TW200810019A - Film forming apparatus, film forming method, computer program and storage medium - Google Patents

Abstract

In a film forming method, a subject to be processed is transferred into a processing chamber which can be vacuumized. At least a transition metal containing material gas including a transition metal and a reducing gas are supplied into a processing container, and the subject to be processed is heated. Then, a thin film is formed in a recessed portion on the surface of the subject by heat treatment. Thus, the recessed portion on the surface of the subject can be filled with a copper film.

Description

200810019 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to, for example, a copper-manganese (CuMi!) alloy film or a manganese (Mn) film as a seed film formed on a semiconductor wafer or the like. A film forming apparatus and a film forming method for treating the surface of the body. [Prior Art] In general, a semiconductor device is manufactured by repeatedly performing various processes such as a film formation process or a pattern etching process on a semiconductor wafer, and manufacturing a desired device. However, it is required to have a higher integration and high fineness of the semiconductor device. The line width or the aperture is more and more refined. Then, the wiring material or the buried material embedded in the concave portion of the channel, the hole, or the like is required to have a smaller electric resistance due to the refinement of various sizes, and therefore copper tends to be small and inexpensive. (Japanese Patent Document 1). Then, 'using copper as the wiring material or embedding material _. In the case of considering the barrier property of copper diffusion to the lower layer, etc., it is generally adopted by Taejin (Ta) or molybdenum nitride (TaN). As a barrier layer. Then, the step of embedding in the recess is to form a thin seed film made of a copper film in the plasma plating apparatus, and the surface of the wafer including the surface of the recess is comprehensive, and then The surface of the wafer is completely coated with copper and completely buried in the recess. Thereafter, honing is performed by a CMP (Chemical Mechanical Polishing) treatment or the like to remove excess copper film on the surface of the wafer. This point will be explained with reference to Fig. 7. Fig. 7 is a view showing a step of generally embedding a concave portion of a semiconductor wafer. On the surface of the insulating layer formed of, for example, an interlayer insulating film or the like of the semiconductor crystal -4-200810019 (2), a via hole or a through hole or a trench (channel or dual) is formed. In the recessed portion 2 corresponding to the Damascene structure, a wiring layer 3 of, for example, a layer composed of copper is formed in an exposed state at the bottom of the recess 2. The recess 2 is miniaturized according to design rules, and the width or inner diameter is extremely small, for example, about 120 nm, and the volume ratio is, for example, about 2 to 4. Further, the diffusion-preventing film, the resist film, and the like are not shown in the drawings, and the shapes are simplistic and described. In the plasma sputtering apparatus, the inner surface of the recessed portion 2 is also formed on the surface of the semiconductor wafer W in advance, and the barrier layer 4 composed of, for example, a laminated structure of a TaN film and a Ta film is formed substantially uniformly ( Refer to Figure 7(A)). Then, a seed film 6 composed of a thin copper film is formed as a metal film by a plasma sputtering apparatus across the entire surface of the wafer including the surface in the concave portion 2 (refer to Fig. 7(B)). When the seed film 6 is formed in the plasma sputtering apparatus, high-frequency bias power is applied to the semiconductor wafer side, and the introduction of copper metal ions is efficiently performed. Further, a copper plating treatment is applied to the surface of the wafer, and the metal film 8 made of, for example, a copper film is embedded in the concave portion 2 (refer to Fig. 7(C)). Thereafter, the ruthenium treatment is performed by the above-described CMP treatment or the like to remove the excess metal film 8, the seed crystal film 6, and the barrier layer 4 on the wafer surface. However, recently, in order to improve the higher reliability of the above-mentioned barrier layer, various bursts have been carried out, in which the self-forming barrier layer of the above-mentioned Ta film or TaN film is replaced by a Μη film or a CuMn alloy film (Japanese Patent) Literature 2). The Μ 膜 film or the CuMn alloy film is formed by a sputtering process, and the Μ 膜 film or the C ii Mn alloy film itself becomes a seed film, so that a copper plating layer can be formed directly thereon. Further, after the film formation is subjected to the annealing treatment, the SiO 2 layer of the insulating film belonging to the lower layer is self-integrated, and MnSixOy (x, is formed at the interface portion between the Si 2 layer and the Mil film or the CuMn alloy film. y: an arbitrary integer) The barrier film of the film has an advantage that the number of processes can be reduced. Further, there is an advantage that the Μn in the Μn film or the CuMn alloy film is preferentially bonded to the halogen element entering the Cu φ film when the Cu film is formed by the CVD method, for example, and is trapped from the Cu film. By collecting the halogen element, the film quality of the Cu film wiring can be improved to improve the reliability of the wiring. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-1 07747. Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. 2005-2773 No. 90, the current practical level, the CuMn alloy film can be formed only by sputtering, but Very fine patterns predicted in the future, such as | line width or channel or hole with a hole diameter of 32 nm or less, the sputtering method is not sufficient, corresponding, the result of step coverage degradation will be high # The concave portion of the degree is buried insufficiently. In addition, as described above, the formation step of the seed film 6, the plating treatment step, and the annealing step must use the respective devices corresponding to the respective steps - 'for example, a sputtering device, a plating treatment, and an annealing device, which may have to be increased. Device cost (equipment cost) issues. Further, there is a problem in that the formation step and the embedding step of the seed crystal film 6 cannot be performed in the in-situ, that is, after the seed film 6 is formed, when the semiconductor wafer is transported to the embedding device, the semiconductor Since the wafer is transported in the atmosphere formed by clean air, the highly reactive CuMn -6-200810019 (4) gold film is oxidized, which results in the embedding of copper into the film, or the seed film. The Μ 氧化物 oxide formed by the oxidation of the Μη component increases the contact resistance. In addition, there are the following problems: In the film formation by sputtering, a seed film thicker than the side wall is formed at the bottom of the concave portion, so that the sidewall of the concave portion is formed very thinly even after the annealing treatment. In the MnSixOy film, the bottom portion still has a large amount of residual manganese, which is larger than copper or the oxide, and the contact resistance is increased. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. It is an object of the present invention to provide, for example, a CuMn alloy film or a Μη film by heat treatment such as CVD, and to bury a stepped ο ν erage even with a fine recess. In addition, it is a film forming method, a film forming apparatus, a computer program, and a memory medium which can continuously reduce the cost of the apparatus by continuously processing the same processing apparatus. φ A film forming method according to the present invention, comprising the steps of: transporting a target object into a vacuum-processable processing container; and supplying at least a transition metal-containing transition metal-containing material gas to the processing container And a raw gas, and the object to be processed is heated, and a film is formed on the surface of the object to be processed via heat treatment. In this way, in the vacuum-processable processing container, the transition metal-containing transition metal-containing gas and the reducing gas are used to form the film on the surface of the object to be processed by heat treatment, so that even a fine recess can be made high. The step coverage is used for embedding, and 200810019 (5) is continuously processed by the same processing device, which can greatly reduce the cost of the device. According to the film forming method of the present invention, the copper-containing raw material gas containing copper and the transition metal-containing transition metal-containing gas and the reducing gas are supplied to the processing container, and the object to be processed is heated. The step of heat treatment to form a film on the surface of the object to be treated. In the vacuum-processable processing container, the film containing the copper-containing φ copper source gas and the transition metal-containing transition metal source gas and the reducing gas is formed on the surface of the object to be processed by heat treatment. Therefore, even in the case of fine recesses, it is possible to perform embedding with a high step coverage: (step coverage), and continuous processing by the same processing device, which can greatly reduce the device cost. In the film forming method according to the above aspect of the invention, the heat treatment is performed by a CVD (Chemical Vapor Deposition) method. In the film forming method according to the above aspect of the invention, the heat treatment is performed by an ALD (Atomic Layer Deposition) method in which the raw material gas and the reducing gas are alternately supplied to form a film. In the film forming method according to the above aspect of the invention, the heat treatment is carried out by alternately supplying the two kinds of source gases alternately during the intermittent period and supplying the reducing gas during the intermittent period. In the above-described film forming method of the present invention, the copper film is deposited on the object to be processed on which the film is formed by the CVD method, and the recessed portion of the object to be processed is subjected to the embedding treatment. In the film forming method according to the above aspect of the invention, the embedding treatment -8-200810019 (6)' is carried out in a processing container in which the film is formed. According to this film formation method, in the same apparatus, that is, the in-situ process is continuously performed, the formation of an unnecessary metal oxide film is suppressed, and as a result, the embedding property can be improved, and the contact resistance can be prevented from becoming large. In the film forming method according to the above aspect of the invention, after the embedding treatment, the object to be processed is subjected to an annealing treatment. In the film forming method according to the above aspect of the invention, the annealing treatment φ is carried out in a processing container in which the film is formed. In the above-described film forming method of the present invention, the copper film is deposited on the object to be processed on which the film is formed by the plating method, and the embossing process of the concave portion of the object to be processed is performed. In the film forming method according to the above aspect of the invention, after the embedding process of the concave portion of the object to be treated is performed, the object to be processed is subjected to annealing treatment. According to the film forming method of the present invention, in order to change the composition ratio of copper to transition metal in the film thickness in the film thickness direction of the film, the copper material is contained in the middle of the heat treatment. The gas-and/or the aforementioned change in the supply amount of the transition metal-containing raw material gas is carried out. According to the film forming method of the present invention, the composition ratio of the transition metal in the film is such that the lower layer side in the film is large, and the smaller the upper layer side is, the more the supply of the raw material gases is controlled. the amount. In the film forming method according to the above aspect of the invention, the amount of the transition metal contained in the film is 0.7 to 200810019 (7) in terms of a film thickness of the pure metal of the transition metal, and is 0.7 to 2.6 nm. Within the scope. In the film forming method according to the above aspect of the invention, the surface of the processing body is a base film of the film, and the base film is made of a SiO 2 film, a SiOC film, a SiCOH film, a film, and a porous cerium oxide. A membrane and a porous methylsilsesquioxane (MSQ) membrane and a polypropyne membrane and a group of SiLK (trade name) membranes and fluorocarbon membranes are composed of one or more membranes selected. φ The film forming method according to the above aspect of the invention, wherein the transition metal-containing material containing the transition metal source gas is composed of an organic metal material or a metal-based material. In the film forming method according to the above aspect of the invention, the organometallic material is M(R-Cp)x (x is a natural number), wherein Μ represents a transition metal, R represents an alkyl group, and H, CH3, One selected from the group of C2H5, C3H7, and C4H9, and Cp is cyclopentandienyl (C 5 Η 4 ). The film forming method according to the above aspect of the invention, wherein the organometallic material is M(R-Cp)x(CO) (x, y is a natural number), wherein Μ is a transition metal, and R is a representation An alkyl group selected from the group consisting of ruthenium, CH3, C2H5, C3H7, and C4H9-, Cp is cyclopentene diene (C5H4), and CO is a carbonyl group. The film forming method according to the above aspect of the invention, wherein the organometallic material is composed of a transition metal, C and ruthenium. In the film forming method according to the above aspect of the invention, the transition metal is from Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh, Tc, Α1 -10- 200810019 (8), Mg, One or more metals selected from the group consisting of Sn, Ge, Ti, and Re. In the film forming method of the present invention, the transition metal is composed of manganese (Mn), and the organic metal material containing the manganese is Cp2Mn[= Mn(C5H5)2], (MeCp)2Mn[= Mn(CH3C5H4)2], (EtCp)2Mn[ = Mn(C2H5C5H4)2], (i-PirCp)2Mn[ = Mn(C3H7C5H4)2] • MeCpMn(CO)3[ = (CH3C5H4)Mn(CO) 3], φ (t-BuCp) 2Mn[ = Mn(C4H9C5H4)2], CH3Mn(CO)5,

Mn(DPM)3[ = Mn(C, iHi9〇2)3] '

Mn(DMPD(EtCp)[ = Mn(C7H1iC2H5C5H4))'

Mn(acac)2[ = Mn(C5H7〇2)2] ' Mn(DPM)2 [ = Mn(C ι ι Η ι 9〇2>2] ' Mn(acac)3[ = Mn(C5H702)3 ] And one or more materials selected from the group consisting of Mn(hfac)2[=Mii(C5HF602)3]. The film forming method according to the above aspect of the invention, wherein the heat treatment is a plasma for use. The film forming method as described above, wherein the raw material gas and the reducing gas are mixed in the processing container. The film forming method according to the above aspect, wherein the reducing gas is H2 gas. A film forming apparatus is a film forming apparatus that forms a transition metal-containing film on a surface of a workpiece by heat treatment, and is characterized in that: a vacuum-processable processing container is provided, and a processing container is provided in the processing container a mounting table structure on which the object to be processed is placed, a heating means for heating the object to be processed, a gas introduction means for introducing a gas into the processing container, and a raw material gas to be supplied to the processing container - 111001 (9) a raw material gas supply means of the gas introduction means, and The reducing gas supply means for supplying the reducing gas to the gas introducing means. The film forming apparatus according to the present invention, wherein the material gas is present in a plurality of types, the raw material gas supply means has a function for each of the material gases. The diverging path of the different material gases, the diverging path of the material gas will meet in the middle. The film forming apparatus of the present invention as described above, wherein the raw material gas is present in a plurality of kinds of the above-mentioned raw material gas supply means for each raw material The divergence path of the different material gases provided in the gas, the diverging paths of the material gases are not merged in the middle, and are respectively connected to the gas introduction means. The film forming apparatus of the present invention as described above, in order to prevent the flow The material gas to the material gas flow path is liquefied, and a flow path heating means for heating is provided in the branch path of the material gas. The film forming apparatus according to the present invention, wherein the material gas ® contains at least: The transition metal contains a transition metal source gas. The present invention is as described above In the film forming apparatus, the raw material gas contains: a copper-containing raw material gas containing copper, and a transition metal-containing and transition metal source gas. The film forming apparatus according to the present invention, wherein the reducing gas is H2 gas A computer program for use in a film forming apparatus for performing a film forming method in a computer, characterized in that the film forming method includes: transporting the object to be processed into a vacuumable processing container The step and the -12-200810019 (10) processing container are provided with at least a transition metal-containing transition metal source gas and a reducing gas, and the object to be treated is heated, and the film is formed in the object to be processed through heat treatment. The steps of the surface. A computer program of the present invention is a computer for performing a film forming method, and the film forming apparatus used in the film forming method has: a vacuum-processable processing container, and is disposed in the processing container for mounting The structure of the substrate to be processed, the heating means φ for heating the object to be processed, the gas introduction means for introducing the gas into the processing container, and the material gas for supplying the material gas to the gas introduction means a supply means, a reducing gas supply means for supplying a reducing gas to the gas introduction means, and a control means for controlling the entire apparatus; and the film forming apparatus is formed by electrothermal treatment to form a film containing a transition metal in the object to be processed A surface computer program characterized in that the film forming method includes: a step of transporting the object to be processed into a vacuum-processable processing container; and supplying at least a transition metal-containing transition metal-containing gas containing a transition metal to the processing container; Reducing the gas body, and heating the object to be processed, forming a film by heat treatment The step of surface treatment thereof. In the computer program according to the above aspect of the invention, the material gas ^ contains a copper-containing material gas containing copper and a transition metal-containing material gas containing a transition metal. A memory medium readable by a computer for storing a computer program is a memory medium for a film forming apparatus for storing a computer program for performing a film forming method in a computer, wherein: the film forming method is provided There are: a process of transporting the object to be evacuated to a vacuumable treatment-13-200810019 (11) in a container, and at least a transition metal-containing gas containing a transition metal and a reducing gas in the processing container, and will be processed The body is heated, and a film is formed on the surface of the object to be processed via heat treatment. The readable memory medium in the computer storing the computer program is stored in a computer program for performing a film forming method in the computer, and the film forming device used in the film forming method has: vacuuming And a processing device provided in the processing container, a mounting table structure on which the object to be processed is placed, a heating means for heating the object to be processed, and a gas to be introduced into the processing container a gas introduction means, a raw material gas supply means for supplying the raw material gas to the gas introduction means, a reducing gas supply means for supplying the reducing gas to the gas introduction means, and a control means for controlling the entire control means; a memory medium in which a transition metal-containing film is formed on the surface of the object to be processed by heat treatment, and the film forming method includes a step of transporting the object to be processed into a vacuumable processing container, and Providing at least a transition metal-containing gas and a reducing gas containing a transition metal in the processing container, and The object to be processed is heated, and a film is formed on the surface of the object to be processed by heat treatment. A memory medium readable by a computer storing a computer program according to the present invention, wherein the material gas contains a copper-containing raw material gas containing copper and a transition metal-containing raw material gas containing a transition metal. As described above, the film forming method and the film forming apparatus of the present invention can exhibit the following excellent effects. -14 - 200810019 (12) The copper-containing raw material gas containing copper, the transition metal-containing raw material gas containing the transition metal, and the reducing gas are supplied to a vacuum-processable processing chamber, and the film is formed into a processed film by heat treatment. The surface of the body. Therefore, even a fine recess can be buried with a high step coverage, and the same processing device can be continuously processed, which can greatly reduce the device cost. • The transition metal-containing gas and the φ reducing gas containing the transition metal are supplied to a vacuum-processable processing chamber, and the film is formed on the surface of the object to be processed by heat treatment. Therefore, even if it is a fine recess, The step coverage can be performed with a high step coverage, and the processing is continuously performed by the same processing device, which can greatly reduce the device cost. Further, according to the present invention, it is possible to carry out the treatment continuously in the same apparatus, that is, in-situ, so that the formation of an unnecessary metal oxide film is suppressed, and as a result, the embedding property can be improved, and the contact #resistance can be prevented. Increasingly, it is possible to improve the reliability of semiconductor devices and improve the yield. According to the present invention, the composition ratio of copper to transition metal in the film is changed in the film thickness direction of the film, and the supply amount of each material gas is changed in the middle of the heat treatment, so that the substrate can be improved. Adhesion of the film. Further, according to the present invention, since the amount of the transition metal contained in the film is optimized, it is possible to prevent deterioration of the film quality of the copper wiring of the transition metal. -15- 200810019 (13) [Embodiment] Hereinafter, embodiments of the film forming method and film forming apparatus of the present invention will be described in detail based on the drawings. Fig. 1 is a view showing the configuration of an example of a film forming apparatus of the present invention. As shown in the figure, the film forming apparatus 1 2 of the present invention has, for example, a processing container 14 made of aluminum having a circular inside shape. A container heating means (not shown) for heating the processing container or the like is provided on the side wall of the processing container 14. The ceiling portion in the processing container 14 is provided with a gas introduction means for introducing a necessary gas, for example, a film forming gas, that is, a shower head 16 is provided. The shower head 16 has a gas ejection surface 18 on the lower surface, and a plurality of gas injection holes 20A and 20B provided in the gas injection surface 18 are directed toward the processing space S to eject the processing gas. In the shower head 16, a hollow gas diffusion chamber 22A, 22B which is separated from the gas injection holes 20A, 20B and which is divided into two, is formed, and the gas diffusion chambers 22A, 22B are introduced into the nozzle head. After the gas is diffused in the planar direction, the gas is ejected from the respective gas injection holes 20A and 20B that communicate with the respective gas diffusion chambers 22 A and 22B. In this case, the gas injection holes 20A and 20B are arranged in a matrix, and the respective gases ejected from the respective gas injection holes 20 A and 20B are mixed in the processing space S. This form of supply is called post-mixing. The entire shower head 16 is formed of a nickel alloy such as nickel or Hastelloy (trade name), aluminum, or aluminum alloy. Further, in the case of film formation by the ALD method described later, the shower head 16 may have one gas diffusion chamber. Then, in the joint portion between the shower head 16 and the upper end opening portion of the processing container 14, the intermediate member-16-200810019 (14) is provided with a sealing member 24 such as a 0-ring or the like, and the processing container 14 is maintained. The air tightness. In addition, a semiconductor wafer W to be treated as a target object is placed on the side wall of the processing container 14, and a loading/unloading port 26 for loading and unloading the inside of the processing container 14 is provided, and the loading/unloading port 26 is air-tightly placed. A switchable gate valve 28 is provided. An exhaust space 32 is then formed at the bottom 30 of the processing vessel 14. With . The body has a large opening 34 formed in the center of the bottom of the container, and the opening φ port 34 is connected to the bottomed cylindrical body partition wall 36 extending downward, and the row is formed inside. Gas space 3 2. Then, the stage structure 40 is placed upright from the bottom portion 3 of the cylindrical portion partition wall 36 of the exhaust space 32. The stage structure 40 includes a columnar column 42 that is erected by the bottom portion 38, and a mounting table 44 that is fixed to the upper end portion of the column 42 and on which the semiconductor wafer W belonging to the object to be processed is placed. Further, the above-described mounting table 44 is composed of, for example, a ceramic material or quartz glass. In the mounting table 44, a resistance heating electric heater 46 composed of, for example, a carbon electric heater or the like that generates heat by energization is housed, and the semiconductor wafer w placed on the upper surface of the mounting table 44 is heated. . In the above-described mounting table 44, a plurality of, for example, three latch insertion holes 48 (only two in the first drawing) are formed in the vertical direction, and the above-described plug insertions are inserted in the slide-fit state so as to be vertically movable. The pin 50 is pushed over the hole 48. At the lower end of the upper push pin 50, a push-up ring 52 made of, for example, aluminum, which is formed in a circular ring shape, is disposed, and is supported by the push-up ring 52 in a state where the lower end of each of the upper push pins 50 is not fixed. The arm portion 54 extending from the push-up ring 52 is coupled to a telescopic rod 56 provided through the bottom portion 30 of the container, and the telescopic rod 56 is extended by an actuator 58 in 200810019 (15). In this manner, each of the upper push pins 50 is expanded and contracted downward from the upper end of each pin insertion hole 48 when the wafer W is transferred. Further, a telescopic bellows 60 is disposed in the middle of the penetrating portion of the bottom of the container of the telescopic rod 56 of the actuator 58, and the telescopic rod 56 can maintain the airtightness in the processing container 14 and ascend and descend. The opening 34 on the inlet side of the ejector space 32 is set to be smaller than the diameter of the carrier 44, and the processor body which is formed to φ outside the peripheral portion of the mounting table 44 flows below the mounting table 44 and flows to the lower side. Opening 3 4 . In the lower side wall of the above-described cylindrical portion partition wall 36, an exhaust port 62 is formed facing the exhaust space 32. The exhaust port 62 is connected to the vacuum exhaust system 64. The vacuum exhaust system 6 has a plurality of exhaust passages 66 connected to the exhaust port 62, and a pressure regulating valve 68 and a vacuum pump 70 are sequentially disposed in the exhaust passage 66, and the processing container 14 is disposed. The atmosphere of the inner and exhaust space 32 can be pressure controlled and evacuated for venting. In order to supply a specific gas to the shower head, a material gas supply means 72 for supplying a material gas and a reducing gas supply means 74 for supplying a reducing gas are connected to the shower head #1 6 '. Specifically, the raw material gas supply means 72 has a raw material gas flow path 7 8 connected to the gas inlet 76 of the gas diffusion chamber 2 2 A of the two gas diffusion chambers. Here, the material gas flow path 78 is divided into two, and one of the branch roads 80' is installed with an on-off valve 8 2 and a flow controller 84 like a mass controller in the middle of the middle, and is connected to the storage section. 1 The first raw material source of the raw material is 8 6 . In the first raw material, a transition metal-containing transition metal material is used, and an inert gas such as an Ar gas controlled by a flow rate is used to carry out the -18-200810019 (16) bubble, and the raw material is gasified, and the inert gas can be mixed. Metal raw material gas. Here, the vapor of the raw material is heated to increase the vapor pressure of the raw material, and the first raw material source is heated. The above transition metal-containing material may be obtained from j (MeCp) 2Mn (precursor). 'In addition, the supply of raw material gas is not only the use of liquid raw material gasification method or solution material gasification method. The material gasification method refers to the use of a gasifier at room temperature to make the liquid method. It means a method in which a raw material is dissolved in a solvent at room temperature to become a liquid, and a gasifier is used. This method is not only suitable for supplying Μη to supply Cu raw material gas. Further, the other branching path 8 8 is in the middle of the valve 90 and the flow controller 92 like the mass controller, and the second material source 94 of the raw material. The second raw material is made of an inert gas containing, for example, an Ar gas controlled by a flow rate, and the raw material is gasified, and may be accompanied by an inert gas - a raw material gas. Here, the vapor pressure of the raw material is very low. The vapor pressure of the raw material is raised, and the second raw material source 94 is used for electricity. As the copper-containing raw material, for example, Cu (hfac) 2, Cu (dibm) 2 or the like (precursor) containing copper may be used. Further, the above-mentioned inert gas for foaming may be replaced by He, Ne, or the like. Then, in order to prevent the material gas from being reliquefied, if the supply pressure is low, the 丨86 electric heater 86a can be electrically charged, for example, with manganese. Here, the raw material of the liquid is vaporized to allow the solution to vaporize the raw material gas in a solid or liquid state, or may be connected to the copper-containing raw material gas containing the second: copper to be activated. In the case where the copper is supplied, in order to heat the Cu (hfac) TMVS Ar gas, the heat exchanger 94a is used as a switch which is formed in the middle of the above-mentioned each -19-200810019 (17) branch roads 80 and 88 and the two branch roads. The valves 82 and 90, the flow controllers 84 and 92, and the material gas flow path 78 are wound around the belt heater 140 to heat these. Further, it is of course possible to provide a plurality of raw material gas supply means in accordance with the raw materials used. Further, the reducing gas supply means 74 has a reducing gas flow path 1A connected to the gas inlet 98 of the other gas diffusion chamber 22B. The reducing gas flow path 1 〇 〇 is provided with a switching valve 1 〇 2 and a flow controller 104 like a mass controller in the middle of the middle, and is connected to a reducing gas source 106 that houses the reducing gas. Here, the reducing gas is H2 gas, but other H20 or vaporized organic solvent may be used. Here, the material gas is connected to the gas diffusion chamber 22A located above the shower head 16 and the reducing gas is connected to the gas diffusion chamber 22B located below. This is because the shower head 16 approaches the mounting table 44 and faces each other, and the temperature of the gas ejection surface 18 tends to rise. Therefore, the material gas is introduced into the gas diffusion chamber 22B of the f-side, and the gas is decomposed. Therefore. Further, an inert gas supply means (not shown) formed for purification is connected to the shower head unit 16, and a purge gas is supplied as needed. As the purge gas, an inert gas such as N2 gas, Ar gas, He gas, or N e gas can be used. Then, in order to control the operation of the entire apparatus, the control means 108 composed of, for example, a microcomputer or the like is formed, and the control of the gas supply start or stop, the control of the supply amount, and the pressure in the processing container 4 are performed. Control, temperature control of wafer W, etc. Then, the control means 1 〇 8 has a memory medium 1 1 0 for storing a computer program for performing the above control. -20- 200810019 (18) The above-described memory medium 110 can use, for example, a floppy disk, a flash memory, a CD (Compact Disc), or the like. Next, the operation of the film forming apparatus configured as described above will be described. First, the unprocessed semiconductor wafer W is held by a transport arm (not shown), and passes through the gate valve 28 in the open state and the loading/unloading port 2 6, moved into the processing container 14 within. After the wafer W is transferred to the raised upper push pin 5 ’, the upper push pin 5 〇 is lowered and placed on the upper surface of the mounting table 44. Then, the raw material gas supply means 72 or the reducing gas supply means 74 are operated, and the flow rate control of the various types of gas, which are sent to the shower head 16 as a processing gas, and the like, are separately supplied and supplied. The gas injection holes 20A and 20B are ejected and ejected, and are introduced into the processing space S. As will be described later, the various gases have various supply forms. Then, the vacuum pump provided in the vacuum exhaust system 64 is continuously driven, and the processing container 14|% or the exhaust space 3 2 is evacuated, and then the opening degree Φ of the pressure regulating valve 6 8 is adjusted, and the processing space S is processed. The atmosphere is maintained at a specific processing pressure. At this time, the temperature of the wafer W is heated by the resistance heating heater 44 provided in the mounting table 44, and maintained at a specific processing temperature. In this way, a desired thin film is formed on the surface of the semiconductor wafer w by heat treatment such as thermal CVD.

In the case where the copper-containing material gas or the manganese-containing material gas flows, the flow path heating means 96 prevents the material gas flow path 78 and the two branch paths 80 and 8 from heating to cause the material gas in the path to liquefy, but at this time The heating temperature varies depending on the raw material gas used. When Cu(hfac)TMVS -21 · 200810019 (19) and (MeCphMn are used as the raw material gas, heating to neither of the two gases will be liquefied and will not thermally decompose. The temperature is, for example, 5 5 to 9 0 t. In addition, the shower head 16 and the processing container itself are heated to 60 to 80 ° C. Next, the film forming method of the present invention will be specifically described with reference to FIGS. 2 to 4 The figure shows the deposition state of the film in each step centering on the concave portion of the semiconductor wafer. Fig. 3 is a flow chart showing the steps of the film formation method of the present invention, and Fig. 3(A) shows In the first embodiment, Fig. 3(B) shows a second embodiment. Fig. 4 is a timing chart for explaining the supply state of various gases by the ALD method in forming a seed crystal film. One of the objects of the method of the present invention is One film forming device (insitu) continuously carries out various kinds For example, when the wafer W is carried into the film forming apparatus 12, as shown in FIG. 2(A), on the surface of the insulating layer 1 such as an interlayer insulating film formed on the wafer W, A recess 2 is formed like a channel or a hole, and a wiring layer 3 composed of a layer of copper or the like is exposed to the bottom of the recess 2. The insulating layer 1 which becomes a base film is an oxide containing germanium, such as Si 2. The composition of the present invention is such that the method of the present invention is based on the surface of the semiconductor wafer W in this state, first forming the seed film 6 in accordance with the seed film forming step as shown in Fig. 2(B). The seed film 6 may be a CuMn alloy film (S1 in Fig. 3(A)) or a Μn film (S1-1 in Fig. 3(B)). Further, the seed film 6 may be formed. In the CVD method, the ALD method can also be used. Here, the ALD method refers to a film forming method in which different film forming gases are alternately supplied to form a film of an atomic standard or a molecular standard layer by layer. -22· 200810019 (20) Second, As shown in FIG. 2(C), the Cii film 8 is formed as a metal film through the embedding step, and the recess 2 is buried. (S2 in Fig. 3(A) and S2 in Fig. 3(B)). The embedding step may be a CVD method or an ALD method, or may be the same as the conventional method, using a PVD method. (sputtering or vapor deposition) or electroplating. Further, in order to form the barrier film reliably, if necessary, the wafer W is exposed to a high temperature for annealing treatment*, as shown in Fig. 2(D) The seed film 6 is self-integratingly reacted with the interface portion of the insulating layer 1 composed of SiO 2 which belongs to the underlying layer, and the barrier layer 12 composed of the MnSixOy (x, y: arbitrary integer) film is surely formed ( S3 in Fig. 3(A) and S3) in Fig. 3(B). Further, if the barrier layer 11 is already formed in the previous step in which the high-disposal treatment has been performed, the annealing treatment may not be performed, but in order to sufficiently form the barrier layer 112, it is preferable to carry out the annealing treatment. Here, each step will be described in detail. First, in the case of forming a CuMn alloy film (S1 in Fig. 3(A)) as the seed crystal film 6, there are three kinds of film forming methods. In the first method of forming a film, a method of forming a CuMn alloy film by a CVD method is carried out by simultaneously flowing a Cu source gas and a gas containing a Μη material and a H2 gas belonging to a reducing gas. The second film forming method is an ALD method as shown in Fig. 4(A), and a Cu-containing material gas and a Μn-containing material gas are synchronously supplied, and the two gases alternately flow alternately with the Η2 gas. The intermittent period Τ 1 between the two gases and η 2 is a purification period, and the residual gas in the processing container 14 may be removed only during evacuation, or an inert gas such as Ν 2 gas may be introduced and evacuated to be removed. This method of purification is also applicable to the method described in the following section -23-200810019 (21). This ALD method is, for example, a period from the supply of the Μη-containing raw material gas to the next supply of the Μn-containing raw material gas, and a CuMn alloy film having a thickness of, for example, about 0.4 to 〇6 nm is formed during this period. Here, the thickness of the seed crystal film 6 is required to be, for example, about 2 nm in terms of the film thickness η of the Mn pure metal in the CuMn film. The film forming process is performed, for example, to about 10,000 cycles. In other words, when the film formation by the ALD method is performed, the controllability of φ high film thickness can be improved, and a film thinner than the CVD method can be formed with good controllability. The processing conditions at this time (including the case of CVD treatment), the treatment temperature is about 70 to 450 ° C, and the treatment pressure is about IPa to 3 Pa. Further, the flow rate of the raw material gas containing Μη is about 0·1 to 10 sccm, and the flow rate of the material containing the Cu raw material is about 1 to 1 〇〇seem, and in any case, the Cu becomes 1 times more than the Μη. There is ample: C u in the composition of the CuMn alloy film. Further, the flow rate of the Η 2 gas is about 5 to 5 0 s c c m . However, the adhesion of φ and C u to the insulating film such as S i 〇 2 is very weak. Therefore, in the initial stage of film formation, the flow ratio of the gas containing the raw material gas containing Μη to the raw material containing Cu can be increased. There is ample Μ η in it. Further, the supply period t1 containing the 原料n material gas is about 10 to 15 sec, and the supply period 12 containing the C u source gas is about 10 sec' Η 2 The supply period 13 of the gas is about 10 sec. 'Intermittent period Τ 1 It is 2 0~1 2 0 sec. Here, as described above, the adhesion of the insulating film of Cu to Si〇2 is weak, so that the supply period 11 of the Mn source gas may be contained in the initial stage of film formation with respect to the f containing the Cu raw material and the hot body. The period 12 should be lengthened ' -24- 200810019 (22) For example, it can be set to 15 sec (indicated by the dotted line 121 in the figure 4 (A)). That is, it is possible to form a treatment formulation by sequentially changing the supply ratio of the 原料η source gas and the Cu-containing material gas in accordance with the film formation time or in accordance with the thickness of the deposited film. In this way, the components in the CuMn alloy film can be gradually changed from the state in which the Μn is abundant to the state in which Cu is abundant. Therefore, the adhesion between the insulating layer 1 and the seed crystal film 6 and between the seed crystal film 6 and the Cu ^ film 8 can be improved, and peeling of the film during film formation or the like can be prevented. φ In the case shown in Fig. 4(A), the η method is the ALD method shown in Fig. 4(B), in which the 原料η source gas and the Cu source gas are simultaneously supplied and discharged. The above two gases are alternately supplied alternately during the intermittent period, and during the above-described intermittent period, the H 2 gas is supplied. In this case, the period of one cycle becomes twice as long as the case shown in the fourth (A) above. Then, it is a seed crystal film 6 in an alloy state in which an Μη film having a film thickness of 0.2 to 0.3 nm and a film film having a very small thickness of 0.2 to 0.3 nm is alternately laminated. At this time, as shown in Fig. 4(B), the initial step 'φ considers that the adhesion between the seed film 6 and the insulating layer 1 and the barrier property' is preferably supplied in advance to contain the Cu source gas. The step of constituting the step is also carried out by supplying a gas containing Μη. Further, both films are very thin, so Μη and _Cu are mutually diffused to become an alloy state. When the film formation is performed by the ALD method, the film adheres sufficiently to the inner wall of the fine concave portion as compared with the film formation by the CVD method, and the step coverage can be further improved. In particular, the size of the concave portion is increased. It becomes more refined, and the ALD rule becomes more effective. Next, the metal film 8 shown in S2 in the second (C) and the third (A) is -25. 200810019 (23). When the Cii film is formed, the Cu material gas and the H2 gas may be simultaneously flowed. The metal film 8 composed of the Cu film is formed by the CVD method, and similarly to the fourth (A) and fourth (B) views, the Cu source gas and the 112 gas may alternately flow in reverse. Alternatively, it is also possible that the H2 gas does not flow, and only the thermal decomposition reaction is used to form a metal film composed of the Cii film. ~ * Processing conditions at this time (including the case of CVD treatment), the treatment temperature is about 70 to 450 ° C, and the treatment pressure is about IPa to 13 Pa. Further, the flow rate of the raw material gas containing Cu is about 1 to 1 〇〇 sccm, and the flow rate of the h2 gas is about 5 to 500 seem. Alternatively, the metal film 8 composed of the Cu film described above may be formed by a conventional PVD method (sputtering or vapor deposition) or plating method to be buried. In particular, in the case of the CVD method or the ALD method, since the film can be easily deposited on the inner wall of the fine concave portion by the plating method, even if the concave portion is made finer, the concave portion can be buried without generating pinholes inside. Next, in the case of the annealing treatment shown by S3 in the second (D) diagram and the third (A) diagram, the wafer W in which the embedding process has been completed is heated to a specific processing temperature, for example, 100. At a temperature of about 450 ° C, the barrier layer 12 formed of a MnSixOy film by self-integration is surely formed on the seed film 6 and the insulating film 1 composed of the SiO 2 film which becomes the base film. Interface section. Further, when the annealing treatment is performed, oxygen may be supplied from the enzyme supply means 73a to the processing container to control the oxygen partial pressure. The purpose of the annealing treatment is to form the barrier layer 112 as described above, -26-200810019 (24) Therefore, the seed film forming step or the Cu film forming step belonging to the previous step is at a very high temperature, for example, 1 50 °. When the temperature is higher than the processing temperature of C or higher, the barrier layer 1 1 3 is formed to have a sufficient thickness, so that the annealing treatment described above is unnecessary. Further, in the case where the plating treatment is carried out in accordance with S2 in Fig. 3(A), the annealing treatment described above is of course performed. Here, the seed crystal film forming step, the Cii film forming step and the annealing treatment by the CVD method or the ALD method may all be continuously performed in the same processing apparatus 1 2 . In the vacuum-processable processing container 14 , a film containing a Cu-containing raw material gas containing copper and a Mn-containing raw material gas containing a manganese-containing transition metal and a ruthenium-containing gas belonging to a reducing gas are formed on the wafer by heat treatment. The surface of W, so even if it is a fine recess 2, it can be buried with a very large step coverage. Further, in the case where the same processing device 12 is continuously processed, the cost of the device can be greatly reduced. Further, it can be continuously processed in the same device 12, that is, in-Situ ^, so that an unnecessary metal oxide film is formed. It is suppressed. 'The result is that the embedding property can be improved, and the contact resistance can be prevented from becoming large. It is possible to improve the reliability of the semiconductor device and improve the yield. In addition, it is necessary to form a Ta film or a TaN film which is conventionally necessary. The steps of forming the barrier layer become unnecessary, and this part can increase the flow rate. Further, in the case where the CuMn alloy film is used as the seed film 6, the C11 belonging to the buried material is partially contained in -27-200810019 (25), so that the adhesion to the metal film 8 of the upper layer can be improved. Here, the ratio of C u and Μ η in the above-mentioned C u Μ η film is described in more detail with respect to the change in the composition ratio of these elements. Fig. 5 is a graph showing an example of the supply amount of the "Μη material gas and the Cu-containing material gas, as the film formation time (heat treatment) is changed. In addition, in the graph, it only indicates the trend of supply, and it is not the absolute flaw of supply. Here, as described above, in order to change the composition ratio of Cu in the film to the transition metal, for example, Μ in the film thickness direction of the film, the copper-containing material gas and/or the above-mentioned copper-containing material gas and/or Or the supply amount of the above-mentioned transition metal-containing gas is changed. Specifically, the composition ratio of the transition metal in the film of the CuMn film belonging to the film is such that the lower layer side in the film is large, and the smaller the upper layer side is, the more the supply amount of each of the above-mentioned raw material gases is controlled. That is, as shown in Fig. 5(A), in the initial stage of film formation, the raw material gas containing Μη flows at a large flow rate, and after a period of time, the flow rate is linearly reduced in sequence, as time passes through the film formation time. * After a few, the last flow becomes about zero. In this regard, at the initial stage of film formation, the Cu-containing material gas hardly flows for a while to form a pure Μ 金属 metal film, and then, corresponding to the reduction of the Μη-containing material gas, the Cu-containing material is required to follow the film formation time. The flow rate of the gas increases, for example, in a straight line. Finally, the supply amount of the raw material gas containing Μη is maintained at zero, and the flow rate of the gas containing the Cu raw material is maintained at 280 - 200810019 (26) to form a film, and here, A pure Cu metal film is formed. In this case, the film is a pure Μ 金属 metal film at the beginning of film formation, and finally becomes a C U Μ η alloy, and the Μ η is sufficiently maintained, and is reversed to a state where Cu is abundant in the middle, and finally becomes a pure Cu metal film. In Fig. 5(B), since the film formation is started, the 原料η material gas is gradually decreased from a certain supply amount, and the Μη source gas is gradually increased from the zero supply. In this case, the entire thickness direction of the film becomes a sinuous CuMn film, and a pure Μn metal film or a pure Cu metal film as shown in Fig. 5(A) is not formed. In addition, in the fifth (A) diagram and the fifth (B) diagram, the characteristic is increased linearly or the characteristic is reduced. However, the supply amount of each of the material gases can be adjusted to cause a characteristic that is curved or increased. To replace this linear characteristic. In the case of the fifth (A) and the fifth (B), the composition ratio of 'Cu to Μ η in the portion of the CuMn alloy film is continuously increased from the state of the Μη to the Cu. status. In the case shown in Fig. 5(C), the case where the raw material gas containing Μη is gradually reduced, and the content of the raw material containing Cu is increased stepwise. In this case, the composition ratio of Cu to Μη in the CuMn alloy film is gradually changed. In addition, the number of stages is not particularly limited. In the case of the fifth (A) to the fifth (C), the lower layer in the film becomes a pure tantalum metal film or a CuMn alloy which is rich in Μη, and the upper layer becomes a CuMn alloy containing a CU source gas or Cu. As described above, the adhesion of the base film Si 02 and the Cu film 8 can be further improved. Further, in the above-described embodiment, the case where the CuMn alloy -29-200810019 (27) film is formed as the seed film 6 (SI of the third (A)) will be described by way of example, but as described above, the Μη film may be formed. (Sb 1 of the third (B)) is used as the seed film 6. In the case of forming the Μn film, a method in which a 原料n source gas and a Η2 gas belonging to a reducing gas are simultaneously flowed, formed by a CVD method, and the above-mentioned 原料n-containing material gas and Η2 gas can be used, as shown in FIG. 4(C) Any method of forming a method by ALD by alternately circulating in an alternating manner. The processing conditions in this case, such as the processing pressure, the processing temperature, and the flow rate φ of each gas, are the same as those described using the fourth (A) and fourth (B) drawings. Further, S2 and S3 in the third (B) diagram are the same as the steps S2 and S3 in the third (A) diagram, and even if this is the case, the barrier layer 1 1 2 is sufficiently formed in the previous step, the description may be omitted. 3 (B) Annealing treatment of S3 in the figure. Further, even in the case where the Cu film is deposited on the Μη film, the two films are treated in the in-situ, and the adhesion between the two metals can be improved. In the case where the Μn film is formed as the seed film 6, the upper Cu wiring layer 8 is formed at the bottom of the concave portion 2, and is connected to the lower Cu wiring layer 3 by the Μ? film # whose resistance 値 is larger than that of the Cu film. However, the seed film 6 is thinner than the tantalum film formed by conventional sputtering, so that most of the Μη* element is diffused into the Cu wiring layer 3 and the Cu wiring layer 8 after annealing treatment or the like, and the Μn layer It does not exist, so the contact resistance of this part does not become high. Further, the amount of the Μn metal in the CiiMn film belonging to the above film (including the case of having a pure Μn metal film or a pure Cu metal film) or the Μη film has the most suitable 値, and the 値 is converted into a pure metal film thickness of Μη. In the range of 0.7 to 2.6 nm, it is preferable to form the above film in such a manner as to conform to the range of conversion of the above-mentioned Μn metal film. That is, in the annealing step, as described above, -30-200810019 (28) Μη is compounded to become a MnSixOy film, and the remaining Μη is discharged to the surface by diffusion into the Cu film, but the amount of Μη is excessively contained. In the film, the Μn component which is not completely discharged is left in the Cu film buried in the concave portion, and the residual Μn portion causes the resistance of the rising Cu wiring to deteriorate the reliability of the wiring. In this case, the content of Μη in the film is set to be in the range of 0.7 to 2.6 nm as in the above-mentioned Μη• pure metal film thickness, so that a sufficient amount of Μη can be maintained in the Cu wiring and the insulating layer. The barrier layer of the interface. When the amount of Μ η is less than the thickness 〇·7 nm, a barrier layer having good characteristics cannot be formed. However, if it is larger than 2.6 nm, as described above, an excessive amount of Μη component may remain in the Cu wiring, resulting in deterioration of the film quality. Further, in the example of the apparatus shown in Fig. 1, the flow paths of the two kinds of material gases of the material gas supply means 72 are combined in the middle, but the invention is not limited thereto, and the two types of materials may be separated. Fig. 6 is a view showing a configuration of a modification of the material gas supply means of the film forming apparatus having such a configuration. The case shown in Fig. 6 shows the shower head 16 and the material gas supply means 72 connected to the shower head, and the same components as those shown in Fig. 1 are the same. The same figure number. Here, the raw material gas flow paths 1 2 0 and 1 2 2 are respectively extended from the first raw material source 86 containing Μη and the second raw material source containing Cu. Then, the respective material gas channels 120 and 122 do not meet in the middle, and the respective tips are directly connected to the gas inlets 76 of the shower heads 16 so that they do not mix with each other during the transportation of the material gases. In the case of being introduced into the shower head 16 - 31 - 200810019 (29) In this case, in each of the above-mentioned material gas flow paths 1 20, 1 22, a flow path composed of, for example, a belt type electric heater 绕 is provided. The heating means 96a, 96b are heated so that the various raw material gases flowing into the flow path are not liquefied. In this case, the respective material gas channels 120 and 122 can be respectively heated and maintained at an optimum temperature corresponding to the flowing material gas. Specifically, when (MeCp) 2Mii is used as a raw material, the flow path heating means 96a is heated, for example, in a range of 70 to 90 ° C, and Cu (hfac) TM VS is used as a raw material, and is set to The flow path heating means 96b is heated, for example, in the range of 5 5 to 70 °C. In this case, the same effects as those described previously can be exerted. Further, the above organometallic material is not limited to the material previously described, and any material may be used if it is composed of a transition metal and C (carbon) and hydrazine (hydrogen). The organometallic material may be M(R-CP)x (x is a natural number), or M(R-Cp)x(CO)y (x, y is a natural number). However, Μ represents a transition metal, R represents an alkyl group, and one selected from the group consisting of Η, CH3, C2H5, C3H7, and C4H9, and Cp is a cyclopentadienyl group ((^〇1〇1^1^311 Taking 61^1; (:5:»4), (:0 is a carbonyl group. In addition, the above-mentioned organometallic material containing the Μn raw material may be used by Cp2Mn[= Mn(C5H5)2], (MeCp) 2Mn[ = Mn(CH3C5H4)2] , (EtCp)2Mn[ = Mn(C2H6C5H4)2], (i-PrCp)2Mn[ = Mn(C3H7C5H4)2], MeCpMn(CO)3[ = (CH3C5H4)Mn( CO)3], (t-BuCp)2Mn[= Mn(C4H9C5H4)2], CH3Mn(CO)5, •32- 200810019 (30)

Mn(DPM)3[ = Mn(C1 jHi9〇2)3] '

Mn (DMPD(EtCp)[ = Mn(C7HiiC2H5C5H4)),

Mn(acac)2[= Mn(C5H7〇2)2], Mn(DPM)2[= Mn(CiiHi9〇2)2], Mn(acac)3[= Mn(C5H7〇2)3], Mn( One or more materials selected from the group of hfac) 2 [ = Mn(C5HF602) 3 ]. Alternatively, an organometallic material may be used, and other metal dislocation materials may also be used. Here, the case where si〇2 is used as the insulating layer 1 belonging to the base film will be described by way of example, but it is not limited thereto, and Low-k (low dielectric) which is used as the interlayer insulating layer may be used. The SiOC film (including the thermal oxide film and the plasma TEOS film), the SiOC film and the SiCOH film, the SiCN film, the porous yttrium oxide film, and the porous body A can be used as the base film. A film selected from the group consisting of a methylsilsesquioxane (MSQ) film and a polypropyne film and a SiLK (trade name) film and a fluorocarbon film, or a laminated film of these. In addition, here, H2 gas is used as the reducing gas, but other organic solvents such as ethanol, isopropanol, acetone, hexane, octane, and butyl acetate may be used. Butyl acetate) and so on. Further, here, the case where Μη is used as the transition metal will be described by way of example, but it is not limited thereto, and other excessive metals such as Mn, Nb, Zr, Cr, V, yttrium, Pd, Ni may be used. One or more metals selected from the group consisting of Pt, Rh, Tc, A1, Mg, Sn, Ge, Ti, and Re. In addition, the film forming apparatus described here is merely an example. For example, in the heating means, a heating lamp such as a halogen lamp may be used instead of the resistance heating electric heater, and the processing apparatus is not only a single piece. It can also be batch type. Further, for example, the shower head 16 is not used as the upper electrode, and the mounting table is used as the lower electrode. For example, high-frequency power is applied between the electrodes to form a plasma. A plasma auxiliary device can be added at the time of film formation. Further, although the semiconductor crystal φ circle of the object to be processed is described by way of example, the present invention is not limited thereto, and the present invention can be applied to any of a glass substrate, an L C D substrate, a ceramic substrate, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a block diagram showing an example of a film forming apparatus of the present invention. Figs. 2(A), (B), (C), and (D) are diagrams showing a recess of a semiconductor wafer. A diagram showing the accumulation of film in each step of the center. φ 3(A) and (B) are flowcharts showing the respective steps of the film formation method of the present invention. 4(A), (B), and (C) are time charts for explaining the supply state of each gas of the ALD method when the seed crystal film is formed. Fig. 5 is a view showing an example of a change in the supply amount of the Mn raw material gas and the Cu containing raw material gas in accordance with the film formation time and the deposition of the heat treatment. Fig. 6 is a partial structural view showing a modification of the material gas supply means of the film forming apparatus. -34- 200810019 (32) Figures 7(A), (B), and (C) are diagrams showing a general embedding step of a concave portion of a semiconductor wafer. [Description of main component symbols] 1 : Insulation layer ' 2 : recessed portion _ 3 : wiring layer 4 : barrier layer 6 : seed film 8 : metal film 1 2 : film forming apparatus 1 4 : processing container 1 6 : shower head 1 8 : gas injection surface _ 20A : gas injection hole 20B : gas injection hole ^ 22A : gas diffusion chamber - 22B : gas diffusion chamber 24 : sealing member 26 : loading and unloading port 28 : gate valve 3 0 : container bottom 32 : row Air space -35- 200810019 (33) 34 : Opening 3 6 : cylindrical partition 3 8 : cylindrical partition wall bottom 40 : mounting table structure 4 2 : pillar 44 : mounting table ^ 46 : resistance heating heater • 48 : Pin insertion hole 50: upper push pin 52: push-up ring 54: arm portion 5 6 : telescopic rod 5 8 : actuator 60 : bellows 62 : exhaust port _ 64 : vacuum exhaust system 66 : exhaust passage - 68 : Pressure regulating valve - 70 0 : Vacuum pump 72 : Raw material gas supply means 74 : Reduced gas supply means 76 : Gas inlet 78 : Raw material gas flow path 8 〇 : Divided road - 36 - 200810019 (34) 82 : On-off valve 84 : Flow controller 8 6 : first raw material source 86 a : electric heater 8 8 : branch circuit 90 : switching valve ~ 92 : flow controller φ 94 : second raw material source 94 a : electric heater 96 a : flow path heating means 96b : flow path heating means 98 : gas inlet 100 : reducing gas flow path 102 : switching valve 104 : flow controller _ 106 : reducing gas source 1 0 8 : control means - 11 〇: memory medium , 1 1 2 : barrier layer 120 : raw material gas flow path 122 : raw material gas flow path - 37

Claims (1)

200810019 (1) X. Patent application scope 1. A film forming method, comprising: the steps of: transporting a workpiece to a vacuumable processing container; and supplying at least a processing container A transition metal-containing transition metal source gas and a reducing gas are contained, and the object to be processed is heated, and a film is formed on the surface of the object to be processed by heat treatment. Φ 2 The film forming method according to the first aspect of the invention, wherein a copper-containing raw material gas containing copper, a transition metal-containing transition metal-containing gas, and a reducing gas are supplied to the processing container, and The body is heated; the film is formed by heat treatment to form a film on the surface of the object to be treated. The film forming method according to the first aspect of the invention, wherein the heat treatment is performed by a CVD (Chemical Vapor Deposition) method. The method of forming a film according to the first aspect of the invention, wherein the first heat treatment is an ALD (Atomic Layer Deposition) method in which the raw material gas and the reducing gas are alternately supplied to form a film. 5. The film forming method according to claim 2, wherein the heat treatment is performed by alternately supplying the two kinds of material gases in an intermittent manner while intermittently, and supplying the reducing gas during the intermittent period. The way to proceed. 6. The film forming method according to the first aspect of the invention, wherein the copper film is deposited on the object to be processed on which the film is formed by a CVD method, and the recessed portion of the object to be processed is subjected to embedding treatment. Way to proceed. -38-200810019 (2) 7. The film forming method according to claim 6, wherein the embedding process is carried out in a processing container in which the film is formed. In the film forming method, after the embedding process, the object to be processed is subjected to an annealing step. 9. The film forming method according to item 8 of the patent application, wherein the annealing treatment is performed on the film. The film forming method according to the first aspect of the invention, wherein Φ is deposited on the surface on which the film is formed by electroplating, and the concave portion of the object to be processed is buried. In the film forming method according to the first aspect of the invention, after the embedding process of the concave portion of the object to be processed is performed, the body is annealed. 12. The film forming method according to claim 2, wherein the composition ratio of the copper metal in the film is changed in the film thickness direction of the film, and the film is made in the middle of the heat treatment. It is carried out in such a manner that there is a change in the copper source gas and/or the aforementioned transition metal-containing gas. The film forming method according to item 12 of the patent application, wherein the film layer side is large in the composition ratio of the transition metal in the film, and the smaller the side is on the upper layer side, the control is performed. The amount of supply of each of the foregoing. 1. The film forming method according to claim 1, wherein the amount of the transition metal in the film is converted to a film thickness of the pure metal, and is in the range of 〜. 7 to 2.6 nm. Inside. In the middle, go ahead. In progress. In the middle, go ahead. In the middle, take the physical line. In the process of processing, in the middle of the supply of the above-mentioned raw material, the method of forming a film according to the first aspect of the patent application, wherein The surface of the treatment body is a base film of the film, and the base film is composed of a SiO 2 film, a SiOC film, a SiCOH film, a SiCN film, a porous oxidized sand film, and a porous methyl sesquisite (1116111715丨). 1565911丨0\3116;]\48(5) One or more membranes selected from the group consisting of membranes and polyacetylene membranes and SiLK (trade name) membranes and fluorocarbon membranes. '16. The film forming method according to the first aspect of the invention, wherein the transition metal raw material containing the transition metal source gas is composed of an organic metal material or a metal complex material. The film forming method according to the above aspect, wherein the organometallic material is M(R-Cp)x (x is a natural number), wherein Μ represents a transition metal, R represents an alkyl group, and is represented by H, CH3, C2H5, One selected from the group of C3H7 and C4H9, Cp is cyclopentane The method of forming a film according to claim 16, wherein φ the foregoing organometallic material is M(R-Cp)x(CO)y (x, y is natural) Number), where Μ is a transition metal, R is an alkyl group, one selected from the group consisting of h, CH3, C2H5', C3H?, C4H9, and Cp is a cyclopentandienyl group (cyclopentandienyl; C5H4), CO is a carbonyl group. The film forming method according to claim 16, wherein the organometallic material is composed of a transition metal and C and ruthenium. The film forming method according to the item 1, wherein the transition metal is from Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh, Tc, A1, Mg, Sn, Ge, Ti, Re - 40 - 200810019 (4) One or more metals selected from the group. 2 1. The film forming method according to claim 16, wherein the transition metal is composed of manganese (Mn) The organometallic material containing ruthenium is composed of Cp2Mn[= Mn(C5H5)2], (MeCp)2Mn[= Mn(CH3C5H4)2], (EtCp)2Mn[= Mn( C2H5C5H4)2], (i-PrCp)2Mn[ = Mn(C3H7C5H4)2], MeCpMn(CO)3[ = (CH3C5H4)Mn(CO)3], '(t-BuCp)2Mn[ = Mn(C4H9C5H4) 2], CH3Mn(CO)5, • Mn(DPM)3[= Mn(Ci iHi9〇2)3] 'Mn(DMPD(EtCp)[ = Mn(C7H n C2H5C5H4)) ' Mn(acac)2[ = Mn(C5H7〇2)2] ' Mn(DPM)2[ = Mn(Ci]Hi9〇2)2] ' Mn(acac)3[ = Mn(C5H7〇2)3], Mn(hfac)2[ = One or more materials selected from the group of Mn(C5HF602)3]. The film forming method according to claim 1, wherein the heat treatment is a plasma. The film forming method according to claim 1, wherein the raw material gas and the reducing gas are mixed in the processing container before the Φ*24. In the membrane method, the reducing gas is Η 2 gas. 25. A film forming apparatus which is a film forming apparatus which forms a film containing a transition metal on a surface of a workpiece to be processed by heat treatment, and is characterized in that: a processing container capable of being evacuated; and a bedding is further described a -41 - 200810019 (5) mounting table structure for placing the object to be processed in the processing container; and a heating means for heating the object to be processed; and a gas introducing hand for introducing a gas into the processing container A raw material means for supplying the raw material gas to the gas introduction means; and a means for reducing the supply of the reducing gas to the gas introduction means. φ 2 6 · The film forming apparatus described in item 25 of the patent application has a plurality of kinds of the raw material gases, and the raw material gas supplies a divergent road of the divergent road gases of different raw material gases provided for each of the raw material gases Meet in the middle. 2-7. The film forming apparatus according to Item 25 of the patent application has a plurality of kinds of the raw material gases, and the diverging path of the divergent road gases of the different raw material gases provided for each of the raw material gases is not In the middle of the meeting, we will connect and introduce the means. 2 8 · In the film formation method described in the Patent Application No. 26 or 27, in order to prevent the above-mentioned raw material from flowing to the raw material gas flow path, the branching path of the raw material gas is provided for heating. Flow segment. A film forming apparatus according to item 25 of the patent application, wherein the material gas contains at least a refrigerant gas containing a transition metal. 3. The film forming apparatus P/Ι» · ττ fe and the gas supply gas supply according to claim 29, wherein the means has the raw material Γ, wherein the means has the raw material r to the gas In the device, the gas is heated by the liquid path, wherein the metal is used, wherein -42 « 200810019 (6) The raw material gas contains: a copper-containing raw material gas containing copper, and a transition metal-containing raw material gas containing a transition metal. The film forming apparatus according to claim 25, wherein the reducing gas is H2 gas. 32. A computer program is a computer program for a film forming apparatus and a computer for performing a film forming method, and is characterized in that: ^ The film forming method has the following steps: φ transporting the object to be vacuumed a step of processing the container; and supplying at least a transition metal-containing gas containing a transition metal and a reducing gas to the processing container, and heating the object to be processed, and forming a film on the surface of the object to be processed by heat treatment . 3 - a computer program for performing a film forming method in a computer, and the film forming device used in the film forming method has: a vacuumable processing container; and is disposed in the processing container for carrying And a heating means for heating the object to be processed; and a gas introducing means for introducing a gas into the processing container; and - supplying the material gas to the gas introducing means a raw material gas supply means; and a reducing gas supply means for supplying a reducing gas to the gas introduction means; and a control means for controlling the entire apparatus; and using the film forming apparatus, a thin metal containing a transition metal is subjected to heat treatment - 43 - 200810019 (7) a computer program in which a film is formed on a surface of the object to be processed, wherein the film forming method includes the steps of: transporting the object to be processed into a vacuumable processing container; and at least processing the container Supplying a transition metal-containing raw material gas containing a transition metal, and a reducing gas, and heating the object to be treated The step of forming a film on the surface of the object to be processed by heat treatment. 34. The computer program of claim 33, wherein the φ raw material gas comprises: a copper-containing raw material gas containing copper, and a transition metal-containing transition metal-containing raw material gas. 3 5 . A readable media in a computer is a memory medium for a film forming apparatus for storing a computer program for performing a film forming method in a computer, characterized in that: the film forming method has the following steps: a step of transporting the body into the evacuatable processing container; and supplying at least a transition metal-containing material gas and a reducing gas containing a transition metal to the processing container, and heating the object to be processed, and heat-treating the film a step of forming a surface on the surface of the object to be processed. - 36 - a readable memory medium for storing a computer program, - storing a computer program for performing a film forming method in the computer, and the film forming method The film forming apparatus used has: a vacuumable processing container; and is disposed in the processing container for placing the object a mounting structure of the body; and a heating means for heating the object to be processed; and -44 - 200810019 (8) a gas introduction means for introducing a gas into the processing container; and supplying the material gas to the gas introduction means a raw material gas supply means; and a reducing gas supply means for supplying a reducing gas to the gas introduction means; and a control means for controlling the entire apparatus; ^ using the film forming apparatus, a thin φ film containing a transition metal is formed by the heat treatment The memory medium on the surface of the object to be processed is characterized in that the film forming method includes the steps of: transporting the object to be processed into the evacuatable processing container; and supplying at least the transition metal in the processing container. a step of storing a film containing a transition metal source gas and a reducing gas, heating the object to be processed, and forming a film on the surface of the object to be processed by heat treatment. 3 7. A computer program as described in claim 36 A readable memory medium in a computer, wherein the raw material gas comprises: • copper has a copper-containing raw material gas, and containing a transition metal of the transition metal-containing raw material gas. -45-