JP5323425B2 - Manufacturing method of semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a semiconductor device of which the reliability is improved by reducing the resistance of copper wiring containing a ruthenium-containing film and a copper-containing film, and to provide a method of manufacturing a semiconductor device. <P>SOLUTION: By a CVD method using a raw material containing an organic ruthenium complex expressed by a general formula 1 and reducing gas, an Ru film is formed on a substrate on which a recess is formed (step S12). By a CVD method using a raw material containing an organic copper complex expressed by a general formula 2 and reducing gas, a Cu film is formed on the Ru film, and copper wiring is formed at the recess (step S14). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for manufacturing a semiconductor device.

  In a semiconductor device, with the progress of miniaturization and multilayering, electromigration (EM) due to an increase in current density becomes serious. A multilayer wiring technique of copper wiring having high EM resistance is indispensable for highly integrating semiconductor devices.

  In the multilayer wiring technology of a semiconductor device, in order to improve the productivity and reliability of metal wiring, a base layer having various functions is generally interposed between the insulating layer and the metal wiring. As the underlayer, for example, a barrier layer that prevents diffusion of metal atoms, an adhesion layer that provides adhesion between the metal wiring and the insulating layer, and a seed layer that promotes film growth of the wiring material are known.

  When aluminum or tungsten is used as the wiring material, tantalum, titanium, tantalum nitride, titanium nitride, or the like is used as the material for the underlayer. On the other hand, in the multilayer wiring technology of copper wiring, since a low dielectric constant film is used as an insulating layer, when these metal materials are applied to the base layer, moisture and oxygen contained in the insulating layer are diffused into the base layer. It easily oxidizes the formation. As a result, the resistance value increases and the adhesion decreases, and the reliability of the semiconductor device is greatly impaired.

Therefore, in the multilayer wiring technology of copper wiring, various proposals related to the material of the underlayer have been conventionally made in order to solve the above problems. In Patent Documents 1 and 2, a ruthenium (Ru) film or a multilayer film including a Ru film is used as a base layer of a copper wiring. Since the oxide of the Ru film has conductivity, the resistance of the underlying layer can be suppressed and the oxidation of the copper wiring can be suppressed. Further, by laminating an adhesion layer on the Ru film, the adhesion between the Ru film and the copper wiring can be further improved.
JP 2005-129745 A JP 2006-328526 A

A so-called damascene method or dual-damascene method is used as a method for manufacturing copper wiring. That is, a trench corresponding to the wiring shape is formed in the insulating layer in advance, a base layer is laminated on the inner surface of the trench, and then a copper material is embedded in the trench to form a copper wiring. Alternatively, both the trench and the via hole (Via-Hole) are formed in the insulating layer in advance, and a base layer is laminated on the inner surface of the trench and the via hole, and then a copper material is embedded in the trench and the via hole to form a copper wiring. And via plugs are formed simultaneously.

  However, when the underlayer (ruthenium film) is formed, oxygen is introduced to decompose the ruthenium raw material complex, and the lower layer wiring with respect to the copper wiring is exposed to the ruthenium film forming space, and its oxidation Progress the state. As a result, in the above copper wiring manufacturing method, the resistance value of the wiring structure including the copper wiring is greatly increased. Therefore, it is necessary to reduce the resistance of the copper wiring by exposing it to a reducing gas atmosphere after forming the ruthenium film. There is.

The present invention has been made in order to solve the above-described problem. By forming a ruthenium-containing film without using oxygen, the ruthenium-containing film can be formed without performing a reduction step after the ruthenium-containing film is formed. An object of the present invention is to provide a method for manufacturing a semiconductor device in which the resistance of a copper wiring including a copper-containing film is reduced and the reliability thereof is improved.

  In order to achieve the above object, the invention according to claim 1 is a method of manufacturing a semiconductor device having a copper wiring, wherein an organic ruthenium complex and a first reducing gas are formed on an object having a recess. Forming a ruthenium-containing film by a CVD method using, and forming a copper-containing film on the ruthenium-containing film by a CVD method using an organic copper complex and a second reducing gas. And a step of embedding the containing film.

  According to the method for manufacturing a semiconductor device according to the first aspect, oxygen is not required and decomposition can be performed with a reducing gas, so that the ruthenium-containing film can be formed without being oxidized. As a result, the resistance of the copper wiring can be reduced. Further, since the reduction process after the formation of the ruthenium-containing film is not necessary, the process time can be shortened.

  According to a second aspect of the present invention, in the method of manufacturing a semiconductor device according to the first aspect, in the step of forming the ruthenium-containing film, the first reducing gas is separated to generate hydrogen radicals or hydrogen ions. The gist is to release.

  According to the second aspect of the present invention, oxygen is not required, and the ruthenium-containing film can be formed without being oxidized because it can be decomposed with a reducing gas. As a result, the resistance of the copper wiring can be reduced. Further, since the reduction process after the formation of the ruthenium-containing film is not necessary, the process time can be shortened.

According to a third aspect of the present invention, in the method of manufacturing a semiconductor device according to the first or second aspect, in the step of forming the ruthenium-containing film, the first reducing gas is hydrogen (H ₂ ). And at least one selected from the group consisting of ammonia (NH ₃ ), hydrazine derivatives, silane (SiH ₄ ), and disilane (Si ₂ H ₆ ).

  According to the third aspect of the present invention, the organic ruthenium complex is decomposed by at least one reduction action selected from the group consisting of hydrogen, ammonia, hydrazine derivatives, silane, and disilane. A ruthenium-containing film can be formed, and the resistance of the copper wiring can be reduced. Further, since the reduction process after the formation of the ruthenium-containing film is not necessary, the process time can be shortened.

  According to a fourth aspect of the present invention, in the method for manufacturing a semiconductor device according to the third aspect, in the step of forming the ruthenium-containing film, the hydrazine derivative is one or two hydrogen atoms of hydrazine. Is substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a linear or branched butyl group.

According to invention of Claim 4, a simpler structure can be used as a hydrazine derivative, and the versatility of this invention can be improved.
According to a fifth aspect of the present invention, in the method for manufacturing a semiconductor device according to any one of the first to fourth aspects, the step of forming the ruthenium-containing film includes an atmosphere of the first reducing gas. Is set to 10 ³ Pa to 10 ⁴ Pa.

  According to the fifth aspect of the invention, by defining the pressure of the first reducing gas, it is possible to give higher reproducibility to the reducing action of the reducing gas, and to reduce the resistance of the copper wiring. In addition, it is possible to give high embedding characteristics to the copper-containing film, and it is possible to more reliably form the object in the recess.

  According to a sixth aspect of the present invention, in the method of manufacturing a semiconductor device according to any one of the first to fifth aspects, the step of forming the ruthenium-containing film includes setting the temperature of the object to 250 ° C. The gist is to set the temperature to ˜400 ° C.

  According to the invention of claim 6, the ruthenium complex can be more reliably decomposed by regulating the temperature of the object, the resistance of the copper wiring is reduced, and the copper-containing film has high embedding characteristics. Can be given.

  According to a seventh aspect of the invention, there is provided the method for manufacturing a semiconductor device according to any one of the first to sixth aspects, wherein the organoruthenium complex is bis (2-methoxy-6-methyl-3,5-heptanedionate). ) -1,5 Hexadiene ruthenium complex.

According to the seventh aspect of the present invention, it is possible to reduce the resistance of the copper wiring and to give high embedding characteristics to the copper-containing film.
The invention according to claim 8 is the method for manufacturing a semiconductor device according to any one of claims 1 to 7, wherein a supply amount of the organic ruthenium complex is 2 × 10 ⁻⁸ to 1 × 10 ^{−. The} summary is ⁵ mol / min · cm ² .

  According to the invention described in claim 8, it is possible to more reliably form a ruthenium-containing film in the concave portion of the object with good coverage and uniformity. In addition, the resistance of the copper wiring can be reduced and high embedding characteristics can be given to the copper-containing film.

  The invention according to claim 9 is the method of manufacturing a semiconductor device according to any one of claims 1 to 8, wherein the organic copper complex is bis (2,6-dimethyl-2- (trimethylsilyl). It is summarized as being an oxy) -3,5-heptanedionato) copper complex.

According to the ninth aspect of the present invention, the resistance of the copper wiring can be reduced, and high embedding characteristics can be given to the copper-containing film.
In invention of Claim 10, It is a manufacturing method of the semiconductor device as described in any one of Claims 1-9, Comprising: The process of embedding the said copper containing film | membrane is per unit area of the surface of the said target object. The supply amount of the copper complex is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol / min · cm ² .

According to the method of manufacturing a semiconductor device according to claim 10, the copper-containing film is reliably deposited by supplying the organocopper complex at a supply amount of 1 × 10 ⁻⁷ mol / min · cm ² or more. be able to. Further, by supplying the organic copper complex at a supply amount of 5 × 10 ⁻⁵ mol / min · cm ² or less, high embedding characteristics can be given to the copper-containing film.

  In invention of Claim 11, It is a manufacturing method of the semiconductor device as described in any one of Claims 1-10, Comprising: The process of embedding the said copper containing film | membrane is 150 degreeC ~ The gist is to set the temperature to 350 ° C.

  According to the eleventh aspect of the present invention, it is possible to give higher reproducibility to the reducing action of the second reducing gas by regulating the temperature of the object, to reduce the resistance of the copper wiring, and to reduce the copper resistance. High embedding characteristics can be imparted to the containing film. Moreover, the growth reaction of the copper-containing film can be promoted by setting the temperature of the object to 150 ° C. or higher. Further, by setting the temperature of the object to 350 ° C. or lower, it is possible to avoid excessive decomposition reaction of organic components and thermal damage of the base material.

According to a twelfth aspect of the present invention, in the method of manufacturing a semiconductor device according to any one of the first to eleventh aspects, the step of embedding the copper-containing film includes the step of filling the second reducing gas with hydrogen. The gist is that the gas contains atoms.

According to the twelfth aspect of the present invention, it is possible to reduce the resistance of the copper wiring and to give high embedding characteristics to the copper-containing film.
According to a thirteenth aspect of the present invention, in the method of manufacturing a semiconductor device according to any one of the first to twelfth aspects, the step of embedding the copper-containing film includes the step of filling the second reducing gas with hydrogen. It is summarized as (H ₂ ).

According to the thirteenth aspect of the present invention, it is possible to reduce the resistance of the copper wiring and to give high embedding characteristics to the copper-containing film.
The invention according to claim 14 is the method for manufacturing a semiconductor device according to any one of claims 1 to 13, wherein the ruthenium-containing film is a fine particle film.

  As a copper material embedding technique, generally, a plating method using an electrochemical reaction and a CVD method using a thermal decomposition reaction of a copper complex are known. Among these, since the CVD method has higher embedding characteristics than the plating method, it is expected as a copper material embedding technique in order to cope with a reduction in design rules. In the case of using such a CVD method, since the growth of the initial film made of a copper material is greatly influenced by the surface condition of the base, the incubation time until the growth rate of the copper-containing film is stabilized, the so-called incubation time Will be very long. According to the invention of claim 9, since the ruthenium-containing film is composed of a fine particle film having a large surface area, such an incubation time can be shortened while reducing the resistance of the copper wiring including the ruthenium-containing film and the copper-containing film. Can also be planned.

The gist of the invention described in claim 15 is that the fine particle film is formed by setting the amount of leakage in the film formation space of the ruthenium-containing film to 10 ⁻² (Pa · m ³ / sec) or less. .

  According to the fifteenth aspect of the present invention, the ruthenium-containing film can be formed into a fine particle film by a simple method that merely sets the amount of leakage in the deposition space of the ruthenium-containing film.

  As described above, according to the present invention, the resistance of a copper wiring including a ruthenium-containing film and a copper-containing film is reduced, and a high embedding characteristic is given to the copper-containing film to improve its reliability. The manufacturing method of can be provided. Further, since the reduction process after the formation of the ruthenium-containing film is not necessary, the process time can be shortened.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, an embodiment of the invention will be described with reference to the drawings. First, a semiconductor device manufacturing apparatus used in the present invention will be described.
FIG. 1 is a plan view schematically showing a semiconductor device manufacturing apparatus 10. In FIG. 1, a manufacturing apparatus 10 includes a load lock chamber FL (hereinafter simply referred to as an LL chamber FL), a transfer chamber FT connected to the LL chamber FL, a Ru chamber F1 connected to the transfer chamber FT, and a pretreatment. It has a chamber F2 and a Cu chamber F3.

  The LL chamber FL has an internal space (hereinafter simply referred to as a storage chamber FLa) that can be decompressed, and carries in and out a plurality of substrates S. The LL chamber FL depressurizes the storage chamber FLa when starting the film formation process of the substrate S, and carries the substrate S into the transfer chamber FT. When the film formation process of the substrate S is completed, the LL chamber FL The substrate S is unloaded to the outside of the manufacturing apparatus 10 after being opened to the atmosphere. As the substrate S, for example, a silicon substrate or a glass substrate can be used.

  The transfer chamber FT has an internal space that can be depressurized (hereinafter simply referred to as a transfer chamber FTa), and a vacuum that is releasably communicated with the LL chamber FL, the Ru chamber F1, the pretreatment chamber F2, and the Cu chamber F3. Make the system formable. The transfer chamber FTa is equipped with a transfer robot RB for transferring the substrate S, and loads the substrate S of the LL chamber FL into the transfer chamber FT when starting the film forming process of the substrate S. The transport robot RB transports the substrate S to the Ru chamber F1, based on the data related to the transport path, and then transports the substrate S to the pretreatment chamber F2, and then to the Cu chamber F3 and unloads it to the LL chamber FL. Alternatively, the transport robot RB transports the substrate S to the Ru chamber F1, based on the data related to the transport path, and then transports the substrate S to the pretreatment chamber F2 and unloads it to the LL chamber FL.

  Next, the Ru chamber F1, the pretreatment chamber F2, and the Cu chamber F3 will be described below. FIG. 2 is a side sectional view schematically showing the configuration of the Ru chamber F1. In addition, since the pretreatment chamber F2 and the Cu chamber F3 are obtained by changing the raw material supply unit SU included in the Ru chamber F1, only the changes of the pretreatment chamber F2 and the Cu chamber F3 will be described.

  The Ru chamber F1 is a chamber having a film formation space for forming a ruthenium-containing film containing ruthenium (hereinafter simply referred to as a Ru film) using a CVD method. The Cu chamber F3 is a chamber for forming a copper-containing film containing copper (hereinafter simply referred to as a Cu film) using a CVD method. The pretreatment chamber F2 performs a predetermined pretreatment on the Ru film before laminating the Cu film on the Ru film to reduce the resistance value of the Ru film, or the adhesion between the Ru film and the Cu film. It is a chamber for improving.

  In FIG. 2, the Ru chamber F1 is connected to the transfer chamber FT and has a bottomed cylindrical chamber main body 21 that opens at the top, and is disposed on the top of the chamber main body 21 so that the upper opening of the chamber main body 21 can be opened and closed. A chamber lid 22 is provided. The chamber body 21 is closed by the chamber lid 22 to form a space surrounded by the chamber body 21 and the chamber lid 22 (hereinafter simply referred to as a processing space Fa, which is a film formation space).

  The processing space Fa includes a stage 23 on which the substrate S is placed, and accommodates the substrate S carried in from the transfer chamber FT. The stage 23 is equipped with a heater H connected to a heater power supply HG, and when the heater H is driven, the substrate S to be placed is heated to a predetermined temperature (for example, 150 ° C. to 500 ° C.).

An exhaust unit PU is connected to the right side of the processing space Fa via an exhaust port P0, and a pressure sensor PG1 that detects the pressure of the processing space Fa and outputs a detection result is connected to the left side of the processing space Fa. Has been. The exhaust unit PU is composed of various exhaust devices P such as an exhaust valve V1, a pressure adjustment valve V2, a raw material trap T, a turbo molecular pump, and a dry pump, and the pressure adjustment valve V2 depends on the detection result of the pressure sensor PG1. When driven, the pressure of the processing space Fa is adjusted to a predetermined pressure (for example, 10 ² Pa to 10 ⁵ Pa). Further, each part of the exhaust unit PU excluding the raw material trap T is adjusted to a predetermined temperature (20 ° C. to 250 ° C.) to avoid liquefaction of the raw material exhausted from the processing space Fa and maintain the exhaust capability.

A shower head 24 for introducing gas into the processing space Fa is disposed above the processing space Fa. The shower head 24 is adjusted to a predetermined temperature (20 ° C. to 250 ° C.) to avoid liquefaction of the introduced raw material SC and to smoothly lead out the raw material SC. The shower head 24 includes a plurality of first supply holes K1 and a plurality of second supply holes K2 that are independent from the first supply holes K1. Each first supply hole K1 is commonly connected to a first port P1 provided on the upper right side of the chamber lid 22, and each second supply hole K2 is a second port provided on the upper left side of the chamber lid 22, respectively. Commonly connected to P2.

The first port P1 is connected to the mass flow controller MFC1 for the reducing gas Gr and the mass flow controller for the carrier gas (for example, helium (He 2), argon (Ar ₂ ), nitrogen (N ₂ ), etc.) via the reducing gas line Lr. Connected to MFC2. The first port P1 uniformly supplies the carrier gas over substantially the entire surface of the substrate S through the first supply holes K1 when the mass flow controller MFC2 introduces a predetermined amount of carrier gas. At this time, when the mass flow controller MFC1 introduces a predetermined amount of the reducing gas Gr, the first port P1 allows the reducing gas Gr conveyed to the carrier gas to flow over substantially the entire surface of the substrate S through the first supply holes K1. Supply evenly.

As the reducing gas Gr, a gas that dissociates and releases hydrogen radicals or hydrogen ions can be used, and hydrogen (H ₂ ), ammonia (NH ₃ ), hydrazine derivatives, silane (SiH ₄ ), disilane ( At least one selected from the group consisting of Si ₂ H ₆ ) can be used. Further, as the hydrazine derivative, one in which one or two hydrogen atoms of hydrazine are substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a linear or branched butyl group is used. Can do. In the case where the flow rate of the reducing gas Gr is sufficiently large so that the supply of the reducing gas Gr can be stabilized, a configuration without the carrier gas, that is, the mass flow controller MFC2 may be used.

  The second port P2 is connected to the raw material supply unit SU constituting the supply unit via the raw material gas line Ls. The raw material supply unit SU includes a raw material tank 25 for storing the Ru film raw material SC, a liquid mass flow controller LMFC connected to the raw material tank 25, and a vaporizer IU connected to the liquid mass flow controller LMFC. The raw material supply unit SU and the raw material gas line Ls are adjusted to a predetermined temperature (20 ° C. to 250 ° C.) to avoid the liquefaction of the raw material SC and smoothly feed the raw material SC.

  As the raw material SC, bis (2-methoxy-6-methyl-3,5-heptanedionato) -1,5 hexadiene ruthenium complex can be used. As the raw material SC, a solution in which the ruthenium complex is dissolved in various solvents (for example, hexane, octane, toluene, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran, etc.) can be used.

The raw material tank 25 receives pressure of a derived gas (for example, He, Ar, N _2, etc.) and derives the stored raw material SC at a predetermined pressure. The liquid mass flow controller LMFC adjusts the raw material SC derived from the raw material tank 25 to a predetermined supply amount and introduces the raw material SC into the vaporizer IU. The vaporizer IU is connected to a mass flow controller MFC3 of a carrier gas (for example, He, Ar, N ₂ etc.), vaporizes the raw material SC from the liquid mass flow controller LMFC, and feeds the raw material SC together with the carrier gas to the second port P2. To derive. The second port P2 uniformly supplies the raw material SC from the vaporizer IU over substantially the entire surface of the substrate S through the second supply holes K2.

  Thereby, the Ru chamber F1 can supply each of the reducing gas Gr and the raw material SC to the processing space Fa through independent paths, and the reducing gas Gr and the raw material SC are mixed only in the processing space Fa. Can do. As a result, even if the raw material SC has a high reactivity with the reducing gas Gr, the reaction related to the raw material SC can be advanced only in the processing space Fa.

In the middle of the raw material gas line Ls, a bypass line Lb leading to the raw material trap T is connected. When supplying the raw material SC toward the processing space Fa, the raw material supply unit SU closes the supply valve V3 and opens the switching valve V4 until the supply amount of the raw material SC is stabilized.
The raw material SC and the carrier gas are led out to the raw material trap T through this bypass line Lb. When the supply amount of the raw material SC is stabilized, the raw material supply unit SU closes the switching valve V4 and opens the supply valve V3 to supply the raw material SC and the carrier gas to the processing space Fa. Thereby, the material supply unit SU can make the response of supply / stop of the material SC to the processing space Fa steep.

In addition, in this process space Fa, the structure which selects the sealing material between each member and each member so that the amount of leaks can be 10 ^<-2 > (Pa * m ^< 3> / sec) or less is preferable. As a measurement of the leak amount in the processing space Fa, first, the exhaust unit PU is driven with the supply valve V3 closed, and the exhaust valve V1 is turned on when the processing space Fa reaches a predetermined ultimate pressure, for example, 10 ⁻¹ Pa. Close, that is, close the processing space Fa. Then, the pressure in the processing space Fa is sequentially measured using the pressure sensor PG1 until a predetermined time, for example, 20 minutes elapses after the exhaust valve V1 is closed, and 1 second of the elapsed time since the exhaust valve V1 is closed. The pressure increase per unit is calculated as the leak amount.

In the processing space Fa, when the leakage amount is 10 ⁻² (Pa · m 3 / sec) or less, it is possible to sufficiently suppress the entry of outside air, that is, oxygen and moisture into the processing space Fa. The influence of oxygen and moisture on the thermal decomposition reaction can be sufficiently suppressed.

When the substrate S is loaded, the Ru chamber F1 supplies the reducing gas Gr to the processing space Fa through the reducing gas line Lr, and adjusts the pressure of the processing space Fa to a predetermined pressure via the exhaust unit PU. . For example, the Ru chamber F1 sufficiently develops the reducing action of the reducing gas Gr by the atmosphere of the reducing gas Gr of 10 ³ Pa or more, and the exhaust unit by the atmosphere of the reducing gas Gr of 10 ⁴ Pa or less. Avoid excessive load on the PU.

  When the substrate S is loaded, the Ru chamber F1 places the substrate S on the stage 23 and raises the temperature of the substrate S to a predetermined temperature via the heater H. For example, the Ru chamber F1 starts a thermal decomposition reaction of the raw material SC by heating at 250 ° C. or higher, and avoids thermal damage to lower layer conductors such as lower layer wiring by adjusting the temperature to 400 ° C. or lower.

  The Ru chamber F1 supplies a predetermined amount of raw material SC to the processing space Fa through the raw material gas line Ls when the atmosphere of the reducing gas Gr is formed and the substrate S is heated to a predetermined temperature, The raw material SC is thermally decomposed under the atmosphere of the reactive gas Gr, and a Ru film is deposited on the substrate S.

As a result, the Ru chamber F1 can reduce the oxide of the lower conductor and the oxide of the Ru film by the reducing gas Gr, respectively, and can be brought close to the metal state. The Ru chamber F1 can connect the lower conductor and the Ru film with low contact resistance while suppressing the intervention of the oxide film between the lower conductor and the Ru film. Further, as described above, when the amount of leakage in the processing space Fa is 10 ⁻² (Pa · m ³ / sec) or less, the thermal decomposition reaction of the raw material SC hardly causes oxygen or moisture from the outside to intervene. Therefore, the growth of crystal grains mainly composed of Ru is promoted, and the Ru film can be formed as a fine particle film composed of such a large number of crystal grains.

The pretreatment chamber F2 is a chamber having substantially the same configuration as the Ru chamber F1, and is different from the Ru chamber F1 in that it does not have the raw material supply unit SU, and the pretreatment gas used by the mass flow controller MFC1 for pretreatment. It differs in that Gp is supplied. As the pretreatment gas Gp, for example, when the pretreatment chamber F2 performs a heat treatment under an inert gas atmosphere, an inert gas (eg, He, Ar, N _2, etc.) can be used.
In addition, as the pretreatment gas Gp, for example, a reducing gas can be used when heat treatment is performed in an atmosphere of a reducing gas.

When the substrate S is loaded, the pretreatment chamber F2 supplies the pretreatment gas Gp to the treatment space Fa through the reducing gas line Lr, and adjusts the pressure of the treatment space Fa to a predetermined pressure by driving the exhaust unit PU. To do. For example, the pretreatment chamber F2 reliably reduces the oxide of the Ru film by the atmosphere of the reducing gas Gr of 10 ² Pa or more, and excessively affects the exhaust unit PU by the reducing atmosphere of 10 ⁵ Pa or less. Avoid the load.

  When the substrate S is loaded, the pretreatment chamber F2 places the substrate S on the stage 23 and adjusts the substrate S to a predetermined temperature via the heater H. For example, the pretreatment chamber F2 raises the temperature of the substrate S to 150 ° C. or higher, and effectively exhausts organic components remaining in the Ru film. Further, the pretreatment chamber F2 adjusts the substrate S to 500 ° C. or less to avoid thermal damage to the lower layer conductor.

Accordingly, the pretreatment chamber F2 can perform a predetermined pretreatment for reducing the resistance of the Ru film deposited on the substrate S.
The Cu chamber F3 is a chamber having substantially the same configuration as the Ru chamber F1, and differs from the Ru chamber F1 in that the raw material SC is an organic copper complex represented by the general formula (2). Has the same configuration as the Ru chamber F1.

  As the copper complex, bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) copper complex can be used. As the raw material SC, a solution in which the copper complex is dissolved in various solvents (for example, hexane, octane, toluene, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran, etc.) can be used.

When the substrate S is loaded, the Cu chamber F3 supplies the reducing gas Gr to the processing space Fa through the reducing gas line Lr and adjusts the pressure of the processing space Fa to a predetermined pressure via the exhaust unit PU. . For example, the Cu chamber F3 sufficiently develops the reducing action of the reducing gas Gr by the atmosphere of the reducing gas Gr of 10 ² Pa or more, and the exhaust unit by the atmosphere of the reducing gas Gr of 10 ⁵ Pa or less. Avoid excessive load on the PU.

  When the substrate S is carried in, the Cu chamber F3 places the substrate S on the stage 23 and raises the temperature of the substrate S to a predetermined temperature via the heater H. For example, the Cu chamber F3 starts a thermal decomposition reaction of the raw material SC by heating at 150 ° C. or higher, and avoids thermal damage to the lower layer wiring, the Ru film, and the Cu film by adjusting the temperature to 350 ° C. or lower.

The Cu chamber F3 supplies a predetermined amount of raw material SC to the processing space Fa through the raw material gas line Ls when the atmosphere of the reducing gas Gr is formed and the substrate S is heated to a predetermined temperature, The raw material SC is thermally decomposed under the atmosphere of the reactive gas Gr, and a Cu film is deposited on the Ru film. For example, the Cu chamber F3 contains 5 × 10 ⁻⁵ mol / min · cm ² to 1 of the organocopper complex.
Supply in the range of × 10 ⁻⁷ mol / min · cm ² . Cu chamber F3 contains the organic copper complex,
By supplying at a supply rate of 1 × 10 ⁻⁷ mol / min · cm ² or more, the Cu film can be reliably deposited. Further, by supplying the organocopper complex at a supply amount of 5 × 10 ⁻⁵ mol / min · cm ² or less, high embedding characteristics can be given to the Cu film.

  As a result, the Cu chamber F3 can reduce the oxide of the Ru film and the oxide of the Cu film with the reducing gas Gr, respectively, so as to be close to the metal state. The Cu chamber F3 can connect the Ru film and the Cu film with a low contact resistance while suppressing the intervention of the oxide film between the Ru film and the Cu film. In addition, when the Ru film is configured as a fine particle film as described above, the surface area of the Ru film can be greatly increased compared to the case where the surface of the Ru film is configured as a smooth surface. The film formation time required for forming the Cu film can be shortened while reducing the contact resistance between the Ru film and the Cu film.

Next, an electrical configuration relating to the semiconductor device manufacturing apparatus 10 will be described below. FIG. 3 is an electric block circuit diagram showing an electrical configuration of the manufacturing apparatus 10.
In FIG. 3, the control device 30 causes the semiconductor device manufacturing apparatus 10 to execute various processing operations such as a substrate S transfer process, a Ru film formation process, a pre-process, and a Cu film formation process. It is. The control device 30 includes an input I / F 30A for inputting various signals, an arithmetic unit 30B for executing various arithmetic processes, a storage unit 30C for storing various data and various programs, An output I / F 30D for outputting a signal is provided.

  The control device 30 includes an input unit 31A, an LL chamber detection unit 32A, a transfer chamber detection unit 33A, a Ru chamber detection unit 34A, a pretreatment chamber detection unit 35A, and a Cu chamber detection unit 36A via an input I / F 30A. It is connected.

  The input unit 31 </ b> A has various operation switches such as a start switch and a stop switch, and inputs data to be used by the manufacturing apparatus 10 for various processing operations to the control apparatus 30. For example, the input unit 31 </ b> A inputs data related to the substrate S transport process, the Ru film deposition process, the pre-process, and the Cu film deposition process to the control device 30.

  That is, the input unit 31 </ b> A inputs data related to the transport path (processing order of various processes) of the substrate S to the control device 30. Further, the input unit 31A relates to film forming conditions (for example, the substrate temperature, the flow rate of the reducing gas Gr, the supply amount of the raw material SC, the film forming pressure, the film forming time, etc.) for executing the Ru film forming process. Data is input to the control device 30. In addition, the input unit 31 </ b> A inputs data related to preprocessing conditions (for example, the substrate temperature, the flow rate of the preprocessing gas Gp, the processing pressure, the processing time, and the like) for executing the preprocessing to the control device 30. Further, the input unit 31A relates to film formation conditions (for example, the substrate temperature, the flow rate of the reducing gas Gr, the supply amount of the raw material SC, the film formation pressure, the film formation time, etc.) for executing the Cu film formation process. Data is input to the control device 30.

The control device 30 receives various data input from the input unit 31A, stores it in the storage unit 30C, and executes various processing operations under conditions corresponding to the various data.
The LL chamber detection unit 32 </ b> A detects the state of the LL chamber FL, for example, the actual pressure in the storage chamber FLa, the number of substrates S, and the like, and inputs the detection result to the control device 30. The transfer chamber detection unit 33A detects the state of the transfer chamber FT, for example, the arm position of the transfer robot RB, and inputs the detection result to the control device 30.

  The Ru chamber detection unit 34A determines the state of the Ru chamber F1, for example, the actual temperature of the corresponding substrate S, the actual pressure of the processing space Fa, the actual flow rate of the reducing gas Gr, the actual supply amount of the raw material SC, the actual processing time, and the like. The detection result is input to the control device 30.

  The preprocessing chamber detection unit 35A detects the state of the preprocessing chamber F2, for example, the actual temperature of the corresponding substrate S, the actual pressure of the processing space Fa, the actual flow rate of the preprocessing gas Gp, the actual processing time, and the like. A signal is input to the control device 30.

  The Cu chamber detection unit 36A determines the state of the Cu chamber F3, for example, the actual temperature of the corresponding substrate S, the actual pressure of the processing space Fa, the actual flow rate of the reducing gas Gr, the actual supply amount of the raw material SC, the actual processing time, etc. The detection result is input to the control device 30.

  An output unit 31B, an LL chamber driving unit 32B, a transfer chamber driving unit 33B, a Ru chamber driving unit 34B, a pretreatment chamber driving unit 35B, and a Cu chamber driving unit 36B are connected to the control device 30 via an output I / F 30D. Has been.

The output unit 31B has various display devices such as a liquid crystal display and outputs various data related to the processing status of the manufacturing apparatus 10.
The control device 30 outputs a drive control signal corresponding to the LL chamber drive unit 32B to the LL chamber drive unit 32B using the detection result from the LL chamber detection unit 32A. The LL chamber drive unit 32B responds to a drive control signal from the control device 30, and allows the substrate S to be loaded or unloaded by depressurizing or opening the accommodation chamber FLa.

  The control device 30 uses the detection result from the transfer chamber detection unit 33A to output a drive control signal corresponding to the transfer chamber detection unit 33A to the transfer chamber drive unit 33B. The transfer chamber drive unit 33B transfers the substrate S in the order of the LL chamber FL, the transfer chamber FT, the Ru chamber F1, the pretreatment chamber F2, and the Cu chamber F3 in response to the drive control signal from the control device 30. .

  The control device 30 uses the detection result from the Ru chamber detection unit 34A to output a drive control signal corresponding to the Ru chamber drive unit 34B to the Ru chamber drive unit 34B. In response to the drive control signal from the control device 30, the Ru chamber drive unit 34B executes the Ru film formation process under the film formation conditions from the input unit 31A.

  The control device 30 uses the detection result from the pretreatment chamber detection unit 35A to output a drive control signal corresponding to the pretreatment chamber drive unit 35B to the pretreatment chamber drive unit 35B. In response to the drive control signal from the control device 30, the preprocessing chamber drive unit 35B performs a predetermined preprocessing under the preprocessing conditions from the input unit 31A.

  The control device 30 uses the detection result from the Cu chamber detection unit 36A to output a drive control signal corresponding to the Cu chamber drive unit 36B to the Cu chamber drive unit 36B. In response to the drive control signal from the control device 30, the Cu chamber drive unit 36B executes a Cu film deposition process under the Cu film deposition conditions from the input unit 31A.

Next, a method for manufacturing a semiconductor device will be described below. FIG. 4 is a flowchart showing a method for manufacturing a semiconductor device.
First, the control device 30 receives an operation signal for forming a copper wiring, and reads a program for forming the copper wiring from the storage unit 30C. Next, the control device 30 inputs the substrate S into the LL chamber FL and receives various data input from the input unit 31A (step S11). Then, the control device 30 detects the state of the LL chamber FL and the state of the transfer chamber FT, and starts the transfer process of the substrate S according to the processing order input from the input unit 31A.

  That is, the control device 30 conveys the substrate S of the LL chamber FL to the Ru chamber F1, and based on the Ru film formation conditions from the input unit 31A, the atmosphere of the reducing gas Gr in the processing space Fa of the Ru chamber F1. Form. Further, the control device 30 drives the heater H of the Ru chamber F1 to raise the temperature of the substrate S, and then supplies the corresponding raw material SC to execute the Ru film forming process (step S12). Then, the control device 30 detects the state of the Ru chamber F1 and determines whether or not the Ru film formation process is completed. When the Ru film formation process is completed, the control device 30 moves the substrate S in the Ru chamber F1 forward. It is conveyed to the processing chamber F2.

  When the controller 30 transports the substrate S to the preprocessing chamber F2, the control device 30 forms an atmosphere of the preprocessing gas Gp in the processing space Fa of the preprocessing chamber F2 based on the preprocessing conditions from the input unit 31A. Further, the control device 30 drives the heater H of the pretreatment chamber F2 to raise the temperature of the substrate S, and executes pretreatment corresponding to the Ru film and the Cu film (step S13). Then, the control device 30 detects the state of the preprocessing chamber F2 and determines whether or not the preprocessing is completed. When the preprocessing is completed, the substrate S is transferred to the Cu chamber F3.

  When the controller 30 transports the substrate S to the Cu chamber F3, the control device 30 forms an atmosphere of the reducing gas Gr in the processing space Fa of the Cu chamber F3 based on the film formation conditions of the Cu film from the input unit 31A. Further, the control device 30 drives the heater H of the Cu chamber F3 to raise the temperature of the substrate S, and then supplies the corresponding raw material SC to execute the Cu film forming process (step S14). Then, the control device 30 detects the state of the Cu chamber F3 to determine whether or not the Cu film forming process is finished. When the Cu film forming process is finished, the control device 30 moves the substrate S in the Cu chamber F3 to LL. Transport to chamber FL.

  Thereafter, similarly, the control device 30 sequentially performs the Ru film formation process, the pre-process, and the Cu film formation process on each of the substrates S to form Cu wirings. When the control device 30 detects the state of the LL chamber FL and forms copper wiring on all the substrates S, the control device 30 opens the LL chamber FL to the atmosphere and carries out all the substrates S to the outside.

Example 1
Next, the embedding property of the copper wiring formed using the semiconductor device manufacturing apparatus 10 will be described below. 4 and 5 are TEM (Transmission Electron Microscope) cross-sectional images showing the embedding property of the Ru film formed using the semiconductor device manufacturing apparatus 10 and the embedding property of the Cu film formed on the Ru film, respectively. is there.

  First, a silicon substrate is used as the substrate S, an insulating layer 41 is formed on the substrate S, and a hole VH (recessed portion) having a hole diameter of 50 nm and an aspect ratio (hole depth / hole diameter) of 8.2 is formed in the insulating layer 41. ) Was formed. Next, a Ru film 42 was formed on the surface of the insulating layer 41 using the following Ru film formation conditions, and a TEM cross-sectional image thereof was taken. Further, the Ru film 42 is pretreated using the following pretreatment conditions, and subsequently, the Cu film 43 is formed on the surface of the Ru film 42 using the Cu film formation conditions shown below. A cross-sectional image was taken.

(Ru film formation conditions)
Raw material SC: 0.5 (mol / L) bis (2-methoxy-6-methyl-3,5-heptanedionato) -1,5 hexadiene ruthenium complex using n-octane as a solvent. 8.5 × 10 −7 (mol / min · cm ² )
・ Reducing gas Gr: flow rate of hydrogen and reducing gas Gr: 3 (L / min)
-Substrate temperature: 270 (° C)
・ Film pressure: 2600 (Pa)
・ Deposition time: 720 (seconds)
(Pretreatment conditions)
-Substrate temperature: 350 (° C)
・ Process gas: Hydrogen ・ Processing pressure: 3500 (Pa)
(Cu film forming conditions)
Raw material SC: 0.5 (mol / L) bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) copper complex with n-octane as a solventSupply amount of raw material SC: 2.4 × 10 ⁻⁶ (mol / min · cm ² )
・ Reducing gas Gr: flow rate of hydrogen and reducing gas Gr: 3 (L / min)
-Substrate temperature: 270 (° C)
・ Film formation pressure: 400 (Pa)
・ Deposition time: 180 (seconds)
In FIG. 5, it can be seen that the Ru film 42 is shown in a dark color region and is uniformly formed with a film thickness of about 20 nm over the upper portion of the insulating layer 41 and the entire inner wall of the hole VH. Thereby, according to the film formation process of the Ru film, that is, the film formation process in which the β-diketonate ruthenium complex is thermally decomposed in a reducing atmosphere, even if the base is the insulating layer 41, the film thickness is high. It can be seen that a Ru film 42 having uniformity and high step coverage can be obtained.

In FIG. 6, the Cu film 43 is shown in a dark color region, and it can be seen that the Cu material is uniformly filled throughout the inside of the hole VH. Thus, according to the Ru film forming process, the pre-processing, and the Cu film forming process, a Cu wiring having high embeddability can be formed. Then, the resistance of the copper wiring can be reduced by reducing the oxide of the underlying wiring, the oxide of the Ru film, and the oxide of the Cu film, respectively, by the treatment in a continuous reducing atmosphere. (Example 2)
The Ru film 42 is formed on the surface of the insulating layer 41 using the following Ru film formation conditions in the processing space Fa in which the leak amount is 10 ⁻² (Pa · m ³ / sec) or less. Got. Then, a TEM cross-sectional image and a TEM plane image of Example 2 were taken, and a full-field electron diffraction image of the Ru film 42 was taken in order to confirm the crystallinity of the Ru fine particles. 7 and 8 show a TEM cross-sectional image and a TEM plane image of Example 2. FIG.

(Ru film formation conditions)
Raw material SC: 0.5 (mol / L) bis (2-methoxy-6-methyl-3,5-heptanedionato) -1,5 hexadiene ruthenium complex using n-octane as a solvent. 0.4 (g / min)
・ Reducing gas Gr: flow rate of hydrogen and reducing gas Gr: 3 (L / min)
-Substrate temperature: 270 (° C)
-Film formation pressure: 3500 (Pa)
・ Deposition time: 720 (seconds)
7 and 8, it can be seen that the Ru film 42 is composed of a large number of Ru fine particles of several nm as shown in shades. In FIG. 9, the Ru film 42 shows a Debye-Scherrer ring RD corresponding to the lattice constant of Ru fine particles, and it can be seen that each of the Ru fine particles is a crystal grain having crystallinity.

(Example 3)
A silicon substrate having a silicon oxide film was used as the substrate S, and a titanium (Ti) film was formed on the silicon oxide film to form a Ru film using the following Ru film formation conditions. Subsequently, Example 3 was obtained by changing the film formation time in the range of 0 to 120 seconds under the following Cu film formation conditions. Further, Comparative Example 1 was obtained by making the other conditions the same as Example 3 without forming the Ru film. Then, XRF measurement was performed on Example 3 and Comparative Example 1, and the peak intensity associated with Cu atoms, which is an index of the thickness of the Cu film, was measured. FIG. 10 is a graph showing the relationship between the deposition time of the Cu film and the XRF intensity of the Cu film.

  In FIG. 10, in Comparative Example 1, a film formation time of about 20 seconds is required from the supply of the Cu film raw material SC until the film formation of the Cu film is started. It can be seen that the film formation starts with the supply of the raw material SC, and that the incubation time is 0 second. Therefore, it can be seen that by forming a fine particle film containing Ru as a main component, the incubation time of the Cu film can be shortened by amplification of the catalytic action by the Ru crystal grains. Moreover, in Example 3, since the increase rate of the XRF intensity with respect to the film formation time is larger than the increase rate in Comparative Example 1, the film formation rate of the Cu film can be increased.

(Ru film formation conditions)
Raw material SC: 0.5 (mol / L) bis (2-methoxyxy-6-methyl-3,5-heptanedionato) -1,5 hexadiene ruthenium complex using n-octane as a solvent. 0.4 (g / min)
・ Reducing gas Gr: flow rate of hydrogen and reducing gas Gr: 3 (L / min)
-Substrate temperature: 270 (° C)
-Film formation pressure: 3500 (Pa)
・ Deposition time: 720 (seconds)
(Cu film forming conditions)
Raw material SC: 0.5 (mol / L) bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) copper complex with n-octane as a solventSupply amount of raw material SC: 1.2 (g / min)
・ Reducing gas Gr: flow rate of hydrogen and reducing gas Gr: 3 (L / min)
-Substrate temperature: 270 (° C)
・ Film formation pressure: 400 (Pa)
Example 4
Using a silicon substrate having a silicon oxide film as the substrate S, a vanadium nitride (VN) film was formed on the silicon oxide film, and a Ru film was formed in the same manner as in Example 3. Subsequently, Example 4 was obtained by changing the film formation time to 60 seconds and the film formation pressure in the range of 400 Pa to 3500 Pa under the Cu film formation conditions in Example 3 and otherwise performing the same as in Example 3. . Further, Comparative Example 2 was obtained by making the other conditions the same as Example 4 without forming a Ru film. Then, XRF measurement was performed on Example 4 and Comparative Example 2, and the peak intensity associated with Cu atoms, which is an index of the thickness of the Cu film, was measured. FIG. 11 is a diagram showing the relationship between the deposition pressure of the Cu film and the XRF intensity of the Cu film.

In FIG. 11, the XRF intensity of Example 4 is larger than the XRF intensity of Comparative Example 2 in all pressure ranges of 400 Pa to 3500 Pa, and the amount of Cu film formed in Example 4 is larger than that of Comparative Example 2. I understand that it is expensive. Therefore, it can be seen that by forming a fine particle film containing Ru as a main component, the deposition rate of the Cu film can be increased by amplification of the catalytic action by the Ru crystal grains. In addition, while the XRF intensity of Comparative Example 2 continues to increase even at 3500 Pa, the XRF intensity of Example 4 is saturated near 1500 Pa, so the Cu film formation process can be rate-controlled on the lower pressure side. It can be seen that the use efficiency of the raw material SC can be improved by forming a fine particle film containing Ru as a main component.

(Semiconductor device)
Next, a semiconductor device manufactured using the semiconductor device manufacturing method will be described below. FIG. 12 is a cross-sectional view of a principal part showing a semiconductor device.

  In FIG. 12, the semiconductor device 50 is, for example, a memory device including various RAMs and various ROMs, a logic device including MPUs, or general-purpose logic. A thin film transistor Tr is formed on the substrate S of the semiconductor device 50, and a copper wiring 51 is connected to the diffusion layer LD of the thin film transistor Tr via a contact plug Pc.

  The copper wiring 51 has a base layer 52 connected to the contact plug Pc and a wiring layer 53 filling the inside of the base layer 52. The underlayer 52 is a layer having a Ru film, and is formed by the Ru film formation process using the Ru chamber F1 and the pretreatment using the pretreatment chamber F2. The wiring layer 53 is formed by a film forming process of the Cu film using the Cu chamber F3. As a result, the wiring layer 53 can reduce the contact resistance between the contact plug Pc and the base layer 52 and the contact resistance between the base layer 52 and the wiring layer 53, thereby improving the reliability. Can be made.

According to the said embodiment, there exist the following effects.
(1) In the above embodiment, a Ru film is formed on the substrate S on which the recesses are formed by the CVD method using the raw material SC containing the organoruthenium complex and the reducing gas Gr (step S12). Then, a Cu film is formed on the Ru film and a copper wiring is formed in the recess by a CVD method using the raw material SC containing the organic copper complex and the reducing gas Gr (step S14).

  Therefore, the Ru film and the Cu film can be formed under a reducing gas atmosphere. As a result, when the Ru film is formed and when the Cu film is formed, the oxide of the underlying wiring and the oxide of the copper wiring can be reduced to approach the metal state. Therefore, the resistance of the copper wiring can be reduced.

(2) In the Ru film forming step (step S12) and the Cu film forming step (step S14) of the above embodiment, a reducing gas Gr that diverges and releases hydrogen radicals or hydrogen ions is used. Alternatively, as the reducing gas Gr, hydrogen (H ₂ ), ammonia (NH ₃
), A hydrazine derivative, silane (SiH ₄ ), or disilane (Si ₂ H ₆ ). Therefore, higher versatility can be given to the manufacturing method of the semiconductor device.

(3) In the Ru film forming step (step S12) of the above embodiment, the supply amount of the organic ruthenium complex per unit area of the surface of the object (the substrate S on which the recesses are formed) is 2 × 10 ^{− 8} mol / min · cm ² to 1 × 10 ⁻⁵ mol / min · cm ² , the pressure of the reducing gas Gr is specified to 10 ³ Pa to 10 ⁴ Pa, and the temperature of the substrate S is 250 ° C. It is specified at ˜400 ° C. Therefore, the growth rate of the Ru film and the reducing action of the reducing gas Gr can be more reliably and uniformly deposited in the concave portion of the target object, and can provide higher reproducibility, and Thermal damage to the base material can be avoided. As a result, higher reproducibility can be given to the electrical characteristics of the copper wiring.

(4) In the above embodiment, the substrate S after the Ru film formation step is placed in the atmosphere of the pretreatment gas Gp, and the pretreatment is performed on the Ru film before forming the Cu film. Therefore, the resistance value of the Ru film can be reduced, or the adhesion between the Ru film and the Cu film can be improved. As a result, the reliability of the copper wiring can be further improved.

(5) In the Cu film forming step (step S14) of the above embodiment, the supply amount of the organocopper complex is set to 5 × 10 ⁻⁵ mol / min · cm ² to 1 × 10 ⁻⁷ mol / min · cm. ^It is specified in the range that satisfies ² . Therefore, the Cu film can be reliably deposited on the Ru film, and high embedding characteristics can be given to the Cu film.

In addition, you may change the said embodiment into the following aspects.
In the above embodiment, the pre-processing step (Step S13) is performed after the Ru film forming step (Step S12). For example, the Cu film forming process (step S14) may be executed subsequent to the Ru film forming process.

  In the above-described embodiment, heat treatment or reduction treatment is performed in the pretreatment process. For example, in the pretreatment step, first, an oxidation process for removing the organic component of the Ru film is performed, and then a reduction process for reducing the oxide of the Ru film to a metal Ru is performed. It may be configured to execute. Alternatively, in the pretreatment step, an adhesion layer may be formed on the Ru film to improve the adhesion between the Ru film and the Cu film. That is, the pretreatment process may be a treatment for reducing the resistance value of the Ru film or improving the adhesion between the Ru film and the Cu film before forming the Cu film.

  In the embodiment described above, the semiconductor device manufacturing apparatus 10 includes the preprocessing chamber F2 for preprocessing the Ru film, and includes the preprocessing chamber detection unit 35A and the preprocessing chamber driving unit 35B. For example, the semiconductor device manufacturing apparatus 10 may have a configuration in which the preprocessing chamber F2 is not mounted and the preprocessing chamber detection unit 35A and the preprocessing chamber driving unit 35B are not included. For example, the semiconductor device manufacturing apparatus 10 may be configured to execute a predetermined pretreatment such as a heat treatment or a reduction treatment using the Ru chamber F1.

  In the embodiment described above, the semiconductor device manufacturing apparatus 10 includes the preprocessing chamber F2 for preprocessing the Ru film, and includes the preprocessing chamber detection unit 35A and the preprocessing chamber driving unit 35B. In addition, a Cu chamber F3 for forming a Cu film is mounted, and a Cu chamber detecting unit 36A and a Cu chamber driving unit 36B are provided. Not limited to this, the manufacturing apparatus 10 may have a configuration in which the pretreatment chamber F2 and the Cu chamber F3 are not mounted. For example, the Ru chamber F1 may be used to perform all processes such as a predetermined pretreatment such as a heat treatment and a reduction treatment and a Cu film formation treatment by performing gas switching.

  In the above embodiment, the Ru chamber F1 and the Cu chamber F3 guide the raw material SC and the reducing gas Gr to the processing space Fa through independent paths, respectively. For example, when the reactivity between the raw material SC and the reducing gas Gr is low, the first port P1 and the second port P2 may be configured as one common port. Further, the first supply hole K1 and the second supply hole K2 may be configured as supply holes that communicate with each other, and the reducing gas Gr may be used as a carrier gas for the mass flow controller MFC3.

That is, the present invention is not limited with respect to the supply path of the raw material SC and the reducing gas Gr, and any structure may be used as long as the raw material SC is thermally decomposed in an atmosphere of the reducing gas Gr.
In the above embodiment, the raw material supply unit SU derives the raw material SC of the raw material tank 25 by pressurizing the derived gas, and supplies the gas of the raw material SC to the processing space Fa by vaporization of the vaporizer IU. For example, the raw material supply unit SU uses a so-called bubbling method in which a carrier gas is introduced into the raw material SC of the raw material tank 25 and a mixed gas of the carrier gas and the raw material SC is supplied to the processing space Fa. It may be.

  In other words, the present invention is not limited to the method for supplying the raw material SC, and any structure may be used as long as the raw material SC is thermally decomposed under the processing space Fa in a reducing atmosphere.

The top view which shows typically the manufacturing apparatus of the semiconductor device of this embodiment. Similarly, the schematic sectional drawing which shows the structure of Ru chamber. Similarly, the electric block circuit diagram which shows the electric constitution of a manufacturing apparatus. Similarly, the flowchart which shows the formation process of copper wiring. Similarly, a TEM cross-sectional image showing the embedding property of the Ru film. Similarly, a TEM cross-sectional image showing Cu film embedding. Similarly, a TEM cross-sectional image showing fine particles in the Ru film. Similarly, a TEM plane image showing fine particles in the Ru film. Similarly, an electron beam diffraction image of a Ru film. Similarly, the figure which shows the relationship between the film-forming time of Cu film | membrane, and the XRF intensity | strength of Cu film | membrane. Similarly, the figure which shows the relationship between the film-forming pressure of Cu film | membrane, and the XRF intensity | strength of Cu film | membrane. Similarly, a cross-sectional view showing a semiconductor device.

Explanation of symbols

  F1 ... Ru chamber, F2 ... Cu chamber, 10 ... Semiconductor device manufacturing apparatus, 50 ... Semiconductor device, 51 ... Copper wiring.

Claims (15)

A method for manufacturing a semiconductor device having copper wiring,
An organic ruthenium complex represented by the general formula (1) (wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms) is formed on the object on which the recess is formed. Forming a ruthenium-containing film by a CVD method using a reducing gas;
On the ruthenium-containing film, an organic copper complex and a second reduction represented by the general formula (2) (wherein R ² represents a linear or branched alkyl group having 1 to 4 carbon atoms). Forming a copper-containing film by a CVD method using a property gas and embedding the copper-containing film in the recess,
A method of manufacturing a semiconductor device. A method of manufacturing a semiconductor device according to claim 1,
The step of forming the ruthenium-containing film includes
The first reducing gas dissociates to release hydrogen radicals or hydrogen ions;
A method of manufacturing a semiconductor device. A method of manufacturing a semiconductor device according to claim 1 or 2,
The step of forming the ruthenium-containing film includes
The first reducing gas is at least one selected from the group consisting of hydrogen (H ₂ ), ammonia (NH ₃ ), a hydrazine derivative, silane (SiH ₄ ), and disilane (Si ₂ H ₆ ). about,
A method of manufacturing a semiconductor device. A method of manufacturing a semiconductor device according to claim 3,
The step of forming the ruthenium-containing film includes
The hydrazine derivative has one or two hydrogen atoms of hydrazine, a methyl group,
Substituted with a group selected from the group consisting of an ethyl group and a linear or branched butyl group;
A method of manufacturing a semiconductor device. It is a manufacturing method of the semiconductor device according to any one of claims 1 to 4,
The step of forming the ruthenium-containing film includes
Setting the atmosphere of the first reducing gas to 10 ³ Pa to 10 ⁴ Pa;
A method of manufacturing a semiconductor device. It is a manufacturing method of the semiconductor device according to any one of claims 1 to 5,
The step of forming the ruthenium-containing film includes
Setting the temperature of the object to 250 ° C. to 400 ° C .;
A method of manufacturing a semiconductor device. A method of manufacturing a semiconductor device according to claim 1,
A method for manufacturing a semiconductor device, wherein the organic ruthenium complex is a bis (2-methoxy-6-methyl-3,5-heptanedionato) -1,5 hexadiene ruthenium complex. A method of manufacturing a semiconductor device according to claim 1,
In the step of forming the ruthenium-containing film, the supply amount of the organic ruthenium complex per unit area of the surface of the object is 2 × 10 ⁻⁸ to 1 × 10 ⁻⁵ mol / min · cm ^2. A method for manufacturing a semiconductor device. A method for manufacturing a semiconductor device according to claim 1,
The method for manufacturing a semiconductor device, wherein the organic copper complex is a bis (2,6-dimethyl-2- (trimethylsilyloxy) -3,5-heptanedionato) copper complex. A method for manufacturing a semiconductor device according to claim 1,
The step of embedding the copper-containing film includes
The method for manufacturing a semiconductor device, wherein the supply amount of the copper complex per unit area of the surface of the object is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol / min · cm ² . It is a manufacturing method of the semiconductor device according to any one of claims 1 to 10,
The step of embedding the copper-containing film includes
Setting the temperature of the object to 150 ° C to 350 ° C,
A method of manufacturing a semiconductor device. It is a manufacturing method of the semiconductor device according to any one of claims 1 to 11,
The step of embedding the copper-containing film includes
The second reducing gas is a gas containing hydrogen atoms;
A method of manufacturing a semiconductor device. A method for manufacturing a semiconductor device according to any one of claims 1 to 12,
The step of embedding the copper-containing film includes
The second reducing gas is hydrogen (H ₂ );
A method of manufacturing a semiconductor device. It is a manufacturing method of the semiconductor device according to any one of claims 1 to 13,
A method for manufacturing a semiconductor device, wherein the ruthenium-containing film is a fine particle film. 15. A method of manufacturing a semiconductor device according to claim 14,
A manufacturing method of a semiconductor device, wherein the fine particle film is formed by setting a leak amount in a film formation space of the ruthenium-containing film to 10 ⁻² (Pa · m ³ / sec) or less.