramic member made of cordierite ceramic is filled with aluminum (Al) and silicon (Si), and silicon (Si) is not contained in aluminum (Al). However, in order to express the volume ratio between aluminum (Al) and silicon (Si) in an aluminum-based material, the expression that aluminum-based material contains silicon is used. The same applies to the following.

When the composition of the ceramic member forming the base material is cordierite ceramics and the composition of the aluminum-based material forming the base material is aluminum (Al) and silicon (Si), the above step (A) is performed in A ceramic member composed of porous cordierite ceramics is placed in a container, and an aluminum-based material composed of molten aluminum and silicon is poured into the container, and the ceramic member is formed by high-pressure casting. Preferably, the method comprises a step of filling an aluminum-based material. In this case, the ceramic member is, for example, a die press molding method,
Forming cordierite ceramics by hydrostatic molding (also called CIP method or rubber press molding method), casting method (also called slip casting method), or slurry casting method, and then firing (sintering). Can be obtained by

The ceramic member can be prepared by forming cordierite ceramic powder and then firing the same. However, a mixture of cordierite ceramic powder and cordierite ceramic fibers is fired (sintered). It is preferable to obtain the porous ceramic member in order to obtain a porous ceramic member and to prevent the ceramic member from being damaged when the base material is manufactured. In the latter case, the ratio of the cordierite ceramic fibers in the fired body (sintered body) is desirably 1 to 20% by volume, preferably 1 to 10% by volume, and more preferably 1 to 5% by volume. The average particle diameter of the cordierite ceramic powder is 1 to 100 μm, preferably 5 to 50 μm, more preferably 5 to 10 μm, and the average diameter of the cordierite ceramic fibers is 2 to 10 μm, preferably 3 to 5 μm. Yes, the average length is desirably 0.1 to 10 mm, preferably 1 to 2 mm. Furthermore, a mixture of cordierite ceramics powder and cordierite ceramics fiber is mixed with 8
00 to 1200 ° C, preferably 800 to 1100
It is desirable to fire (sinter) at ゜ C. The porosity of the ceramic member is 25 to 75%, preferably 5 to 75%.
It is desirably 0 to 75%.

The temperature of the ceramic member when the molten aluminum material is poured into the container is set to 500 to 1000 ° C., preferably 700 to 800 ° C.
When the temperature of the aluminum-based material at the time of pouring the molten aluminum-based material into the container is set to 700 to 1000 ° C., preferably 750 to 900 ° C., The absolute pressure to be applied is desirably 200 to 1500 kgf / cm ² , preferably 800 to 1000 kgf / cm ² .

Alternatively, the composition of the ceramic member forming the base material is aluminum nitride (AlN), and the composition of the aluminum-based material forming the base material is aluminum (A
l) or aluminum (Al) and silicon (Si), and the material constituting the ceramic layer is Al ₂ O ₃ or AlN
It can be. In addition, for example, TiO ₂ or Y _x O _y may be added to the material constituting the ceramic layer in order to adjust the coefficient of linear expansion and the electrical characteristics of the ceramic layer. In this case, it is preferable to determine the volume ratio between aluminum nitride and the aluminum-based material so as to satisfy the relationship of (α ₁ −3) ≦ α ₂ ≦ (α ₁ +3). Alternatively, the volume ratio of the aluminum nitride / aluminum-based material is 40/60 to 80/20, preferably 60/40.
It is desirable to set it to 70/30. With such a volume ratio, not only the control of the coefficient of linear expansion of the base material, but also the base material has a value closer to the metal than the electrical conductivity or thermal conductivity of pure ceramics, A bias can be applied to such a base material as well as a voltage.

When the composition of the ceramic member forming the base material is aluminum nitride (AlN) and the composition of the aluminum-based material forming the base material is aluminum (Al), the above-mentioned step (A) is performed under the non-pressurized condition. Based on the metal infiltration method,
Preferably, the method comprises a step of infiltrating an aluminum-based material containing molten aluminum into a ceramic member formed from aluminum nitride particles in a non-pressurized state. The ceramic member is formed by, for example, a die press molding method, a hydrostatic molding method, a casting method, or a slurry casting method, and then fired at a temperature of 500 to 1000 ° C., preferably 800 to 1000 ° C. (Sintering). In this case, the average particle size of the aluminum nitride particles is 10 to 100.
μm, preferably 10 to 50 μm, more preferably 1 μm
Desirably, the thickness is 0 to 20 μm.

Alternatively, the composition of the ceramic member forming the base material is silicon carbide (SiC), and the composition of the aluminum-based material forming the base material is aluminum (Al) or aluminum (Al) and silicon (Si); The material constituting the ceramic layer can be Al ₂ O ₃ or aluminum nitride (AlN). Note that, for example, TiO ₂ may be added to the material forming the ceramic layer in order to adjust the coefficient of linear expansion and the electrical characteristics of the ceramic layer. In this case, it is preferable to determine the volume ratio between silicon carbide and the aluminum-based material so as to satisfy (α ₁ -3) ≦ α ₂ ≦ (α ₁ +3). Alternatively, the volume ratio of the silicon carbide / aluminum-based material is set to 40/60 to 8
0/20, preferably 60/40 to 70/30. With such a volume ratio, not only the control of the coefficient of linear expansion of the base material, but also the base material has a value closer to the metal than the electrical conductivity or thermal conductivity of pure ceramics, A bias can be applied to such a base material as well as a voltage. still,
When the composition of the aluminum-based material constituting the base material is aluminum and silicon, the aluminum-based material contains silicon in an amount of 12 to 35% by volume, preferably 16 to 35% by volume, and more preferably 20 to 35% by volume. Is desirable to satisfy (α ₁ −3) ≦ α ₂ ≦ (α ₁ +3).

The ceramic layer is preferably formed on the surface of the base material by a thermal spraying method, or is preferably attached to the surface of the base material by a brazing method. Here, the linear expansion coefficient [unit: 10 ⁻⁶ / K] of the brazing material is also (α ₁ −3), where the linear expansion coefficient of the base material is α ₁ [unit: 10 ⁻⁶ / K].
As described above, it is desirable that the value be in the range of (α ₁ +3) or less.

By fabricating the substrate mounting stage from such a composite material, the base material has intermediate properties between the ceramic member and the aluminum-based material. It can be adjusted to a value. Therefore, it is possible to avoid the occurrence of damage to the ceramic layer due to the thermal expansion between the base material and the ceramic layer, and it is possible to reliably use the base mounting stage made of the composite material at a high temperature. Moreover, since the base material has a high thermal conductivity, the base can be efficiently heated by the base mounting stage. Thus, the plasma CVD is performed under accurate temperature control in the film forming process while the substrate is securely mounted on the substrate mounting stage by the electrostatic chuck function of the substrate mounting stage.
The barrier metal layer can be formed by the method. Further, since the ceramic layer is provided, it is possible to prevent the occurrence of metal contamination and to effectively prevent the corrosion of the composite material due to the halogen-based gas.

When a barrier metal layer is formed on a substrate by a plasma CVD method, a material constituting the barrier metal layer is deposited on a chamber side wall or a top plate of a CVD apparatus, and as a result, this deposit becomes a particle source. There is a possibility that it will end up. In such a case, the temperature of the chamber side wall and the top plate of the CVD apparatus is set to a predetermined temperature (preferably 100 to 50).
It is desirable to perform the plasma CVD while maintaining the temperature at 0 ° C., more preferably 200 to 500 ° C.).

The side wall and the top plate of the chamber are made of a composite material comprising a base material in which the structure of a ceramic member is filled with an aluminum-based material and a ceramic layer provided on the surface of the base material. Is preferred.
The composite material is provided with a temperature control means, and this temperature control means is preferably constituted by a heater. The heater may be provided outside the composite material or inside the base material. In the latter case, the coefficient of linear expansion of the base material is α ₁
[Unit: 10 ^-6 / K] when the coefficient of linear expansion alpha _H [unit: 10 ^-6 / K] of the material constituting the heater (α ₁ -3) ≦
It is preferable to satisfy the relationship α _H ≦ (α ₁ +3).

[0030] The chamber side wall and the top plate are combined with a base material in which the structure of a ceramic member is filled with an aluminum-based material.
If it is made of a composite material comprising a ceramic layer provided on the surface of the base material, the temperature of the chamber side wall and the ceiling is set to a sufficiently high temperature to prevent the material forming the barrier metal layer from being deposited on the chamber side wall and the top plate. Even if the plate is held, the ceramic layer is not damaged. Further, since the ceramic layer is provided, it is possible to prevent the occurrence of metal contamination and to effectively prevent the corrosion of the composite material due to the halogen-based gas.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings based on embodiments of the invention (hereinafter abbreviated as embodiments).

(Embodiment 1) FIG. 1 shows a conceptual diagram of a bias CVD apparatus 20 (hereinafter simply abbreviated as CVD apparatus 20) suitable for use in Embodiment 1. CVD equipment 2
The substrate mounting stage 10 for holding and fixing the silicon semiconductor substrate 40 is disposed in the chamber 21 of the “0”.

Base mounting stage 1 according to the first embodiment
FIG. 2A is a schematic cross-sectional view of FIG. The substrate mounting stage 10 is made of a composite material 11.
The composite material 11 includes a base material 12 (corresponding to a temperature control jacket) in which the structure of the ceramic member is filled with an aluminum-based material, and a ceramic layer 13 provided on the surface of the base material 12. This substrate mounting stage 10
Has an electrostatic chuck function and is equipped with temperature control means. Specifically, the ceramic layer 13 as a dielectric layer has an electrostatic chuck function. Further, on the lower surface of the base material 12, a PBN heater (pyrolytic boron nitride nitride pyrolytic
A heater 14 made of a graphite heater is attached. A pusher pin (not shown) for pushing up, for example, the silicon semiconductor substrate 40 mounted and held on the ceramic layer 13 is embedded in the base mounting stage 10. The pusher pin is provided with a mechanism (not shown) for projecting the pusher pin above the top surface of the ceramic layer 13 or burying the pusher pin below the top surface.

The composite material 11 according to the first embodiment is, specifically, a mother material in which the structure of a ceramic member made of cordierite ceramic is filled with an aluminum-based material made of aluminum (Al) and silicon (Si). It is composed of a material 12 and a ceramic layer 13 made of Al ₂ O ₃ provided on the surface of the base material 12 (the surface and the side surface on the chamber 21 side). Also, based on the aluminum-based material, the aluminum-based material contains 20% silicon.
% By volume. The shape of the base material 12 is a disk shape.
Here, cordierite ceramics means that about 13% by weight of MgO, about 52% by weight of SiO _{2 and} about ₃ % by weight of Al ₂ O 3.
Ceramics adjusted to a composition ratio of 5% by weight. The coefficient of linear expansion of cordierite ceramics is 0.1 ×
10 ⁻⁶ / K.

The ceramic member was a fired body (sintered body) of a mixture of cordierite ceramic powder and cordierite ceramic fiber, and the ratio of the cordierite ceramic fiber in the fired body was 5% by volume. Here, the average particle diameter of the cordierite ceramic powder is 10 μm, the average diameter of the cordierite ceramic fibers is 5 μm, and the average length is 2 mm.
The porosity of the ceramic member is about 50%, and the pore diameter is about 1 to 2 μm. Therefore, the volume ratio of cordierite ceramics / aluminum-based material is about 1/1. The linear expansion coefficient of the base material 12 having such a configuration is 100 to
About 10.6 × 10 ⁻⁶ / K at an average value at 300 ° C.
It is. That is, α ₁ = 10.6. Further, since the volume ratio of cordierite ceramics / aluminum-based material is about 1/1, the base material 12 has a value closer to the metal than the electrical conductivity or thermal conductivity of pure ceramics. Therefore, the substrate mounting stage 10 made of such a base material 12 has higher thermal conductivity than the substrate mounting stage made of only ceramics, and applies not only a voltage but also a bias. Is also possible.

The material forming the ceramic layer 13 is T
Al ₂ O ₃ to which about 2.5% by weight of iO ₂ was added was used. The ceramic layer 13 having a thickness of about 0.2 mm is formed on the surface of the base material 12 by a thermal spraying method. The coefficient of linear expansion of the ceramic layer 13 having such a composition is about 9 × 10 ⁻⁶ / K on average at 100 to 300 ° C. Therefore, α ₂
Is about 9, and the coefficient of linear expansion α ₂ of the ceramic layer 13 satisfies the relationship of (α ₁ -3) ≦ α ₂ ≦ (α ₁ +3). The linear expansion coefficient of Al ₂ O ₃ itself is about 8 × 10 ⁻⁶ /.
K.

By adding about 2.5% by weight of TiO ₂ to Al ₂ O ₃ , the volume resistivity of the ceramic layer 13 can be adjusted to the order of 10 ¹¹ Ω / □. As a result, the ceramic layer 13 functions as a dielectric, and can exhibit a function as an electrostatic chuck. The reason for adjusting the volume resistivity as described above is that if the ceramic layer 13 exceeds the order of 10 ¹¹ Ω / □, when used as an electrostatic chuck, the attraction force of the ceramic layer 13 becomes too weak, and the silicon semiconductor substrate 40 This is because it may be difficult to make the ceramic layer 13 sufficiently adsorb. On the other hand, when the ceramic layer 13 has a thickness of 10 ¹¹ Ω /
If the order is less than the order, when the substrate mounting stage 10 is used at a high temperature, the resistance value of the ceramic layer 13 is further reduced, and a current may be generated at the interface between the silicon semiconductor substrate 40 and the ceramic layer 13. In addition, although it depends on use conditions,
In general, by the addition of TiO ₂ 0 to about 10 wt%, the volume resistivity of the ceramic layer 10 ¹¹ -
It is desirable to be 10 ¹⁶ Ω / □.

A method of manufacturing the substrate mounting stage 10 made of the composite material 11 will be described below. The composite material 11 comprises: (A) a step of filling a structure of a ceramic member with an aluminum-based material, thereby producing a base material in which the structure of the ceramic member is filled with an aluminum-based material; and (B) a base material. It is produced from the step of providing a ceramic layer on the surface of the substrate. Specifically, in this step (A), a ceramic member composed of porous cordierite ceramics is disposed in a container, and an aluminum-based material composed of molten aluminum and silicon is disposed in the container. The method comprises a step of pouring and filling a ceramic member with an aluminum-based material by high-pressure casting.

A ceramic member composed of porous cordierite ceramic is made porous in a sintering process when the ceramic member is manufactured. In the first embodiment, the porous cordierite ceramic fiber is a sintered body obtained by sintering cordierite ceramic powder and cordierite ceramic fiber as the porous cordierite ceramic. A board (hereinafter, abbreviated as a fiber board) was used. Whereas general powder sintered ceramics are sintered at a high temperature of about 1200 ° C, fiberboard is about 800 ° C.
The cordierite ceramic powder is sintered around the cordierite ceramic fiber so as to be in close contact with a binder via a binder, and is made porous. Therefore, for example, by changing the volume ratio between the cordierite ceramic powder and the cordierite ceramic fiber, the porosity and the pore diameter of the ceramic member having the obtained porous cordierite ceramic are adjusted. It is possible.

To manufacture the substrate mounting stage 10, first, a fiber board formed into a predetermined disk shape is prepared. Then, a fiber board is arranged at the bottom of the container (mold). A hole for embedding a pusher pin or the like is formed in the fiber board in advance.

Next, the ceramic member made of the fiber board is preheated to about 800 ° C., and subsequently, is heated to about 800 to 850 ° C. in a container (mold) to obtain an aluminum-based material (in a molten state). Al 80% by volume-
(20% by volume of Si). Then, a high-pressure casting method in which a high pressure of about 1 ton / cm ² is applied in the container (mold) is performed. As a result, a porous fiber board
The structure of the ceramic member is filled with an aluminum-based material. Then, the base material 12 is produced by cooling and solidifying the aluminum-based material.

Next, the upper surface of the base material 12, that is, the top surface and the side surface on the heater side are polished. Then, on this polished surface, A
About 2.5% by weight of TiO ₂ mixed with l ₂ O ₃ has a particle size of about 1
The mixed powder of 0 μm is sprayed in a molten state by a vacuum spraying method and solidified. As a result, the volume resistivity value becomes 1
A ceramic layer 13 having a thickness of about 0.2 mm on the order of 0 ¹¹ Ω / □ can be formed by thermal spraying. Prior to the formation of the ceramic layer 13, for example, nickel (Ni-5% by weight Al) containing about 5% by weight of aluminum is sprayed as a thermal spray underlayer, and the ceramic layer 13 is sprayed on the thermal spray underlayer. It may be formed by a method. Thereafter, a heater 14 composed of a PBN heater is attached to the lower surface of the base material 12, that is, the surface opposite to the surface on which the ceramic layer 13 is provided, and the substrate mounting stage 10 is obtained.

The substrate mounting stage 10 obtained in this manner is composed of a ceramic member made of a porous cordierite ceramic fiber board and 80% by volume of Al.
-Si20 volume percent of aluminum-based material preform obtained by filling the is constituted by (temperature regulating jacket) 12, the linear expansion coefficient alpha ₁ of the matrix 12 ceramic layer 13
Has a value close to the coefficient of linear expansion α ₂ . Therefore, the degree of expansion and contraction of the base material 12 and the ceramic layer 13 due to heating and cooling of the base mounting stage 10 is almost the same. Therefore,
Due to the difference between the linear expansion coefficients α ₁ and α ₂ between these materials, damage such as cracking occurs in the ceramic layer 13 when the substrate mounting stage 10 is heated at a high temperature or when the substrate mounting stage 10 is returned from a high temperature to a normal temperature. Can be reliably avoided.

In the method of manufacturing the substrate mounting stage 10, a porous cordierite ceramic fiber board is particularly used. Fiberboard can withstand the impact of As a result, the occurrence of cracks in the fiber board can be suppressed. That is, in a ceramic member made of porous cordierite ceramics obtained by a normal powder sintering method,
Cracks are likely to occur during high pressure casting. However, by using a porous cordierite ceramic fiber board, the occurrence of cracks in the ceramic member during high-pressure casting can be suppressed.

Since the occurrence of cracks or the like in the fiber board during high-pressure casting can be avoided, it is possible to more reliably prevent the ceramic layer provided on the surface of the base material from being damaged by cracks or the like. That is, even if a crack occurs in the fiber board, when the structure of the ceramic member made of the fiber board is filled with the aluminum-based material, the base material can be obtained as a result of the aluminum-based material acting as a kind of adhesive. However, in the base material thus obtained, a layer made of an aluminum-based material is formed in gaps such as cracks generated in the fiber board. As a result, the ceramic layer provided on the surface of the base material is
When 0 is used, it becomes impossible to follow the temperature change, and the ceramic layer is easily cracked. In other words, the ceramic layer is sprayed with a mixed powder having a particle size of about 10 μm and assimilated with the base material.
It is hardly affected by the thermal expansion of the aluminum-based material itself filled in the 2 μm pores. However,
The layer made of the aluminum-based material existing in the gap between the cracked portions of the fiberboard has a length or width larger than the diameter of the particles forming the ceramic layer. Therefore, the influence of the thermal expansion of such a layer made of an aluminum-based material on the ceramics layer is not negligible, and the probability of cracks occurring in the ceramics layer 13 is increased.

Since the ceramic layer is formed on the base material by a thermal spraying method, the base material 12 and the ceramic layer 13 are further integrated. Thereby, stress relaxation between the base material 12 and the ceramic layer 13 can be achieved, and the base material 12
The heat transfer from the substrate to the ceramic layer 13 becomes quick, and the temperature of the substrate held and fixed to the ceramic layer 13 constituting the substrate mounting stage 10 can be quickly and reliably controlled.

As shown in the schematic cross-sectional view of FIG. 2B, a ceramic layer is provided on the surface (and, if necessary, the side surface) of the base material 12 by a brazing method instead of a thermal spraying method. Is also good. In this case, Al ₂ produced by the sintering method
A ceramic layer 16 made of an O ₃ ceramic plate is
For example, it may be attached to the surface of the base material 12 by a brazing method using an Al-Mg-Ge-based brazing material 17 at a temperature of about 600 ° C. In addition, alloys composed of titanium, tin, antimony, and magnesium can be used as the brazing material. If necessary, the base mounting stage 10
An annular cover made of a ceramic material may be attached to the side surface of.

The CVD apparatus 20 of the first embodiment further includes
A chamber 21 and an inductive coupling coil 24 are provided. The chamber 21 includes a side wall 22 made of quartz and a top plate 23 made of a composite material. The method of manufacturing the top plate 23 will be described later.

The substrate mounting stage 10 for holding and fixing the silicon semiconductor substrate 40 is provided in the chamber 21.
(See FIG. 2). Base mounting stage 10
Is connected to a high-frequency power supply 25 for controlling the ion energy incident on the substrate, and further connected to a DC power supply 26 for exerting an electrostatic attraction force on the ceramic layer 13 as a dielectric member. . Further, the heater 14 of the substrate mounting stage 10 is connected to a power supply 27. Further, a fluorescent fiber thermometer 28 for measuring the temperature of the silicon semiconductor substrate 40 is provided in the CVD apparatus 20. The temperature of the substrate mounting stage 10 is controlled by controlling the temperature detected by the fluorescent fiber thermometer 28 with a control device (PI
(D controller) 29 to control the power supply 27 for supplying electric power to the heater 14. In FIG. 1, details of a CVD apparatus such as a CVD source gas introduction unit and a gate valve are omitted.

Next, the plasma C using the CVD device 20
A method for forming a barrier metal layer based on the VD method will be described with reference to FIGS. Embodiment 1
, The barrier metal layer has a two-layer structure of Ti / TiN. After forming the barrier metal layer, a contact hole (contact plug) made of tungsten is formed. The base is a silicon semiconductor substrate and an insulating layer (interlayer insulating layer) formed on the silicon semiconductor substrate, and has a configuration in which an opening is formed in the insulating layer (interlayer insulating layer).

First, Si is placed on the silicon semiconductor substrate 40.
After an interlayer insulating layer 41 made of O _{2 is} formed by a CVD method, an opening 42 is formed in the interlayer insulating layer 41. Although an element isolation region, a source / drain region, a channel formation region, and a gate electrode are formed on the silicon semiconductor substrate 40, these are not shown. Next, based on the barrier metal layer forming method of the present invention, a barrier metal layer 43 is formed on the interlayer insulating layer 41 including the inside of the opening 42 by a plasma CVD method. That is, the silicon semiconductor substrate 4
0 is placed on the substrate mounting stage 10 in the CVD apparatus 20 shown in FIG.
Hold on 0 and fix. Then, the temperature of the substrate mounting stage 10 is controlled by the operation of the heater 14, and the substrate is adjusted to the set temperature shown in Table 1 below. Then, the barrier metal layer 43 is formed under the plasma CVD conditions exemplified in Table 1. This state is shown in a schematic partial cross-sectional view of FIG. 3A, in which the barrier metal layer 43 is represented by one layer.

[0052]

Table 1 Formation of Ti layer Gas used: TiCl ₄ / H ₂ / Ar = 5/150/150 sccm Pressure: 0.7 Pa RF power: 2.5 kW RF bias: 0 W Substrate temperature: 400 ° C. Formation of TiN layer Gas: TiCl ₄ / H ₂ / Ar / N ₂ = 5/150/150/50 sccm Pressure: 0.7 Pa RF power: 2.5 kW RF bias: 0 W Substrate temperature: 400 ° C.

Thereafter, blanket tungsten CVD
Based on the method, the inside of the opening 42 is filled with tungsten,
A tungsten plug 44 is formed (see FIG. 3B). Tables 2 and 3 below show blanket tungsten CVD conditions and tungsten and barrier metal layer etching conditions.

[0054]

[Table 2] Tungsten CVD film forming conditions Gas used: WF ₆ / H ₂ / Ar = 40/400/2250 sccm Pressure: 10.7 × 10 ³ Pa Film forming temperature: 450 ° C.

Table 3 Etching conditions for tungsten layer and barrier metal layer First stage etching: Tungsten layer etching Gas used: SF ₆ / Ar / He = 110: 90: 5 sccm Pressure: 46 Pa RF power: 275 W Second stage etching : Etching condition of barrier metal layer Gas used: Ar / Cl ₂ = 75/5 sccm Pressure: 6.5 Pa RF power: 250 W

Thereafter, an aluminum-based wiring material layer is formed on the entire surface by sputtering, and the wiring 45 is completed by patterning the aluminum-based wiring material layer. This state is shown in FIG.

When the barrier metal layer is formed based on the plasma CVD method, a large amount of heat is input to the substrate due to generation of plasma. However, the temperature detected by the fluorescent fiber thermometer 28 is detected by the control device (PID controller) 29, and the heater 14 is controlled based on the detected value, so that the temperature of the base is set to the set temperature (the substrate temperature in Table 1). ) To maintain. As described above, since the temperature of the base can be stabilized with high accuracy, it is possible to form a barrier metal layer having stable film quality without characteristic fluctuation in the film thickness direction. That is,
The amount of chlorine remaining in the barrier metal layer can be reduced. When the residual chlorine in the barrier metal layer was measured based on the Rutherford back scattering method, it was 0.1%, and a good quality barrier metal layer could be formed.

(Embodiment 2) FIG. 4 shows a conceptual diagram of a bias CVD apparatus 20A suitable for use in Embodiment 2. In the second embodiment, base mounting stage 10A
As shown in a schematic sectional view of FIG. 5A, a temperature control unit is provided with a heater 14 disposed inside a base material 12A.
A, and a pipe 15A through which a heat medium for temperature control disposed inside the base material 12A flows. As the heater 14A, a large-capacity sheathed heater corresponding to the area (bottom area) of the base material 12A was used. The heater 14A is a known heater including a heater body (not shown) and a sheath tube (not shown) provided outside the heater body and protecting the heater body. The heater 14A is connected to a power supply 27 (see FIG. 4) via wiring. The thermal expansion of the heater 14A affects the base mounting stage 10A. Accordingly, the linear expansion coefficient α of the base material 12A and the ceramic layer 13A
_1, it is preferable to use a material having a value close to alpha _2.
Specifically, titanium or stainless steel or the like, it is preferable that the linear expansion coefficient which sheath tube made from the material of the ^{9 × 10 -6 / K~12 × 10} -6 / K. That is, the heater 14A
The coefficient of linear expansion α _H [unit: 10 ⁻⁶ / K] of the material (material of the sheath tube in contact with the base material 12 </ b> A) is (α ₁ -3) ≦ α _H
It is preferable to satisfy the relationship of ≦ (α ₁ +3). still,
The linear expansion coefficient of the main body of the heater 14A is
There is no particular limitation because it does not affect 0A.

A pipe 15A provided in the base material 12A of the base mounting stage 10A is connected to a temperature control heating medium supply device 32 (see FIG. 4) via pipes 30A and 30B. And it is made of metal or alloy. The temperature control heat medium supplied from the temperature control heat medium supply device 32 is supplied to the pipe 15A in the base mounting stage 10A.
, The temperature of the substrate mounting stage 10A can be controlled. The thermal expansion of the pipe 15A also affects the base mounting stage 10A. Therefore, the base material 12A
It is preferable to use a material having values close to the linear expansion coefficients α ₁ and α ₂ of the ceramic layer 13A. Specifically, such as titanium or stainless steel, the coefficient of linear expansion is 9 × 10 ⁻⁶ / K
It is preferable to use a pipe 15A made of a material of about 12 × 10 ⁻⁶ / K. That is, the linear expansion coefficient α _P [unit: 10 ⁻⁶ / K] of the material constituting the pipe 15A is (α _1-3 )
It is preferable to satisfy the relationship of ≦ α _P ≦ (α ₁ +3).

The temperature control heating medium supply device 32 is composed of, for example, a chiller for supplying a low temperature (eg, 0 ° C.) temperature control heating medium (refrigerant) such as Freon gas.
The temperature control heat medium supply device 32 is a low-temperature (eg, 0 ° C.) temperature control heat medium (refrigerant) such as Freon gas.
(In some cases, a temperature control heat medium such as silicon oil) is supplied to the pipe 15A of the substrate mounting stage 10A via the pipe 30A, and the temperature control heat medium sent out from the pipe 15A via the pipe 30B is discharged. Then, the temperature control heat medium is cooled to a predetermined temperature. As described above, by circulating the heat medium for temperature control in the pipe 15A, the temperature of the substrate held and fixed on the substrate mounting stage 10A can be controlled. A control valve 31 capable of operating at a high temperature is provided in a pipe 30A connected to the heat medium supply device 32 for temperature control. on the other hand,
A control valve 31 is also provided on a bypass pipe 30C between the pipe 30A and the pipe 30B. Then, under such a configuration, the supply amount of the heat medium for temperature control to the pipe 15A is controlled by controlling the opening / closing degree of the control valve 31. Also, the temperature detected by the fluorescent fiber thermometer 28 is detected by a control device (PID controller) 29,
The controller 29 determines the supply amount of the heat medium for temperature control so that the supply amount is determined in advance by experiment or calculation from the difference from the preset substrate temperature.

The substrate mounting stage 1 shown in FIG.
At 0 A, although it depends on the set temperature of the substrate, usually,
Main temperature control is performed by heating by the heater 14A. The temperature control of the substrate mounting stage 10A by the temperature control heat medium is an auxiliary temperature control for stabilizing the temperature of the substrate. That is, when the barrier metal layer is formed by the plasma CVD method, the substrate receives heat input from the plasma, and as a result, it may be difficult to maintain the substrate at the set temperature only by heating with the heater 14A. In such a case, in addition to the heating of the heater 14A, a temperature control heating medium at a temperature lower than the set temperature (for example, 0 ° C.) is supplied to the pipe 15A so as to offset the heat input from the plasma in order to maintain the base at the set temperature. Pour into Thus, the base can be more reliably stabilized at the set temperature.

A method for manufacturing the base mounting stage 10A composed of the composite material 11A will be described below. The composite material 11A is also prepared by: (A) a step of filling a structure of a ceramic member with an aluminum-based material to prepare a base material in which the structure of the ceramic member is filled with an aluminum-based material; It is produced from the step of providing a ceramic layer on the surface of the substrate. Specifically, in this step (A), a ceramic member composed of porous cordierite ceramics is disposed in a container, and an aluminum-based material composed of molten aluminum and silicon is disposed in the container. The method comprises a step of pouring and filling a ceramic member with an aluminum-based material by high-pressure casting.

In order to manufacture the substrate mounting stage 10A,
First, a first fiber board formed into a predetermined disk shape is prepared. The first fiber board is provided with a groove for arranging the heater 14A. Also,
A second fiber board different from the first fiber board is prepared. A groove for arranging the pipe 15A is formed in the second fiber board. Then, the first fiber board is arranged on the bottom of the container (mold), and the heater 14A is arranged in a groove provided in the first fiber board. Next, the second fiber board is placed on the first fiber board, and the pipe 15A is arranged in a groove provided in the second fiber board. And
Further, a third fiber board is placed on the second fiber board. In addition, holes for embedding pusher pins and the like are formed in these fiber boards in advance.

Next, the ceramic member made of the fiber board is preheated to about 800 ° C., and then heated to a temperature of about 800 to 850 ° C. in a container (mold) to form an aluminum-based material. Material (Al80
(% By volume-20% by volume of Si). Then, a high-pressure casting method in which a high pressure of about 1 ton / cm ² is applied in the container (mold) is performed. As a result, the porous fiber board, that is, the structure of the ceramic member is filled with the aluminum-based material. Then, the base material 12A is manufactured by cooling and solidifying the aluminum-based material.

Next, the upper surface of the base material 12A, that is, the surface on the heater side is polished. Then, T on the polished surface, the Al ₂ O ₃
A mixed powder having a particle size of about 10 μm in which about 2.5% by weight of iO ₂ is mixed is sprayed in a molten state by a vacuum spraying method to be solidified.

The method of forming the barrier metal layer based on the plasma CVD method using the substrate mounting stage 10A can be substantially the same as the method described in the first embodiment. Is omitted.

As shown in the schematic cross-sectional view of FIG. 5B, in the substrate mounting stage 10B, a ceramic layer is provided on the surface of the base material 12A by a brazing method instead of a thermal spraying method. . In this case, a ceramic layer 1 made of an Al ₂ O ₃ ceramic plate manufactured by a sintering method is used.
6A, for example, at a temperature of about 600 ° C.
The base material 12 is formed by a brazing method using a Ge brazing material 17A.
What is necessary is just to attach to the surface of A. If necessary, an annular cover made of a ceramic material may be attached to the side surface of the base mounting stage 10B. Also, in some cases,
The pipe 15A may be omitted, or the heater 14A may be omitted and only the pipe 15A may be used, as in a substrate mounting stage 10C shown in the schematic cross-sectional view of FIG. Further, the heater may be attached to the lower surface of the base material instead of being embedded in the base material 12A.

(Embodiment 3) Embodiment 3 is also a modification of Embodiment 1. Embodiment 3 is different from Embodiment 1 in that the composition of the ceramic member forming the base material in the composite material is aluminum nitride (TiN), and the composition of the aluminum-based material forming the base material is aluminum (Al). It is in the point which was. The structure of the base mounting stage 10 in the third embodiment is the same as that shown in the schematic cross-sectional view of FIG.

In the third embodiment, the composition of the ceramic member forming base material 12 is aluminum nitride (Al
N). The coefficient of linear expansion of aluminum nitride is 5.1.
× 10 ^-6 / K and thermal conductivity of 0.235 cal / c
m · sec · K. The composition of the aluminum-based material constituting the base material was aluminum (Al). (Α ₁ −
3) The volume ratio between aluminum nitride and aluminum is determined so as to satisfy the relationship of ≦ α ₂ ≦ (α ₁ +3), and specifically, the volume ratio of aluminum nitride / aluminum is 70/30. . The linear expansion coefficient of the base material 12 is
8.7 × 10 ⁻⁶ / average at 100 to 300 ° C.
K. That is, α ₁ is 8.7. The material constituting the ceramic layer 13 was Al ₂ O ₃ to which about 2.5% by weight of TiO ₂ was added. The ceramic layer 13 is formed on the surface of the base material 12 by a thermal spraying method. Ti to Al ₂ O ₃
By adding O ₂ , the coefficient of linear expansion becomes 100
About 9 × 10 ^-6 / K (α ₂
= About 9), and substantially the same value as the linear expansion coefficient alpha ₁ of the matrix 12. Accordingly, it is possible to effectively prevent the ceramic layer 13 from being damaged by a temperature change due to high-temperature heating of the base material 12. Also, Al ₂ O ₃
By adding TiO ₂ to the ceramic layer 13
Can be adjusted to the order of 10 ¹¹ Ω / □. Thereby, the ceramic layer 13 effectively exerts a function as an electrostatic chuck. That is, if a DC voltage is applied from a power source to the base material 12 of the base mounting stage 10 via wiring (not shown), the base material 12 can be used as an electrode, and the ceramic layer 13 functions as an electrostatic chuck. I do. A pusher pin (not shown) for pushing up, for example, a silicon semiconductor substrate mounted and held on the ceramic layer 13 is embedded in the base mounting stage 10. The pusher pin is provided with a mechanism (not shown) for projecting the pusher pin above the top surface of the ceramic layer 13 or burying the pusher pin below the top surface.

The heater 14 in the third embodiment is also
This is a PBN heater capable of heating at 0 ° C. or more. By attaching the heater 14 to the outer surface of the base material 12, it is possible to control the temperature of the base material 12 from room temperature to 500 ° C. or more.

A method for manufacturing the substrate mounting stage 10 made of the composite material 11 will be described below. The composite material 11 is basically (A) a structure of a ceramic member filled with an aluminum-based material, and thus the structure of the ceramic member is filled with an aluminum-based material, similarly to the first embodiment. It is produced from a step of producing a base material and a step (B) of providing a ceramic layer on the surface of the base material. In the third embodiment, in this step (A), based on a non-pressurized metal infiltration method, an aluminum-based material having a composition of aluminum melted in a ceramic member formed from aluminum nitride particles is applied in a non-pressurized state. Permeation step.

Specifically, after AlN particles having an average particle diameter of 10 μm are formed by a slurry casting method, the temperature is reduced to about 1000 ° C.
By performing firing (sintering) at the temperature described above, a ceramic member as a preform formed of AlN particles was produced. Then, the ceramic member is preheated to about 800 ° C., and the aluminum melted by heating to about 800 ° C. is infiltrated into the ceramic member without pressure.
Thereby, the base material 12 having a configuration of 70% by volume of AlN-30% by volume of Al can be manufactured. Then, the base material 1
2 is formed into a disk shape. Next, the top and side surfaces of the base material 12 thus obtained are polished. Thereafter, a mixed powder of about 2.5% by weight of TiO ₂ mixed with Al ₂ O ₃ having a particle size of about 10 μm is sprayed on the polished surface in a molten state by a vacuum spraying method to be solidified. Thereafter, a heater 14 composed of a PBN heater is attached to the lower surface of the base material 12, that is, the surface opposite to the surface on which the ceramic layer 13 is provided, and the substrate mounting stage 10 is obtained. Prior to the formation of the ceramic layer 13, for example, nickel containing approximately 5% by weight of aluminum (Ni-5% by weight Al) is used as a thermal spray underlayer.
Is sprayed, and a ceramic layer 1
3 may be formed by thermal spraying.

In the base stage 10 thus manufactured, the coefficient of linear expansion α ₂
Is almost the same value as the linear expansion coefficient α ₁ of the base material 12.
Therefore, even if the base material 12 changes in temperature due to high-temperature heating or the like, the ceramic layer 13 does not suffer damage such as cracks. Further, by adjusting the volume ratio between aluminum nitride and aluminum, further, if necessary,
By adjusting the addition ratio of TiO ₂ in the ceramic layer 13 made of ₂ O _3, the linear expansion coefficient α ₁
And the coefficient of linear expansion α ₂ of the ceramic layer 13 is (α ₁ -3) ≦
The relationship may satisfy the relationship α ₂ ≦ (α ₁ +3). As a result, it is possible to effectively prevent damage such as cracking of the ceramic layer 13 due to a temperature change of the base mounting stage 10.

Further, since the ceramic layer 13 is formed on the base material 12 by the thermal spraying method, the base material 12 and the ceramic layer 1 are formed.
3 is further integrated. Thereby, stress relaxation between the base material 12 and the ceramic layer 13 can be achieved,
Heat conduction from the base material 12 to the ceramic layer 13 is quickened.

The plasma CVD apparatus of the third embodiment having the substrate mounting stage 10 made of the composite material 11 can be the same as the plasma CVD apparatus described in the first embodiment, Description is omitted.
The method for forming a barrier metal layer based on the plasma CVD method in the third embodiment may be substantially the same as the method for forming a barrier metal layer based on the plasma CVD method described in the first embodiment. Since it is possible, detailed description is omitted. The temperature of the substrate mounting stage 10 is controlled by detecting a temperature detected by a fluorescent fiber thermometer 28 with a control device (PID controller) 29 and controlling a power supply 27 for supplying power to the heater 14. It can be carried out.

As shown in the schematic cross-sectional view of FIG. 2B, the ceramic layer may be provided on the surface (and, if necessary, the side surface) of the base material 12 by a brazing method instead of a thermal spraying method. Good. In this case, Al ₂ produced by the sintering method
A ceramic layer 16 made of an O ₃ ceramic plate is
For example, it may be attached to the surface of the base material 12 by a brazing method using an Al-Mg-Ge-based brazing material 17 at a temperature of about 600 ° C. If necessary, the base mounting stage 10
An annular cover made of a ceramic material may be attached to the side surface of. Alternatively, a temperature control means similar to that of the substrate mounting stage in the second embodiment can be used.

Although the composition of the aluminum-based material constituting the base material was aluminum, the composition of the aluminum-based material constituting the base material was changed to aluminum and silicon (for example, Al 80 vol% -Si 20 vol%). It can be. By the composition of the aluminum-based material and aluminum and silicon, it is possible to control the alpha ₁ the linear expansion coefficient of the base material, it is possible to reduce the difference more linear expansion ratio alpha ₂ of the ceramic layer Become.
Further, instead of forming the ceramic layer from Al ₂ O ₃ , the ceramic layer may be formed from aluminum nitride (AlN).

(Embodiment 4) Embodiment 4 is also a modification of Embodiment 1. Embodiment 4 is different from Embodiment 1 in that the composition of the ceramic member forming the base material in the composite material is silicon carbide (SiC), and the composition of the aluminum-based material forming the base material is aluminum (Al).
It is in the point.

Base Mounting Stage 1 in Embodiment 4
The structure of No. 0 is the same as that shown in the schematic sectional view of FIG.

In the fourth embodiment, the composition of the ceramic member forming base material 12 is silicon carbide (SiC). The linear expansion coefficient of silicon carbide is 4 × 10 ⁻⁶ / K, and the thermal conductivity is 0.358 cal / cm · sec · K (15
0 W / m · K). The composition of the aluminum-based material constituting the base material was aluminum (Al). (Α
_{1 -3) ≦ α 2 ≦ (} α 1 +3) volume ratio of silicon carbide and aluminum so as to satisfy is determined, specifically, the volume ratio of silicon carbide / aluminum 70/30
It is. The linear expansion coefficient of the base material 12 is 6.2 × 10 ⁻⁶ / K as an average value at 100 to 300 ° C. That is, α ₁ = 6.2. The material constituting the ceramic layer 13 is Al ₂ O to which about 1.5% by weight of TiO ₂ is added.
_{It was set to 3} . The ceramic layer 13 is formed by spraying the base material 12
Are formed on the top surface and the side surfaces. Al ₂ O ₃ is originally the linear expansion coefficient of about 8 × 10 ^-6 / K, Ti to Al ₂ O ₃
By adding O ₂ , the coefficient of linear expansion becomes 100
About 8 to 9 × 10 ⁻⁶ / K at an average value of about 300 ° C.
(The alpha ₂ about 8-9), and the relation between the linear expansion coefficient alpha ₂ of the linear expansion coefficient alpha ₁ and the ceramic layer 13 of the matrix 12, (alpha ₁ -3)
≦ α ₂ ≦ (α ₁ +3). Thereby, the base material 1
2, it is possible to effectively prevent the ceramic layer 13 from being damaged due to a temperature change due to high-temperature heating or the like. Also, by adding TiO ₂ to Al ₂ O ₃ , the volume specific resistance value of the ceramic layer 13 is set to 10 ¹¹ Ω /
Can be adjusted to the order of □. by this,
The ceramic layer 13 effectively exhibits a function as an electrostatic chuck.

As in the first embodiment, the heater 14
It is a BN heater. By mounting the heater 14 on the back of the temperature control jacket, which is the base material 12, the base material 12
Can be controlled within a range from normal temperature to about 500 ° C. or more. Alternatively, a temperature control means similar to that of the substrate mounting stage in the second embodiment can be used. When a DC voltage is applied to the base material 12 of the base mounting stage 10 via wiring (not shown), the base material 12
Can be used as an electrode, and the ceramic layer 13 functions as an electrostatic chuck. A pusher pin (not shown) for pushing up, for example, a silicon semiconductor substrate mounted and held on the ceramic layer 13 is embedded in the base mounting stage 10. Further, the pusher pin is provided with a ceramic layer 13.
A mechanism (not shown) for projecting above the top surface or burying below the top surface is attached.

A method for manufacturing the substrate mounting stage 10 will be described below. The composite material 11 is basically (A) a structure of a ceramic member filled with an aluminum-based material, and thus the structure of the ceramic member is filled with an aluminum-based material, similarly to the first embodiment. It is produced from a step of producing a base material and a step (B) of providing a ceramic layer on the surface of the base material. In the fourth embodiment, this step (A) is based on a non-pressurized metal infiltration method, in which an aluminum-based material having a composition of aluminum melted in a ceramic member formed from silicon carbide particles is pressed in a non-pressurized state. Permeation step.

Specifically, a volume ratio of SiC particles having an average particle size of 15 μm to SiC particles having an average particle size of 60 μm is 1: 4.
After shaping the mixture mixed by the casting slurry forming method,
By firing at a temperature of about 800 ° C., the SiC
A ceramic member, which is a preform formed from particles, was produced. Then, the ceramic member is preheated to about 800 ° C., and the aluminum melted by heating to about 800 ° C. is infiltrated into the ceramic member without pressure. Thereby, SiC 70 volume% -Al 30 volume%
Can be manufactured. Next, the base material 12 is formed into a shape of a disc-shaped temperature control jacket. A hole for embedding a pusher pin or the like is formed in the base material 12 in advance. Next, the top and side surfaces of the base material 12 thus obtained are polished.
Then, about 1.5 times of TiO ₂ was added to Al ₂ O ₃ on the polished surface.
A mixed powder having a particle size of about 10 μm mixed by weight% is sprayed in a molten state by a vacuum spraying method and solidified. As a result, a ceramic layer 13 having a thickness of about 0.2 mm and a volume resistivity of the order of 10 ¹¹ Ω / □ can be formed. Thereafter, the bottom surface of the base material 12, that is, the ceramic layer 13
A heater 14 composed of a PBN heater is attached to the surface opposite to the top surface on which the substrate is provided, and the substrate mounting stage 10 is obtained.
Prior to the formation of the ceramics layer 13, for example, nickel (N
i-5% by weight of Al) may be sprayed, and the ceramic layer 13 may be formed on the sprayed underlayer by a spraying method.

The method for manufacturing the substrate mounting stage 10 is as follows.
It is not limited to the method described above. In the above step (A), as in Embodiment 1, a ceramic member having a composition of silicon carbide is disposed in a container (mold), and aluminum having a composition of molten aluminum is provided in the container (mold). It can also be constituted by a step of pouring a system material and filling the ceramic member with an aluminum material by high-pressure casting. That is, to manufacture the substrate mounting stage 10, first, a preform made of SiC formed into a predetermined disk shape is prepared. A hole for embedding a pusher pin or the like is formed in the preform in advance. Next, a ceramic member made of a preform
Preliminarily heated to ゜ C, and subsequently, molten aluminum is poured into a container (mold) by heating to about 800 ゜ C. Then, a high-pressure casting method in which a high pressure of about 1 ton / cm ² is applied in the container (mold) is performed. As a result, the structure of the ceramic member is filled with aluminum.
Then, the base material 12 is manufactured by cooling and solidifying the aluminum. Hereinafter, the substrate mounting stage 10 may be manufactured by the same method as described above.

In the substrate mounting stage 10 manufactured as described above, the ceramic layer 13 does not suffer damage such as cracks even when the base material 12 changes in temperature due to high temperature heating or the like. Further, by adjusting the volume ratio between silicon carbide and the aluminum-based material, if necessary, the Ti in the ceramic layer 13 made of Al ₂ O ₃ may be used.
By adjusting the addition rate of O _2, the linear expansion coefficient alpha ₂ of the linear expansion coefficient alpha ₁ and the ceramic layer 13 of the preform 12, (alpha ₁
-3) ≦ α ₂ ≦ (α ₁ +3). As a result, it is possible to effectively prevent damage such as cracking of the ceramic layer 13 due to a temperature change of the base mounting stage 10.

Further, since the ceramic layer 13 is formed on the base material 12 by a thermal spraying method, the base material 12 and the ceramic layer 1 are formed.
3 is further integrated. Thereby, stress relaxation between the base material 12 and the ceramic layer 13 can be achieved,
The heat conduction from the base material 12 to the ceramic layer 13 becomes faster, and the temperature of the base (for example, a silicon semiconductor substrate) held and fixed to the ceramic layer 13 can be quickly and reliably controlled.

As shown in the schematic cross-sectional view of FIG. 2B, the ceramic layer may be provided on the top surface (and, if necessary, the side surface) of the base material 12 by a brazing method instead of a thermal spraying method. Good. In this case, a ceramic layer 16 made of an Al ₂ O ₃ ceramic plate manufactured by a sintering method was used, for example, using an Al—Mg—Ge brazing material 17 at a temperature of about 600 ° C. What is necessary is just to attach to the top surface of a base material by the brazing method.

Although the composition of the aluminum-based material constituting the base material was aluminum, the composition of the aluminum-based material constituting the base material was changed to aluminum and silicon (for example, Al 80 vol% -Si 20 vol%). It can be. By setting the composition of the aluminum-based material to aluminum and silicon, the coefficient of linear expansion of the base material α
It is possible to control the _1, it is possible to reduce the difference between the linear expansion coefficient alpha ₂ of the further ceramic layer. Also, instead of forming the ceramic layer from Al ₂ O ₃ ,
It may be made of aluminum nitride (AlN).

(Embodiment 5) In Embodiment 5, as a plasma CVD apparatus, a bias ECR CVD apparatus whose conceptual diagram is shown in FIG. 6 was used.

This bias ECR CVD apparatus 20B
(Hereinafter, abbreviated as CVD apparatus 20B) includes a chamber 51 in which a side wall 51A is formed from a composite material, and a substrate mounting stage (wafer stage) 1 shown in FIG.
0 is provided. The substrate mounting stage 10 is disposed at the bottom of the chamber 51. Side wall 51 from composite material
The method for producing A will be described later.

A window 51 made of quartz is provided on the top surface of the chamber 51.
B is provided. A microwave generating means 52 is provided above the window 51B. In addition, a heater 53 is provided on the outer peripheral surface of the side wall 51A, so that the inside of the chamber 51 can be heated to a predetermined temperature.
Further, a solenoid coil 54 is disposed in a peripheral portion on the upper side of the chamber 51. A pump 55 is provided on the exhaust side of the chamber 51. The substrate mounting stage 10 is connected to an RF bias power supply 56.
In addition, a DC power supply 57 for causing the ceramic layer 13 to exert an electrostatic attraction force is connected to a temperature control jacket corresponding to the base material 12. Further, the heater 14 provided in the base material 12 is connected to a power supply 58. The illustration of the fluorescent fiber thermometer 28 and the control device (PID controller) 29 is omitted. The temperature control means may be the same as that of the substrate mounting stage in the second embodiment.

In the CVD apparatus 20B having such a configuration, an ECR discharge is generated by the resonance action of the microwave supplied from the microwave generation means 52 through the window 51B and the magnetic field by the solenoid coil 54, and is generated here. The ions are incident on a base (eg, a silicon semiconductor substrate 40) on the base mounting stage 10. Therefore, a highly accurate gap fill can be realized in the CVD apparatus 20B by such a mechanism. The CVD apparatus 20B is supplied with a source gas for CVD processing in the chamber 51.
There is provided a pipe (not shown) for supplying the air to the air.

Plasma CVD using CVD apparatus 20B
FIG. 7A shows a method of forming a barrier metal layer based on the method of FIG.
And (B). In the fifth embodiment, the barrier metal layer has a two-layer structure of Ti / WN. After forming the barrier metal layer based on the dual damascene process, via holes and trench wirings made of copper are simultaneously formed. The base is a lower wiring formed on the base insulating layer, and an insulating layer (interlayer insulating layer) formed on the entire surface including the lower wiring, and the insulating layer (interlayer insulating layer)
Has an opening and a groove communicating with the opening.

First, a silicon semiconductor substrate 40 (not shown)
After a base insulating layer 60 made of SiO ₂ is formed thereon by a CVD method, a lower wiring 61 is formed by a known method. Next, an interlayer insulating layer 62 made of SiO _{2 is} formed on the entire surface by CVD.
Is formed, an opening 63 is formed in the interlayer insulating layer 62 above the lower wiring 61, and a groove 64 for forming a groove wiring is formed above the opening 63.

Thereafter, based on the barrier metal layer forming method of the present invention, the barrier metal layer 65 is formed by plasma CVD.
Is formed on the interlayer insulating layer 62 including the inside of the opening 63 and the groove 64. That is, the silicon semiconductor substrate is placed on the substrate mounting stage 10 in the CVD apparatus 20B shown in FIG. Hold on
Fix it. Then, the temperature of the base mounting stage 10 is controlled by the operation of the heater 14, and the silicon semiconductor substrate 4 is controlled.
Adjust 0 to the set temperature shown in Table 4 below. Then, the barrier metal layer 6 is formed under the plasma CVD conditions exemplified in Table 4.
5 is formed. This state is shown in a schematic partial cross-sectional view of FIG. 7A, in which the barrier metal layer 65 is represented by one layer.

[0095]

Table 4 Formation of Ti layer Gas used: TiCl ₄ / H ₂ / Ar = 5/150/150 sccm Pressure: 0.7 Pa Microwave power: 3 kW RF bias: 0 W Substrate temperature: 400 ° C. Formation of WN layer : WF ₆ / H ₂ / Ar / N ₂ = 5/150/150/100 sccm Pressure: 0.7 Pa Microwave power: 3 kW RF bias: 0 W Substrate temperature: 400 ° C.

Thereafter, a copper layer is deposited on the barrier metal layer 65 including the inside of the opening 63 and the groove 64 under the CVD conditions shown in Table 5 below. ), The copper layer and the barrier metal layer 65 on the interlayer insulating layer 62 are polished and removed. Thus, FIG.
As shown in (B), a structure in which the lower wiring 61 and the upper wiring 66 are connected by the via hole 67 can be obtained. In Table 5, HFA is an abbreviation for hexafluoroacetylacetonate.

[0097]

[Table 5] Copper CVD film forming conditions Gas used: Cu (HFA) ₂ / H ₂ = 10/1000 sccm Pressure: 2.6 × 10 ³ Pa Substrate heating temperature: 350 ° C.

When the barrier metal layer is formed based on the plasma CVD method, a large amount of heat is input to the substrate due to generation of plasma. However, the temperature detected by the fluorescent fiber thermometer 28 is detected by the control device (PID controller) 29, and the heater 14 is controlled based on the detected value, so that the temperature of the base is set to the set temperature (the substrate temperature in Table 4). ) To maintain. As described above, since the temperature of the base can be stabilized with high accuracy, it is possible to form a barrier metal layer having stable film quality without characteristic fluctuation in the film thickness direction. That is,
The amount of chlorine remaining in the barrier metal layer can be reduced.

Incidentally, the barrier metal layer may be made of Ta / TaN. Table 6 below shows examples of the plasma CVD conditions in this case.

[0100]

Table 6 Formation of Ta layer Gas used: TaBr ₅ / H ₂ / Ar = 10/1000/1000 sccm Pressure: 0.5 Pa Microwave power: 3 kW RF bias: 0 W Substrate temperature: 350 ° C. Formation of TaN layer : TaBr ₅ / H ₂ / Ar / N ₂ = 10/1000/900/50 sccm Pressure: 0.5 Pa Microwave power: 3 kW RF bias: 0 W Substrate temperature: 350 ° C.

Although the present invention has been described based on the embodiments, the present invention is not limited to these embodiments. The structure of the plasma CVD apparatus described in the embodiment of the invention is an example, and the design can be changed as appropriate. The various processing conditions described in the embodiments of the invention are also examples, and can be changed as appropriate. Furthermore,
The composition of the composite material and the physical properties of the cordierite ceramic fiberboard are also examples, and can be changed as appropriate.

In the embodiments of the present invention, the base mounting stage is manufactured exclusively from the integrally formed base material. However, the base mounting stage may be manufactured from a combination of an aluminum material and a base material. Can also. FIGS. 8 and 9 are schematic cross-sectional views of such a substrate mounting stage. The base mounting stage 110 is manufactured by fixing a composite material 111 to an aluminum disk-shaped member 118 by brazing or screwing. The brazing material or screw is not shown in FIGS. 8 and 9 and FIGS. 12 to 14 described later. In the structure shown in FIG. 8, the top surface of base mounting stage 110 is covered with ceramic layer 113. The side surface of the substrate mounting stage 110 may be covered with the ceramic layer 113 as necessary. On the other hand, in the structure shown in FIG. 9, a ceramic layer 116 made of, for example, an Al ₂ O ₃ ceramic plate is attached to the top surface of the base mounting stage 110 by a brazing material 117. In FIG. 8A or FIG. 9A, an aluminum disk-shaped member 118 is shown.
Is provided with a pipe 115. The base material 11
2 are fixed to the upper and lower surfaces of the disk-shaped member 118. Composite material 11 fixed on the upper surface of disc-shaped member 118
The structure 1 and the structure of the base material 112 fixed to the lower surface of the disc-shaped member 118 may be the same as the structure of the composite material and the structure of the base material described in the first to fourth embodiments. it can. In FIG. 8B or FIG. 9B, the base material is omitted on the lower surface of the disc-shaped member 118 made of aluminum. 8 (C) or FIG. 9 (C)
, A PBN heater 114 is attached to the lower surface of a disc-shaped member 118 made of aluminum. And
The composite material 111 is fixed on the upper surface of the disk-shaped member 118.

The side wall 51 of the chamber of the plasma CVD apparatus
A or the top plate 23 is preferably made of a composite material. Plasma CVD apparatus 20B shown in FIG.
10 to 14 are schematic partial cross-sectional views of the chamber side wall 51A of the chamber 51 in FIG. The chamber side wall 51A includes a base material 212 in which the structure of the ceramic member is filled with an aluminum-based material,
2 is made of a composite material 211 comprising a ceramic layer 213 provided on the surface of the composite material 211.

A heater 214 composed of a known sheathed heater is disposed inside the chamber side wall 51A (see FIGS. 10A and 10B). The heater 214
It comprises a heater body (not shown) and a sheath tube (not shown) provided outside the heater body and protecting the heater body. The heater 214 is connected to a power supply (not shown) via a wiring. The thermal expansion of the heater 214 affects the chamber side wall 51A. Therefore, it is preferable to use a material having values close to the linear expansion coefficients α ₁ and α ₂ of the base material 212 and the ceramic layer 213. Specifically, titanium or stainless steel or the like, it is preferable that the linear expansion coefficient which sheath tube made from the material of the ^{9 × 10 -6 / K~12 × 10} -6 / K. That is, the heater 2
14 (material of the sheath tube in contact with the base material 212)
The coefficient of linear expansion α _H [unit: 10 ⁻⁶ / K] is (α ₁ -3) ≦
It is preferable to satisfy the relationship α _H ≦ (α ₁ +3).
The coefficient of linear expansion of the main body of the heater 214 is not particularly limited since it does not affect the chamber side wall 51A. In some cases, at the same time as providing the heater 214, a pipe having the same structure as the pipe 15A described above may be provided inside the chamber side wall 51A.
14 instead of arranging the chamber side wall 51A.
It may be arranged inside.

Alternatively, as shown in a schematic cross-sectional view of FIG.
The ceramic layer 216 may be provided on the surface of the base material 212 by a brazing method instead of the thermal spraying method. In this case, the ceramic layer 216 made of a ceramic annular member made of Al ₂ O ₃ manufactured by the sintering method is applied, for example, to about 600 ° C.
May be attached to the surface of the base material 212 by the brazing method using the Al-Mg-Ge brazing material 217 at the temperature described above.
In addition, alloys composed of titanium, tin, antimony, and magnesium can be used as the brazing material.

Alternatively, as shown in the schematic cross-sectional views of FIGS.
Instead of being buried in, the outer surface of the chamber side wall 51A (the surface opposite to the surface facing the chamber 51) is, for example,
A heater 214A composed of a PBN heater may be attached.

FIGS. 12 to 14 show schematic cross sections of a side wall of a CVD apparatus manufactured by fixing the composite material 211 to a hollow cylindrical member 218 made of stainless steel or aluminum by brazing or screwing. The figure is shown. FIG.
2 (A) or (B), the hollow cylindrical member 2
A heater 214 (which may be a pipe) is provided inside 18. The base material 212 is fixed to the inner surface and the outer surface of the hollow cylindrical member 218. The structure of the composite material 211 fixed to the inner surface (the chamber 51 side) of the hollow cylindrical member 218 has the same structure as the composite material described in the embodiment. 13A or 13B, the base material 212 on the outer surface of the hollow cylindrical member 218 is omitted. 14A or 14B, a PBN heater 214B is attached to the outer surface of the hollow cylindrical member 218. Then, the composite material 211 is the hollow cylindrical member 2
18 are fixed to the inner surface.

The top plate 23 of the plasma CVD apparatus may have the same structure. In addition, the chamber side wall 51A or the top plate 23 of these plasma CVD apparatuses is the same as the first embodiment.
Since the composite material can be manufactured based on the same method as the method for manufacturing a composite material described in Embodiment Mode 4, detailed description is omitted.

[0109]

According to the method for forming a barrier metal layer of the present invention, the characteristic variation in the film thickness direction during the formation of the barrier metal layer can be suppressed, so that the amount of halogen remaining in the barrier metal layer can be reduced. be able to. As a result, a semiconductor device having high reliability can be manufactured.

Further, since the composite material is composed of the base material and the ceramic layer, the base material has properties intermediate between the ceramic member and the aluminum-based material. The value can be adjusted. Therefore, the occurrence of damage to the ceramic layer due to the thermal expansion between the base material and the ceramic layer can be avoided, and the composite material can be reliably used at a high temperature. In addition, since the base material has a high thermal conductivity, the base can be efficiently heated, and the composite material can be efficiently heated by, for example, a temperature control unit. Further, with the conventional technology, it is possible to perform high-precision temperature control at the time of high-temperature heating, which could not be performed due to cracking of the ceramic layer or the like. It can be executed stably with accuracy. In addition, for example, a substrate mounting stage having a large diameter of about 300 mm can be realized, which makes it possible to sufficiently cope with a future increase in the diameter of a wafer. Further, since the ceramic layer is provided, it is possible to effectively prevent metal contamination and effectively prevent the composite material from being corroded by a halogen-based gas.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a helicon wave plasma CVD apparatus suitable for use in Embodiment 1 of the present invention.

FIG. 2 is a schematic sectional view of a substrate mounting stage according to Embodiment 1 of the present invention.

FIG. 3 is a schematic partial cross-sectional view of a semiconductor substrate and the like for describing a method of forming a barrier metal layer in the first embodiment.

FIG. 4 is a conceptual diagram of a helicon wave plasma CVD apparatus suitable for use in Embodiment 2 of the present invention.

FIG. 5 is a schematic sectional view of a substrate mounting stage according to Embodiment 2 of the present invention.

FIG. 6 is a conceptual diagram of a bias ECR CVD apparatus.

FIG. 7 is a schematic partial cross-sectional view of a lower wiring and the like for describing a method of forming a barrier metal layer in a fifth embodiment.

FIG. 8 is a schematic sectional view of another embodiment of the substrate mounting stage.

FIG. 9 is a schematic sectional view of another embodiment of the substrate mounting stage.

FIG. 10 is a schematic partial cross-sectional view of a chamber side wall.

FIG. 11 is a schematic partial sectional view of a chamber side wall.

FIG. 12 is a schematic partial cross-sectional view of a chamber side wall.

FIG. 13 is a schematic partial cross-sectional view of a chamber side wall.

FIG. 14 is a schematic partial sectional view of a chamber side wall.

[Explanation of symbols]

10, 10A, 10B, 10C, 110: substrate mounting stage, 11, 11A, 111, 211 ... composite material, 12, 12A, 112, 212 ... base material, 13,
13A, 113, 213 ... ceramic layer, 14,
14A, 114, 214, 214A, 214B ... heater, 15A, 115 ... piping, 16, 16A, 11
6,216 ... ceramic layer, 17, 17A, 11
7,217: brazing material, 118: disk-shaped member, 2
18 ... hollow cylindrical member, 20, 20A, 20B ...
CVD apparatus, 21 ... chamber, 22 ... side wall (chamber side wall), 23 ... top plate, 24 ... inductive coupling coil, 25 ... high frequency power supply, 26 ... DC power supply, 27 ..Power supply, 28 ... fluorescent fiber thermometer,
29: control device, 30A, 30B, 30C: pipe, 31: control valve, 32: heat medium supply device for temperature control, 40: silicon semiconductor substrate, 41 ...
· Interlayer insulating layer, 42 ··· opening, 43 ··· barrier metal layer, 44 ··· tungsten plug, 45 ··· wiring, 51 ··· chamber, 51A ··· chamber side wall, 51B ··· Quartz window, 52 ... microwave generating means, 53 ... heater, 54 ... solenoid coil, 55 ... pump, 56 ... RF bias power supply,
57 DC power supply, 58 power supply, 60 base insulating layer, 61 lower wiring, 62 interlayer insulating layer,
63 ... opening, 64 ... groove, 65 ... barrier metal layer, 66 ... upper wiring, 67 ... via hole

Claims (12)

[Claims] 1. A composite material comprising a base material in which the structure of a ceramic member is filled with an aluminum-based material, and a ceramic layer provided on the surface of the base material, having a function of an electrostatic chuck, And forming a barrier metal layer made of a high melting point metal or a compound thereof on the substrate by a plasma CVD method in a state where the substrate is mounted on a substrate mounting stage provided with a temperature control means. The method of forming the layer. 2. The method according to claim 1, wherein the substrate mounting stage is used as an electrode, and the ceramic layer has an electrostatic chuck function. 3. The method according to claim 1, wherein a temperature control means is provided on the substrate mounting stage, and the temperature control means comprises a heater. 4. The heater is disposed inside the base material, and when the linear expansion coefficient of the base material is α ₁ [unit: 10 ⁻⁶ / K], the linear expansion coefficient α of the material forming the heater is α. _H [Unit: 10
^-6 / K], wherein (α ₁ -3) ≦ α _H ≦ (α ₁ +3) is satisfied. 5. A temperature control means is disposed on the substrate mounting stage, and the temperature control means is constituted by a pipe for flowing a heat medium for temperature control disposed inside the base material. Is the linear expansion coefficient of α ₁ [unit: 10 ⁻⁶ / K], the linear expansion coefficient α _P [unit: 10 ⁻⁶ / K] of the pipe is (α ₁ −
3) The method for forming a barrier metal layer according to claim 1, wherein satisfies ≦ α _P ≦ (α ₁ +3). 6. The coefficient of linear expansion of the base material is α ₁ [unit: 10 ⁻⁶ /
When the K], linear expansion coefficient alpha ₂ [units of the ceramic layer: 10 ^-6 / K] is claim 1, characterized by satisfying the _{(α 1 -3) ≦ α 2} ≦ (α 1 +3) 3. The method for forming a barrier metal layer according to item 1. 7. The composition of the ceramic member forming the base material is cordierite ceramics, the composition of the aluminum-based material forming the base material is aluminum and silicon, and the material forming the ceramic layer is Al ₂ O _3. The method for forming a barrier metal layer according to claim 6, wherein 8. The composition of the ceramic member constituting the base material is aluminum nitride, the composition of the aluminum-based material constituting the base material is aluminum or aluminum and silicon, and the material constituting the ceramic layer is Al ₂ O _3. 7. The method according to claim 6, wherein the barrier metal layer is aluminum nitride. 9. The composition of a ceramic member forming a base material is silicon carbide, the composition of an aluminum-based material forming a base material is aluminum or aluminum and silicon, and the material forming a ceramic layer is Al ₂ O _3. 7. The method according to claim 6, wherein the barrier metal layer is aluminum nitride. 10. The method according to claim 1, wherein the ceramic layer is formed on the surface of the base material by a thermal spraying method. 11. The method according to claim 1, wherein the ceramic layer is attached to a surface of the base material by a brazing method.
3. The method for forming a barrier metal layer according to item 1. 12. The refractory metal or its compound constituting the barrier metal layer may be Ti, TiN, Ta, TaN,
The method according to claim 1, wherein the material is at least one material selected from the group consisting of W, WN, Mo, and MoN.