JP2006299407A - Film-deposition method, film-deposition apparatus and computer readable storage medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-deposition method by which a continued Cu film having satisfactory adhesiveness to a substrate and a prescribed thickness can be film-deposited. <P>SOLUTION: A wafer W is disposed in a chamber 1 and a raw substance of bivalent Cu is supplied onto the wafer W (STEP3), supply of the raw substance is stopped and then a residual gas in the chamber 1 is removed (STEP4), an H<SB>2</SB>gas is supplied to the wafer W while the H<SB>2</SB>gas is made radical by plasma to deposit a Cu film 50a of a first step (STEP5), supply of the H<SB>2</SB>gas is stopped and then a residual gas in the chamber 1 is removed (STEP6), a raw substance of monovalent Cu is supplied together with a H<SB>2</SB>gas to the wafer W and a Cu film of a second step is deposited on the Cu film 50a of the first step to film-deposit the continued Cu film 50b (STEP7). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film forming method for forming copper (Cu) on a semiconductor substrate, a film forming apparatus used for executing this film forming method, and a computer-readable storage medium.

  Recently, Cu having higher conductivity than aluminum and having good electromigration resistance has attracted attention as a wiring material in response to higher speed of semiconductor devices, finer wiring patterns, higher integration, and the like. .

  As a Cu film-forming method, CVD (chemical vapor deposition) is performed by performing a thermal decomposition reaction of a source gas containing Cu or a film by reducing and depositing Cu on a substrate by a reaction between a source gas containing Cu and a reducing gas. ) The law is known. A Cu film formed by such a CVD method has high coverage and is excellent in embedding characteristics by forming a film in a long and narrow pattern, and is suitable for forming a fine wiring pattern. A source gas containing monovalent or divalent Cu is used for CVD of such a Cu film (see, for example, Patent Document 1).

  However, in a CVD process using a source gas containing monovalent Cu, for example, when a Ta film is formed as a barrier film, water is added to form a Cu film on the Ta film. Such treatment is required. When water is used in this way, the surface of the Ta film is oxidized and resistance increases, and it is difficult to achieve high adhesion to the Ta film. Further, not only the Ta film but also a CVD process using a source gas containing monovalent Cu has a problem that it is difficult to form a Cu film on a TaN film or a Ti film.

On the other hand, in the CVD process using a source gas containing divalent Cu, there is almost no dependency on the base such as Ta film, TaN film, Ti film, etc., so that the adhesion to the base substrate is high and the nuclear density is high. However, there is a problem that the Cu film has a large nucleus as it grows and is difficult to be a continuous film.
JP 2000-144420 A

  The present invention has been made in view of such circumstances, and a film forming method capable of forming a continuous Cu film having a predetermined thickness with good adhesion to a substrate, and such a film forming method. An object of the present invention is to provide a film forming apparatus and a computer-readable storage medium for executing the above.

In order to solve the above problems, according to a first aspect of the present invention, a step of forming a first-stage Cu film on a substrate using a divalent Cu source material;
Forming a second stage Cu film on the first stage Cu film using a monovalent Cu source material;
There is provided a film forming method characterized by comprising:

According to a second aspect of the present invention, a step of arranging a substrate in a processing container;
Forming a first stage Cu film on the substrate by CVD using a divalent Cu source material;
Forming a second stage Cu film on the first stage Cu film by CVD using a monovalent Cu source material;
There is provided a film forming method characterized by comprising:

  In the film forming method according to the second aspect, the step of forming the first stage Cu film is preferably performed by a PEALD (Plasma Enhanced Atomic Layer Deposition) method. That is, the process of forming the first-stage Cu film includes (a) a process of supplying and adsorbing a divalent Cu source material on the substrate, and (b) after stopping the supply of the source material, (C) supplying a reducing gas to the substrate, radicalizing the reducing gas by plasma, and reducing the divalent Cu source material adsorbed on the substrate. , A step of forming a Cu film on the substrate, and (d) a step of removing residual gas in the processing container after the supply of the reducing gas is stopped. The steps (a) to (d) are more preferably repeated a predetermined number of times until a Cu film having a desired thickness is formed. The step of forming the second stage Cu film is preferably performed by supplying a monovalent Cu source material to the substrate together with a reducing gas.

As the monovalent Cu source material, Cu (hfac) atoms or Cu (hfac) TMVS is suitable, and as the divalent Cu source material, Cu (divm) ₂ , Cu (hfac) ₂ , Cu ( edmdd) ₂ is preferred.

Such a Cu film forming method is suitable for a film forming process on a barrier film made of Ta, TaN, Ti, TiN, W, or WN formed on a substrate. Furthermore, Ru, Mg, In, Al, Ag, Co, Nb, B, V, Ir, Pd, Mn, Mn oxide (MnO, Mn ₃ O ₄ , Mn ₂ O ₃ , MnO ₂ , When the adhesion layer made of any of Mn ₂ O ₇ ) is formed, a Cu film having further excellent adhesion can be formed.

According to a third aspect of the present invention, a film forming apparatus for performing the film forming method, that is, a processing container accommodating a substrate and capable of being evacuated,
A first Cu raw material supply mechanism for supplying a monovalent Cu raw material in gaseous form to the processing vessel;
A second Cu raw material supply mechanism for supplying a divalent Cu raw material in gaseous form to the processing vessel;
A first-stage Cu film is formed on the substrate accommodated in the processing vessel using a divalent Cu source material, and then the first-stage Cu film is formed using a monovalent Cu source material. A controller for controlling the first and second Cu raw material supply mechanisms so as to form a second-stage Cu film thereon;
A film forming apparatus is provided.

  According to a fourth aspect of the present invention, there is provided a computer-readable storage medium storing a control program that operates on a computer, wherein the control program forms a Cu film on a substrate by a CVD method. Using a divalent Cu source material, a first-stage Cu film is deposited on a computer that controls the deposition apparatus, and then using a monovalent Cu source material on the first-stage Cu film. A computer-readable storage medium is provided that performs a process of forming a second stage Cu film.

  According to the present invention, the first-stage Cu film is formed on the substrate (underlying) using the divalent Cu source material, so that the denseness with high adhesion to the substrate and high nuclear density is achieved. Cu film can be formed. Further, since the second stage Cu film is formed on the Cu film using a monovalent Cu source material, the Cu film can be grown as a continuous film. As described above, the present invention has an excellent effect that the adhesion to the substrate is high and a continuous smooth Cu film can be formed. In addition, although the divalent Cu source material is stable, in the film formation using this, the substrate temperature can be lowered by using the PEALD method, and the film formation using the monovalent Cu source material. Can be performed at a low substrate temperature. Thus, the Cu film can be formed without damaging the wiring elements formed on the substrate.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a cross-sectional view showing a schematic configuration of a film forming apparatus 100 for carrying out a film forming method according to an embodiment of the present invention. The film forming apparatus 100 includes a substantially cylindrical chamber 1 that is hermetically configured, and a susceptor 2 for horizontally supporting a wafer W that is an object to be processed is a cylindrical support member. 3 is supported in a state supported by 3. A guide ring 4 for guiding the wafer W is provided on the outer edge of the susceptor 2. Further, a heater 5 is embedded in the susceptor 2, and the heater 5 is connected to a heater power source 6 and heats the wafer W to a predetermined temperature. The susceptor 2 is provided with a grounded lower electrode 2a.

  A shower head 10 is provided on the top wall 1 a of the chamber 1 via an insulating member 9. The shower head 10 includes an upper block body 10a, a middle block body 10b, and a lower block body 10c. Discharge holes 17 and 18 for discharging gas are alternately formed in the lower block body 10c, and a first gas inlet port 11 and a second gas inlet port 12 are formed on the upper surface of the upper block body 10a. Has been. In the upper block body 10a, a large number of gas passages 13 are branched from the first gas introduction port 11. A gas passage 15 is formed in the middle block body 10b. The gas passage 13 communicates with the gas passage 15, and the gas passage 15 communicates with the discharge hole 17 of the lower block body 10c.

  In the upper block body 10a, a large number of gas passages 14 are branched from the second gas introduction port 12. Gas passages 16 are formed in the middle block body 10 b, and the gas passage 14 communicates with these gas passages 16. Further, the gas passage 16 communicates with the discharge hole 18 of the lower block body 10c. The first and second gas inlets 11 and 12 are connected to a gas line of the gas supply mechanism 20.

The gas supply mechanism 20 includes, for example, a first Cu source supply source 21a that supplies a monovalent Cu source material such as Cu (hfac) atoms or Cu (hfac) TMVS, Cu (divm) ₂ , Cu (hfac) ₂ , a second Cu source supply source 21b for supplying a source material of divalent Cu such as Cu (edmdd) ₂ , an Ar gas supply source 23 for supplying Ar gas which is an inert gas as a carrier gas, H ₂ gas as the reducing gas and a H ₂ gas supply source 24 for supplying.

As the carrier gas, an inert gas such as N ₂ gas, He gas, or Ne gas may be used instead of Ar gas. Further, as the reducing gas, any one of NH ₃ gas, N ₂ H ₄ gas, NH (CH ₃ ) ₂ gas, N ₂ H ₃ CH gas, and N ₂ gas may be used instead of H _2. Alternatively, a mixed gas of a plurality of gases selected from these may be used.

A first source gas line 25a is provided for the first Cu source supply source 21a, a second source gas line 25b is provided for the second Cu source supply source 21b, and a second source gas line 25b is provided for the Ar gas source 23. A gas line 27 to be joined and a gas line 28 are connected to the H ₂ gas supply source 24, respectively. The first source gas line 25a and the second source gas line 25b each have a mass flow controller 30 and a valve 29 provided downstream thereof, and the gas lines 27 and 28 sandwich the mass flow controller 30 and the mass flow controller 30 therebetween. Two valves 29 are provided.

The first and second Cu raw material supply sources 21a and 21b and the first and second raw material gas lines 25a and 25b connected thereto are heated by the heater 22 to a predetermined temperature, for example, 50 ° C. to 200 ° C. It has become so. When the Cu raw material is solid at normal temperature and normal pressure (Cu (hfac) ₂ , Cu (divm) ₂ ), the heater 22 uses the first and second Cu raw material supply sources 21 a and 21 b and the first and second Cu raw materials. The second raw material gas lines 25a and 25b are heated, and the pressure inside the chamber 1 is depressurized as will be described later, thereby sublimating the Cu raw material and supplying the Cu raw material to the chamber 1 in a gas state. On the other hand, when the Cu raw material is liquid at normal temperature and normal pressure (Cu (hfac) atoms, Cu (hfac) TMVS, Cu (edmdd) ₂ ), the heater 22 supplies the first and second Cu raw materials. By heating the sources 21a, 21b and the first and second source gas lines 25a, 25b, the Cu source material can be evaporated and supplied to the chamber 1 in a gas state.

First and second source gas lines 25a and 25b extending from the first and second Cu source supply sources 21a and 21b are connected to the first gas introduction port 11 via insulators 31a and 31b, respectively. . A gas line 28 extending from the H ₂ gas supply source 24 is connected to the second gas inlet 12 via an insulator 31c.

  At the time of wafer processing (film formation processing), the divalent Cu source material gas from the second Cu source supply source 21b is supplied to the Ar gas supplied from the Ar gas supply source 23 through the gas line 27. The carrier is carried to reach the shower head 10 from the first gas inlet 11 of the shower head 10 through the second source gas line 25b, and is discharged from the discharge hole 17 into the chamber 1 through the gas passages 13 and 15. . In addition, in FIG. 1, although it has the structure which supplies Ar gas which is carrier gas through the gas line 27 to the 2nd raw material gas line 25b, a carrier gas line is connected to the 2nd Cu raw material supply source 21b, Ar gas may be supplied.

  Further, the monovalent Cu source material gas is sent from the first Cu source supply source 21a to the shower head 10 through the first source gas line 25a and the first gas introduction port 11, and the gas passages 13, 15 are supplied. Then, the ink is discharged from the discharge hole 17 into the chamber 1. The monovalent Cu source material gas may be supplied to the chamber 1 by being carried by the Ar gas supplied from the Ar gas supply source 23 through the gas line 27.

Further, the H ₂ gas reaches the second gas inlet 12 of the shower head 10 from the H ₂ gas supply source 24 through the gas line 28, and then passes through the gas passages 14 and 16 formed in the shower head 10. It is discharged from the discharge hole 18 into the chamber 1.

A high frequency power source 33 is connected to the shower head 10 via a matching unit 32, and the high frequency power is supplied from the high frequency power source 33 between the shower head 10 and the lower electrode 2a. The H ₂ gas as the reducing gas supplied into the chamber 1 is converted into plasma.

  An exhaust pipe 37 is connected to the bottom wall 1 b of the chamber 1, and an exhaust device 38 is connected to the exhaust pipe 37. By operating the exhaust device 38, the inside of the chamber 1 can be depressurized to a predetermined degree of vacuum. Further, a gate valve 39 is provided on the side wall of the chamber 1, and the wafer W is carried into and out of the outside with the gate valve 39 opened.

  Each component of the film forming apparatus 100 is connected to and controlled by a control unit (process controller) 95. In addition, the control unit 95 includes a user interface that includes a keyboard on which a process manager inputs commands to manage the film forming apparatus 100, a display that visualizes and displays the operating status of the film forming apparatus 100, and the like. 96 is connected.

  Further, the control unit 95 executes a process on each component of the film forming apparatus 100 in accordance with a control program for realizing various processes executed by the film forming apparatus 100 under the control of the control unit 95 and processing conditions. A storage unit 97 in which a program (that is, a recipe) is stored is connected. The recipe may be stored in a hard disk, a semiconductor memory, or the like, or set at a predetermined position in the storage unit 97 while being stored in a portable storage medium readable by a computer such as a CD-ROM or DVD-ROM. You may come to do.

  Then, if desired, an arbitrary recipe is called from the storage unit 97 by an instruction from the user interface 96 and is executed by the control unit 95, so that a desired value in the film forming apparatus 100 is controlled under the control of the control unit 95. Is performed.

  Next, a process for forming a Cu film on the wafer W by the film forming apparatus 100 configured as described above will be described. FIG. 2 is a flowchart showing a Cu film forming process, and FIG. 3 is a diagram schematically showing a Cu film forming process.

  First, the gate valve 39 is opened, and the wafer W is loaded into the chamber 1 and placed on the susceptor 2 (STEP 1). Then, the inside of the chamber 1 is evacuated by the exhaust device 38 to maintain the inside of the chamber 1 at a predetermined pressure of 13.33 Pa (0.1 torr) to 1333 Pa (10 torr). The pressure in the chamber 1 is maintained in this range until the step 8 described later is completed. In addition, the wafer 5 is heated and held by the heater 5 at a temperature at which the divalent Cu source material supplied later into the chamber 1 is not decomposed, for example, a predetermined temperature of 50 to 400 ° C., preferably 50 to 200 ° C. (STEP 2).

Next, a first-stage Cu film is formed using a divalent Cu source material. That is, in the second Cu source supply source 21b, a divalent Cu source material such as Cu (hfac) ₂ is gasified, for example, Cu source gas flow rate; 10 to 1000 mg / min, Ar flow rate; 50 to Wafer introduced into chamber 1 under the conditions of 2000 mL / min (flow rate converted to standard state (sccm)) and supply time: 0.1 seconds to 10 seconds, and the divalent Cu source material is heated to a predetermined temperature Adsorbed on the entire surface of W (STEP 3). Next, the supply of the divalent Cu source gas is stopped, and the excess divalent Cu source gas is exhausted and removed from the chamber 1 (STEP 4). At this time, Ar gas may be supplied into the chamber 1 at, for example, an Ar flow rate; 50 to 5000 mL / min (sccm), and the remaining gas may be exhausted and removed while purging the chamber 1. As the purge gas, H ₂ gas supplied into the chamber 1 next may be used.

Thereafter, the _{H 2} gas into the chamber 1 as a reducing gas from the _{H 2} gas supply source 24, for example, flow rate; introduced at 50~5000mL / min (sccm), a high frequency power from the high frequency power source 33 to the case, for example , is applied between the shower head 10 and the lower electrode 2a is 50 to 1000 W, to generate hydrogen radicals _(H ^{2 *)} into plasma of _{H 2} gas, the surface of the wafer W by the hydrogen radicals _(H ^{2 *)} The divalent Cu raw material adsorbed on is reduced to form a first-stage Cu film on the wafer W (STEP 5). The step 5 is performed, for example, for 0.1 seconds to 10 seconds.

Thereafter, the supply of H ₂ gas and the application of high frequency power are stopped, and the H ₂ gas is exhausted and removed from the chamber 1 (STEP 6). In this STEP 6, similarly to the previous STEP 4, Ar gas may be supplied into the chamber 1 and purged while the residual gas is exhausted.

  Such processing of STEPs 3 to 6 is repeated until the Cu thin film formed on the wafer W reaches a target film thickness, for example, 1 nm to 100 nm. Thus, a dense Cu film 50a (first-stage Cu film) having high adhesion to the wafer W and high nucleus density as shown in FIG. 3A can be formed.

For example, conventionally, when a barrier film made of Ta, TaN, Ti, TiN, W, or WN is formed on the surface of the wafer W, it is necessary to take measures such as adding water. Although the film was oxidized and the adhesion was lowered and the resistance was increased, according to the above STEP 3 to 6, since such an additive is not required, the barrier film is damaged. A first-stage Cu film having good adhesion can be formed without giving. Ru, Mg, In, Al, Ag, Co, Nb, B, V, Ir, Pd, Mn, Mn oxide (MnO, Mn ₃ O ₄ , Mn ₂ O ₃ , MnO ₂ , Mn ₂ are formed on the surface of the barrier film. In the case where an adhesion layer made of any of O ₇ ) is formed, a first-stage Cu film with higher adhesion can be formed.

Next, after the end of STEP 6, a second-stage Cu film is formed by a monovalent Cu source material by, for example, a thermal CVD method. That is, the holding temperature of the wafer W is adjusted as necessary, and then a monovalent Cu source material such as Cu (hfac) TMVS is gasified in the first Cu source supply source 21a, for example, Cu source was supplied to the chamber 1 at 10 to 1000 mg / min, which the _{H 2} gas as the reducing gas from the _{H 2} gas supply source 24 into the chamber 1 at the same time, for example, flow rate; gas flow rate 50~1000mL / min (sccm ) Until the second-stage Cu film has a desired thickness, for example, 1 nm to 1000 nm (STEP 7). As a result, a second-stage Cu film grows on the first-stage Cu film 50a previously formed by a reduction reaction using the monovalent Cu source gas and H ₂ gas.

  According to this STEP7 process, the second-stage Cu film is formed on the previously formed first-stage Cu film, so the second-stage Cu film portion newly formed by the STEP7 process is The adhesion with the first-stage Cu film 50a obtained after completion of the step 6 is extremely high. In this manner, as shown in FIG. 3B, a Cu film 50b having substantially continuity (integration) can be formed. Further, it is difficult to form a flat film by repeating the steps 3 to 6 because the nucleus of the first stage Cu film 50a grows. However, the second stage Cu film is formed by the process of STEP7. By forming, a flat Cu film 50b can be formed.

  Note that the processing temperature of the wafer W in STEP 7 is preferably set in the range of 50 ° C. to 400 ° C., preferably in the range of 50 to 200 ° C. Even if it is different from the processing temperature of the wafer W in STEP 3 to 6. However, if it is the same as the processing temperature of the wafer W in STEP 3 to 6, the time for adjusting the temperature of the wafer W is not required, so that the throughput can be improved.

  After the step 7 is finished, the residual gas in the chamber 1 is exhausted and removed (STEP 8). In the process of STEP 8, Ar gas may be supplied into the chamber 1 at, for example, an Ar flow rate; 50 to 5000 mL / min (sccm), and the remaining gas may be exhausted and removed while purging the chamber 1. When the residual gas is removed from the chamber 1 in this way, the gate valve 39 is opened, the wafer W is carried out of the chamber 1 and the gate valve 39 is closed (STEP 9). At this time, it is also preferable to carry the wafer W to be processed next into the chamber 1.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to such a form. For example, in the first stage formation of a Cu film using a divalent Cu source material (STEPs 3 to 6), a reducing gas is turned into plasma with high-frequency energy and the reduction reaction of the source material proceeds to form a Cu composition. Although the film forming method has been exemplified, depending on the reducing property of the reducing gas, the high frequency is not applied, and the thermal energy when the wafer W is heated to a predetermined temperature by the heater 5 provided in the susceptor 2 or the like. Film formation can also be performed by advancing the reduction reaction of the source material. Also, due to the nature of the divalent Cu raw material, when film formation is possible by the method of supplying the divalent Cu raw material together with the reducing gas to the substrate without using the PEALD method described above, the film quality, throughput, A film forming method determined to be appropriate may be used in consideration of processing costs and the like.

  A vaporizer may be used in the case of using a solid material at normal temperature and pressure as the Cu raw material. In other words, solid Cu raw material is dissolved in a predetermined solvent and stored in a tank or the like, and a pressurized gas such as He gas is introduced into the tank so that the liquid raw material in the tank is provided outside the tank at a constant flow rate through the pipe. In this vaporizer, the liquid material thus pumped is sprayed and vaporized by a carrier gas such as an inert gas supplied from another line, and is supplied to the chamber together with this carrier gas. Also good. The gas line from the vaporizer to the chamber is preferably maintained at a predetermined temperature by a heater or the like in order to prevent solidification of the vaporized Cu raw material.

1 is a cross-sectional view showing a schematic configuration of a film forming apparatus for carrying out a film forming method according to the present invention. The flowchart which shows the film-forming process of Cu film | membrane. The figure which shows typically the film-forming process of Cu film | membrane.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Chamber 2; Susceptor 2a; Lower electrode 3; Support member 5; Heater 10; Shower head 20; Gas supply mechanism 21a; First Cu raw material supply source 21b; Gas source 24; H ₂ gas source 25a; first source gas line 25b; second source gas line 95; controller W; wafer

Claims (18)

Forming a first stage Cu film on the substrate using a divalent Cu source material;
Forming a second stage Cu film on the first stage Cu film using a monovalent Cu source material;
A film forming method comprising: Placing a substrate in a processing vessel;
Forming a first stage Cu film on the substrate by CVD using a divalent Cu source material;
Forming a second stage Cu film on the first stage Cu film by CVD using a monovalent Cu source material;
A film forming method comprising:   The step of forming the first-stage Cu film includes (a) a step of supplying and adsorbing a divalent Cu source material on the substrate, and (b) after stopping the supply of the source material, (C) supplying a reducing gas to the substrate, radicalizing the reducing gas with plasma, and adsorbing the divalent Cu source material adsorbed on the substrate. The process according to claim 2, further comprising: a step of reducing and forming a Cu film; and (d) a step of removing residual gas in the processing container after the supply of the reducing gas is stopped. Membrane method.   4. The film formation according to claim 2, wherein the step of forming the second stage Cu film is performed by supplying a monovalent Cu source material together with a reducing gas to the substrate. Method. The reducing gas is any one of H ₂ , NH ₃ , N ₂ H ₄ , NH (CH ₃ ) ₂ , N ₂ H ₃ CH, N ₂ , or a mixed gas selected from these gases. The film forming method according to claim 3, wherein the film forming method is provided.   3. The substrate temperature in the step of forming the first-stage Cu film is substantially the same as the substrate temperature in the step of forming the second-stage Cu film. The film forming method according to claim 5.   The film forming method according to claim 1, wherein a thickness of the first stage Cu film is 1 nm or more and 100 nm or less.   The film forming method according to claim 1, wherein the monovalent Cu source material is Cu (hfac) atoms or Cu (hfac) TMVS. The source material of the divalent Cu is any one of Cu (divm) ₂ , Cu (hfac) ₂ , and Cu (edmddd) ₂ , according to any one of claims 1 to 8. The film-forming method of description.   The substrate is provided with a barrier film made of any one of Ta, TaN, Ti, TiN, W, and WN, and the first-stage Cu film is formed on the barrier film. Item 10. The film forming method according to any one of Items 9 to 9. The barrier film has Ru, Mg, In, Al, Ag, Co, Nb, B, V, Ir, Pd, Mn, and Mn oxide (MnO, Mn ₃ O ₄ , Mn ₂ O ₃ , MnO ₂ , The film forming method according to claim 10, further comprising: an adhesion layer made of any of Mn ₂ O ₇ ), and forming the first-stage Cu film on the adhesion layer. A processing container accommodating a substrate and capable of being evacuated;
A first Cu raw material supply mechanism for supplying a monovalent Cu raw material in gaseous form to the processing vessel;
A second Cu raw material supply mechanism for supplying a divalent Cu raw material in gaseous form to the processing vessel;
A first-stage Cu film is formed on the substrate accommodated in the processing vessel using a divalent Cu source material, and then the first-stage Cu film is formed using a monovalent Cu source material. A controller for controlling the first and second Cu raw material supply mechanisms so as to form a second-stage Cu film thereon;
A film forming apparatus comprising: A gas supply mechanism for supplying a reducing gas to the processing container;
A plasma generation mechanism for converting the reducing gas supplied into the processing vessel into plasma,
The control unit supplies a predetermined amount of the divalent Cu source material onto the substrate and adsorbs it, then exhausts the inside of the processing vessel and supplies the reducing gas to the substrate while supplying the reducing gas to plasma. The divalent Cu source material adsorbed on the substrate is reduced by radicalization by forming a Cu film, and after the supply of the reducing gas is stopped, the process container is evacuated a predetermined number of times. The film forming apparatus according to claim 12, wherein the gas supply mechanism and the plasma generation mechanism are further controlled so that the first-stage Cu film is formed by. A gas supply mechanism for supplying a reducing gas to the processing container;
The control unit supplies the monovalent Cu source material to the substrate accommodated in the processing vessel together with the reducing gas so that the second stage Cu film is formed. The film forming apparatus according to claim 12, further controlling the supply mechanism. A substrate heating mechanism for heating the substrate contained in the processing container to a predetermined temperature;
The control unit further controls the substrate heating mechanism so that the first-stage and second-stage Cu films are formed in a state where the substrate is heated to a predetermined temperature. The film-forming apparatus of any one of Claims 12-14. A computer-readable storage medium storing a control program that runs on a computer,
The control program forms a first-stage Cu film using a divalent Cu source material on a computer that controls a film forming apparatus that forms a Cu film on a substrate by a CVD method, and then What is claimed is: 1. A computer-readable storage medium, characterized in that a second stage Cu film is formed on a first stage Cu film using a monovalent Cu source material.   In the process of forming the first-stage Cu film on the computer, the control program (a) supplies and adsorbs a divalent Cu source material in a gaseous state on a substrate housed in a processing vessel. (B) after the supply of the raw material is stopped, the residual gas in the processing vessel is removed, and (c) a predetermined reducing gas is supplied to the substrate, and at that time, the reducing gas is radicalized by plasma. The divalent Cu source material adsorbed on the substrate is reduced to form a Cu film, and (d) a series of processes for removing residual gas in the processing container after the supply of the reducing gas is stopped. The computer-readable storage medium according to claim 16, wherein the film forming apparatus is controlled such that the predetermined number of times is performed a predetermined number of times.   In the process of forming the second-stage Cu film, the control program is configured to supply a monovalent Cu source material together with a predetermined reducing gas to a substrate accommodated in the processing container. The computer-readable storage medium according to claim 16 or 17, wherein the film forming apparatus is controlled.

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