Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
  • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
  • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
  • H01L23/53204—Conductive materials
  • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
  • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
  • H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
  • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
  • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45563—Gas nozzles
  • C23C16/45565—Shower nozzles
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45563—Gas nozzles
  • C23C16/45574—Nozzles for more than one gas
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  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
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  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
  • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
  • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
  • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
• • H—ELECTRICITY
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
  • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
  • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
  • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
  • H01L21/28562—Selective deposition
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  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
• • H—ELECTRICITY
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  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
  • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
  • H01L21/76831—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers in via holes or trenches, e.g. non-conductive sidewall liners
• • H—ELECTRICITY
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  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
  • H01L21/76841—Barrier, adhesion or liner layers
  • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
  • H01L21/76844—Bottomless liners
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  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
  • H01L21/76841—Barrier, adhesion or liner layers
  • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
  • H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
  • H01L21/76864—Thermal treatment
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  • H01L21/76841—Barrier, adhesion or liner layers
  • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
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  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
  • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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  • H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
  • H01L2221/1068—Formation and after-treatment of conductors
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  • H01L2221/1084—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
  • H01L2221/1089—Stacks of seed layers
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  • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
  • H01L2924/097—Glass-ceramics, e.g. devitrified glass
  • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Definitions

• Film forming apparatus film forming method, computer program, and storage medium
• the present invention relates to a film forming apparatus and a film forming method for forming, for example, a copper manganese (CuMn) alloy film or a manganese (Mn) film as a seed film on the surface of an object to be processed such as a semiconductor wafer. .
• a film forming apparatus and a film forming method for forming, for example, a copper manganese (CuMn) alloy film or a manganese (Mn) film as a seed film on the surface of an object to be processed such as a semiconductor wafer.
• a semiconductor device is manufactured by repeatedly performing various processes such as a film forming process and a pattern etching process on the semiconductor wafer.
• the semiconductor device is further highly integrated.
• line widths and hole diameters are becoming increasingly finer due to the demand for higher miniaturization.
• copper which has a very small electrical resistance pile and is inexpensive, is required because the electrical resistance needs to be reduced by miniaturizing various dimensions.
• Patent Document 1 When copper is used as this wiring material or embedding material, it is generally considered that tantalum metal (Ta), tantalum nitride film (TaN), etc. Is used as a barrier layer.
• a thin layer or seed film made of a copper film is formed on the entire wafer surface including the entire wall surface in the recess in the plasma sputtering apparatus, and then A copper plating process is applied to the entire wafer surface to completely fill the recess. Thereafter, an excess copper thin film on the wafer surface is removed by polishing by CMP (Chemical Mechanical Polishing) or the like.
• CMP Chemical Mechanical Polishing
• FIG. 7 is a diagram showing a general loading process of the concave portion of the semiconductor wafer.
• a recess 2 corresponding to a via hole, a through hole, a groove (trench or Dual Dam ascene structure) is formed.
• the concave portion 2 has a very small width or inner diameter of, for example, about 120 nm as the design rule becomes finer.
• the aspect ratio is about 2 to 4, for example. Note that the diffusion prevention film, the etching stop film, and the like are not shown and simplified in shape.
• a barrier layer 4 made of, for example, a stacked structure of Ta N film and Ta film is formed in advance by a plasma sputtering apparatus, including the inner surface in the recess 2. (See Figure 7 (A)). Then, a seed film 6 made of a thin copper film is formed as a metal film over the entire wafer surface including the surface in the recess 2 by a plasma sputtering apparatus (see FIG. 7B). When the seed film 6 is formed in the plasma sputtering apparatus, high frequency bias power is applied to the semiconductor wafer side to efficiently attract copper metal ions.
• the recess 2 is filled with a metal film 8 made of, for example, a copper film (see FIG. 7C). Thereafter, the excess metal film 8, seed film 6 and barrier layer 4 on the wafer surface are removed by polishing using the above-described CMP process or the like.
• MnSixOy (x, y: any integer) film is formed at the boundary between the 22 n film and the CuMn alloy film, there is an advantage that the number of manufacturing processes can be reduced.
• Mn in the Mn film or CuMn alloy film is preferentially combined with the halogen element incorporated into the Cu film when the Cu film is formed by the CVD method, for example, and this halogen element is incorporated into the Cu film.
• This also has the advantage that the reliability of the wiring can be improved by improving the film quality of the Cu film wiring.
• Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-107747
• Patent Document 2 JP 2005-277390 A
• the above-mentioned CuMn alloy can only be formed by a sputtering method.
• an extremely fine pattern such as a line width and a hole diameter of 32 ⁇ is expected.
• the sputtering method cannot sufficiently cope with it, and as a result of poor step coverage (step coverage), there is a high possibility that the recesses will not be sufficiently filled.
• the semiconductor wafer since the seed film 6 formation process and the loading process cannot be performed in-situ, that is, when the semiconductor wafer is transferred to the embedding apparatus after the seed film 6 is formed, the semiconductor wafer is removed from the clean air. As a result, the highly reactive Cu Mn alloy film is oxidized, and as a result, the copper embedded film is hindered or the Mn component in the seed film is oxidized. There was a problem that Mn oxide would increase the contact resistance.
• the seed film is formed on the bottom of the recess to be thicker than the side wall thereof, so even if a sufficiently thin MnSixOy film is formed on the side wall of the recess by annealing, There was a problem that in this part, a large amount of manganese and its oxide remained higher in resistance than copper, and the contact resistance further increased.
• the present invention has been devised to pay attention to the above problems and to effectively solve them.
• An object of the present invention is to form a CuMn alloy film, Mn film, etc. by heat treatment such as CVD, so that even a minute recess can be loaded with high step coverage, and the same processing apparatus. It is an object of the present invention to provide a film forming method, a film forming apparatus, a computer program, and a storage medium that can significantly reduce the apparatus cost by performing continuous processing.
• the present invention provides a process of transporting an object to be processed into a processing container that can be evacuated, a transition metal-containing source gas containing at least a transition metal in the processing container, and a reducing gas. And heating the object to be processed to form a thin film on the surface of the object by heat treatment. [0013] In this way, a thin film is formed by heat treatment on the surface of the object to be processed by the transition metal-containing source gas containing the transition metal and the reducing gas in the processing container that can be evacuated. Even a fine recess can be loaded with high step coverage, and the apparatus cost can be greatly reduced by performing continuous processing with the same processing apparatus.
• a copper-containing source gas containing copper, a transition metal-containing source gas containing a transition metal, and a reducing gas are supplied into a processing container, and the target object is heated to supply the surface of the target object. And forming a thin film by heat treatment.
• a thin film is formed by heat treatment on the surface of the object to be processed by using a copper-containing source gas containing copper, a transition metal-containing source gas containing a transition metal, and a reducing gas in a processing vessel that can be evacuated.
• a copper-containing source gas containing copper a copper-containing source gas containing copper
• a transition metal-containing source gas containing a transition metal a reducing gas in a processing vessel that can be evacuated.
• the present invention is a film forming method characterized in that the heat treatment is a CVD (Chemical Vapor Deposition) method.
• CVD Chemical Vapor Deposition
• the present invention is a film forming method characterized in that the heat treatment is an ALD (Atomic Layer Deposition) method in which film formation is performed by alternately and repeatedly supplying the source gas and the reducing gas.
• ALD Atomic Layer Deposition
• the present invention is characterized in that in the heat treatment, the two source gases are alternately and repeatedly supplied over an intermittent period, and the reducing gas is supplied during the intermittent period. Is the method.
• the present invention provides a film forming method characterized in that a copper film is deposited by a CVD method on the object to be processed on which the thin film has been formed, and the concave portion of the object to be processed is loaded.
• the present invention is the film forming method characterized in that the embedding process is performed in a processing container in which the thin film is formed.
• the present invention is a film forming method characterized in that after the embedding process is performed, an annealing process is performed on the object to be processed.
• the present invention is a film forming method characterized in that the annealing process is performed in a processing container in which the thin film is formed.
• the present invention provides a film forming method characterized in that a copper film is deposited on the object to be processed on which the thin film has been formed by a plating method to carry out the recessing process of the concave part of the object to be processed.
• the present invention is the film forming method characterized in that after the recess processing of the object to be processed is performed, annealing is performed on the object to be processed.
• the present invention provides the supply amount of the copper-containing source gas and Z or the transition metal-containing source gas in order to change the composition ratio of copper and transition metal in the thin film in the film thickness direction of the thin film.
• the film forming method is characterized in that it is changed during the heat treatment.
• the supply amount of each source gas is controlled so that the composition ratio of the transition metal in the thin film becomes smaller as the lower layer side in the thin film becomes larger toward the upper layer side. This is a characteristic film forming method.
• the present invention is characterized in that the amount of the transition metal contained in the thin film is within a range of 0.7 to 2.6 nm in terms of the film thickness of the pure metal of the transition metal. This is a film forming method.
• the surface of the treatment body is the base film of the thin film
• the base film includes a SiO film, a SiOC film, a SiCOH film, a SiCN film, a porous silica film, and a porous methylsilce.
• a film forming method comprising: one or more films selected from the group consisting of a skioxane film, a polyarylene film, a SiLK (registered trademark) film, and a fluorocarbon film.
• the present invention is the film forming method, wherein the transition metal-containing source of the transition metal-containing source gas is made of an organic metal material or a metal complex material.
• the organometallic material is M (R_Cp) x (x is a natural number), where M represents a transition metal, R represents an alkyl group, and H, CH, CH, CH From the group consisting of CH
• One of the selected Cp is a cyclopentanegenyl group (C H).
• the organometallic material is M (R—Cp) x (CO) y (x and y are natural numbers), wherein M represents a transition metal, and R represents an alkyl group. From H, CH, CH, CH, CH, CH
• Cp is a cyclopentanegenyl group (C H)
• CO is a cal
• the present invention is the film forming method, wherein the organometallic material comprises a transition metal, C and H.
• the transition metal is selected from the group consisting of Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh, Tc, Al, Mg, Sn, Ge, Ti, and Re. It is a film forming method characterized by being one or more metals.
• Mn (acac) [ Mn (C H O)]
• Mn (hfac) [ Mn (C HF O)]
• the film forming method is characterized in that it is one or more materials selected from the above.
• the present invention is a film forming method characterized in that plasma is used in combination in the heat treatment.
• the present invention is characterized in that the source gas and the reducing gas are mixed for the first time in the processing vessel. This is a film forming method.
• the present invention is the film forming method, wherein the reducing gas is H gas.
• the present invention provides a film forming apparatus for forming a thin film containing a transition metal on a surface of an object to be processed by a heat treatment, a processing container that can be evacuated, and a processing container provided in the processing container.
• a mounting table structure for mounting a body, a heating means for heating the object to be processed, a gas introducing means for introducing a gas into the processing container, and a raw material gas for supplying a raw material gas to the gas introducing means
• a film forming apparatus comprising: a supply unit; and a reducing gas supply unit that supplies a reducing gas to the gas introduction unit.
• the source gas supply means has different source gas branch paths provided for each source gas, and the source gas branch paths merge in the middle.
• the film forming apparatus is characterized in that the film is formed.
• the source gas supply means has different source gas branch paths provided for each source gas, and the source gas branch paths merge in the middle.
• the film forming apparatus is characterized in that it is commonly connected to the gas introducing means without being connected.
• the present invention is characterized in that a flow path heating means for heating is provided in the branch path of the raw material gas in order to prevent liquefaction of the raw material gas flowing in the raw material gas flow path.
• the film forming apparatus is characterized in that a flow path heating means for heating is provided in the branch path of the raw material gas in order to prevent liquefaction of the raw material gas flowing in the raw material gas flow path.
• the present invention is the film forming apparatus, wherein the source gas contains a transition metal-containing source gas containing at least a transition metal.
• the present invention is the film forming apparatus, wherein the source gas includes a copper-containing source material containing copper and a transition metal-containing source gas containing a transition metal.
• the present invention is the film forming apparatus characterized in that the reducing gas is H gas.
• the present invention is a computer program that is used in a film forming apparatus and causes a computer to execute a film forming method.
• the film forming method transports an object to be processed into a processing container that can be evacuated. And a step of supplying a transition metal-containing source gas containing at least a transition metal in the processing vessel and a reducing gas, heating the target object, and forming a thin film on the surface of the target object by heat treatment. It is a computer program characterized by having it.
• the present invention relates to a processing container that can be evacuated, a mounting table structure that is provided in the processing container for mounting the processing object, and a heating unit that heats the processing object.
• a gas introduction means for introducing gas into the processing vessel, a raw material gas supply means for supplying a raw material gas to the gas introduction means, a reducing gas supply means for supplying a reducing gas to the gas introduction means, and an entire apparatus
• the film forming method includes: Can not be evacuated A process for transporting the object to be processed into the treated container, a transition metal-containing source gas containing at least a transition metal and a reducing gas in the process container, and heating the object to be treated. And a step of forming a thin film on the surface by heat treatment.
• the present invention is a computer program characterized in that the source gas includes a copper-containing source gas containing copper and a transition metal-containing source gas containing a transition metal.
• the present invention is used in a film forming apparatus, and in a storage medium storing a computer program for causing a computer to execute a film forming method, the film forming method is contained in a processing container that can be evacuated.
• a process of transporting the object to be processed, a transition metal-containing source gas containing at least a transition metal in the processing container, and a reducing gas are supplied, the object to be processed is heated, and a thin film is formed on the surface of the object to be processed by heat treatment.
• a computer-readable storage medium storing a computer program.
• the present invention provides a processing container that can be evacuated, a mounting table structure that is provided in the processing container for mounting a processing object, and a heating unit that heats the processing object.
• a gas introduction means for introducing gas into the processing vessel, a raw material gas supply means for supplying a raw material gas to the gas introduction means, a reducing gas supply means for supplying a reducing gas to the gas introduction means, and an entire apparatus
• a storage medium storing a computer program for causing a computer to execute a film forming method for forming a thin film containing a transition metal on a surface of the object to be processed by heat treatment using a film forming apparatus having a control means for controlling.
• the film forming method includes a step of transporting an object to be processed into a processing container that can be evacuated, a transition metal-containing source gas containing at least a transition metal in the processing container, and a reducing gas. Together by heating the object to be processed, a computer-readable storage medium storing a computer program, characterized in that example Bei forming a thin film, the heat treatment on the surface of the object.
• the present invention provides a computer-readable storage medium storing a computer program, wherein the source gas includes a copper-containing source gas containing copper and a transition metal-containing source gas containing a transition metal.
• a copper-containing source gas containing copper, a transition metal-containing source gas containing a transition metal, and a reducing gas are supplied to the surface of the object to be processed, and a thin film is formed by heat treatment. Form. For this reason, even a minute recess can be embedded with high step coverage, and the apparatus cost can be greatly reduced by performing continuous processing with the same processing apparatus.
• the supply amount of each source gas is changed during the heat treatment so that the composition ratio of copper and transition metal in the thin film is changed in the film thickness direction of the thin film. It is possible to improve the adhesion.
• the amount of transition metal contained in the thin film is optimized, it is possible to prevent deterioration of the film quality characteristics of the copper wiring due to an excessive amount of transition metal.
• FIG. 1 is a block diagram showing an example of a film forming apparatus according to the present invention.
• FIGS. 2 (A), (B), (C), and (D) are diagrams showing the deposition state of a thin film in each process centering on a recess of a semiconductor wafer.
• FIGS. 3 (A) and 3 (B) are flowcharts showing each step of the film forming method of the present invention.
• FIGS. 4 (A), 4 (B), and 4 (C) are timing charts for explaining supply states of respective gases by the ALD method when forming a seed film.
• Fig.5 shows Mn-containing source gas and Cu-containing source gas with deposition time and heat treatment deposition It is a graph which shows an example of the change of the supply amount.
• FIG. 6 is a partial configuration diagram showing a modification of the raw material gas supply means of the film forming apparatus.
• FIGS. 7A, 7B and 7C are diagrams showing a general embedding process of a recess of a semiconductor wafer.
• FIG. 1 is a block diagram showing an example of a film forming apparatus according to the present invention.
• a film forming apparatus 12 according to the present invention includes an aluminum processing container 14 having a substantially circular cross section.
• a container heating means (not shown) such as a heater rod for heating the processing container 14 is provided on the side wall of the processing container 14.
• a ceiling head 16 is provided on the ceiling of the processing container 14 as a gas introducing means for introducing a necessary processing gas, for example, a film forming gas.
• the shutter head section 16 has a gas injection surface 18 on its lower surface, and a processing gas is injected toward the processing space S from a number of gas injection holes 20A, 20B provided in the gas injection surface 18.
• the shower head portion 16 there are formed two hollow gas diffusion chambers 22A and 22B communicating with the gas injection holes 20A and 20B, which are introduced into the gas diffusion chambers 22A and 22B.
• the processed gas diffused in the plane direction and then blown out from the gas injection holes 20A and 20B communicated with the gas diffusion chambers 22A and 22B.
• the gas injection holes 20A and 20B are arranged in a matrix shape, and the gases injected from the injection holes 20A and 20B of the respective gases are mixed in the processing space S.
• Such a gas supply form is referred to as postmix.
• the entire shower head portion 16 is formed of nickel alloy such as Nikkenore or Hastelloy (registered trademark), anoreminium, or anoreminium alloy.
• the shower head unit 16 may have one gas diffusion chamber.
• a sealing member 24 made of, for example, an O-ring is interposed at the joint between the shower head portion 16 and the upper end opening of the processing vessel 14 to maintain the airtightness in the processing vessel 14. It is like that.
• the side wall of the processing container 14 has a semiconductor as an object to be processed with respect to the inside of the processing container 14.
• a loading / unloading port 26 for loading / unloading the body wafer W is provided, and the loading / unloading port 26 is provided with a gate valve 28 that can be opened and closed airtightly.
• An exhaust space 32 is formed in the bottom 30 of the processing container 14. Specifically, a large opening 34 is formed in the central portion of the container bottom 30, and a cylindrical partition wall 36 having a bottomed cylindrical shape extending downward is connected to the opening 34. The exhaust space 32 is formed.
• a mounting table structure 40 is provided on the bottom 38 of the cylindrical partition wall 36 that partitions the exhaust space 32 so as to stand up from the bottom 38.
• the mounting table structure 40 includes a cylindrical column 42 standing upright from the bottom 38, and a mounting table 44 that is fixed to the upper end of the column 42 and mounts a semiconductor wafer W as an object to be processed on the upper surface. including.
• the mounting table 44 is made of, for example, a ceramic material made of quartz glass.
• a resistance heating heater 46 made of, for example, a carbon wire heater or the like that generates heat when energized is accommodated as a heating means, and the semiconductor wafer W mounted on the upper surface of the mounting table 44 is heated. I can get it.
• the mounting table 44 is formed with a plurality of, for example, three pin through holes 48 penetrating in the vertical direction (only two are shown in FIG. 1).
• a push-up pin 50 inserted in a loosely-fitted state so as to be vertically movable is arranged in 48.
• a push-up ring 52 made of ceramics such as alumina formed in a circular ring shape is disposed at the lower end of the push-up pin 50, and the lower end of each push-up pin 50 is not fixed to the push-up ring 52. It is supported in the state.
• the arm portion 54 extending from the push-up ring 52 is connected to an in / out rod 56 provided through the container bottom 30, and this in / out rod 56 can be moved up and down by an actuator 58.
• an actuator 58 As a result, the push-up pins 50 are raised and lowered from the upper ends of the pin insertion holes 48 when the wafer W is transferred.
• an extendable bellows 60 is interposed in the through-hole at the bottom of the container of the retracting rod 56 of the actuator 58, and the retracting rod 56 can be moved up and down while maintaining the airtightness in the processing container 14.
• the opening 34 on the inlet side of the exhaust space 32 is set to be smaller than the diameter of the mounting table 44, and the processing gas flowing outside the peripheral edge of the mounting table 44 rotates below the mounting table 44. And flows into the opening 34.
• On the lower side wall of the cylindrical partition wall 36 this An exhaust port 62 is formed so as to face the exhaust space 32, and a vacuum exhaust system 64 is connected to the exhaust port 62.
• the evacuation system 64 has an exhaust passage 66 connected to the exhaust port 62.
• a pressure regulating valve 68, a vacuum pump 70, and the like are sequentially disposed, and the inside of the processing vessel 14 is disposed.
• the atmosphere in the exhaust space 32 can be evacuated by evacuating while controlling the pressure.
• a raw material gas supply means 72 for supplying a raw material gas and a reducing gas supply means 74 for supplying a reducing gas are connected.
• the source gas supply means 72 has a source gas flow path 78 connected to the gas inlet 76 of one gas diffusion chamber 22A of the two gas diffusion chambers.
• This source gas channel 78 is branched into two here, and one branch channel 80 is provided with a first source material by sequentially providing an on-off valve 82 and a flow rate controller 84 such as a mass flow controller in the middle. Is connected to a first source 86 containing
• a transition metal-containing raw material containing a transition metal is used as the first raw material.
• the raw material is gasified to contain the transition metal.
• the source gas can be supplied along with the inert gas.
• the first raw material source 86 is heated by the heater 86a in order to increase the vapor pressure of the raw material.
• the transition metal-containing raw material for example, (MeCp) Mn (precursor) containing manganese can be used.
• the supply of the raw material gas may use not only the publishing method but also a liquid raw material vaporization method or a solution raw material vaporization method.
• the liquid raw material vaporization method refers to a method in which a raw material that is liquid at room temperature is vaporized with a vaporizer
• the solution raw material vaporization method refers to a solution in which a raw material that is solid or liquid at room temperature is dissolved in a solvent to form a liquid.
• Such a system can be applied to supply of Cu source gas as well as supply of Mn source gas.
• the other branch path 88 is connected to a second raw material source 94 that accommodates the second raw material by sequentially providing an on-off valve 90 and a flow rate controller 92 such as a mass flow controller on the way. ing.
• a copper-containing raw material containing copper is used as the second raw material.
• the second raw material a copper-containing raw material containing copper is used.
• an inert gas such as Ar gas whose flow rate is controlled
• the feed gas can be supplied with the inert gas.
• the second raw material source 94 is heated by the heater 94a in order to increase the vapor pressure of the raw material.
• the copper-containing raw material include Cu (hfac) TMVS, Cu (hfac), Cu containing Cu
• He, Ne, or the like can be used instead of Ar gas as the inert gas for bubbling.
• each of the branch paths 80 and 88, the on-off valves 82 and 90 interposed therebetween, the flow rate controllers 84 and 92, and the source gas passage 78, tape is used to prevent the source gas from being liquefied again.
• a heater 96 is provided so as to heat them.
• a plurality of raw material gas supply means may be installed according to the raw material to be used.
• the reducing gas supply means 74 has a reducing gas passage 100 connected to the gas inlet 98 of the other gas diffusion chamber 22B.
• This reducing gas flow path 100 is connected to a reducing gas source 106 for containing reducing gas through an on-off valve 102 and a flow rate controller 104 such as a mass flow controller in the middle.
• H gas is used as the reducing gas.
• the source gas is connected to the gas diffusion chamber 22A located above the shower head section 16, and the reducing gas is connected to the gas diffusion chamber 22B located below.
• the shower head section 16 faces and is close to the mounting table 44, and therefore the temperature of the gas injection surface 18 tends to rise.For this reason, when the raw material gas is introduced into the lower gas diffusion chamber 22B, the gas flows. This is because there is a risk of disassembly.
• an inert gas supply means for purging is connected to the shower head section 16 so as to supply purge gas as required.
• purge gas inert gas such as N gas, Ar gas, He gas, Ne gas can be used.
• control means 108 made of, for example, a microcomputer, and controls the start and stop of the supply of each gas, the control of the supply amount, The pressure in the processing container 14 is controlled, and the temperature of the wafer W is controlled.
• the control means 108 is a computer program for performing the control described above.
• Storage medium 110 for storing.
• a flexible disk, a flash memory, a hard disk, a CD (Compact Disc), or the like can be used.
• an unprocessed semiconductor wafer W is carried into the processing container 14 through the gate vano lev 28 and the carry-in / out port 26 which are opened by being held by a transfer arm (not shown).
• the wafer W is delivered to the raised push-up pin 50 and then placed on the upper surface of the placing table 44 by lowering the push-up pin 50.
• the raw material gas supply means 72 and the reducing gas supply means 74 are operated to supply predetermined respective gases such as a film forming gas as a processing gas to the shower head unit 16 while controlling the flow rate. Gas is blown out from the gas injection holes 20A and 20B and injected, and introduced into the processing space S. There are various ways of supplying each gas, as will be described later.
• the vacuum pump 70 provided in the vacuum exhaust system 64 the atmosphere in the processing vessel 14 and the exhaust space 32 is evacuated, and the valve opening of the pressure control valve 68 is adjusted. Maintain the atmosphere of the processing space S at the specified process pressure.
• the temperature of the wafer W is heated by a resistance heater 46 provided in the mounting table 44 and maintained at a predetermined process temperature. As a result, a desired thin film is formed on the surface of the semiconductor wafer W by a heat treatment such as a thermal CVD method.
• the source gas passage 78 and both branch passages 80 and 88 are heated by the passage heating means 96 to prevent the source gas flowing therethrough from being liquefied. Power
• the heating temperature at this time depends on the raw material gas used.
• Cu (Mac) TMVS and (MeCp) Mn are used as the raw material gas, both gases are not liquefied and are heated.
• the shower head 16 and the processing container 14 themselves are heated to about 60 to 80 ° C.
• FIG. 2 is a view showing the deposition state of a thin film in each step centering on the concave portion of the semiconductor wafer
• FIG. 3 is a flowchart showing each step of the film forming method of the present invention
• FIG. 3 (A) is the first implementation. An example is shown
• FIG. 3B shows a second embodiment.
• Figure 4 shows the ALD method used to form the seed film. It is a timing chart explaining the supply state of each gas by.
• One of the objects of the method of the present invention is to perform each film forming process and annealing process continuously in one film forming apparatus (in situ). For example, when the wafer W is carried into the film forming apparatus 12, as shown in FIG. 2A, trenches or holes are formed on the surface of the insulating layer 1 formed on the wafer W, such as an interlayer insulating film. Such a recess 2 is formed, and a lower wiring layer 3 made of copper or the like is exposed at the bottom of the recess 2.
• the insulating layer 1 serving as a base film is made of an oxide containing silicon, for example, SiO.
• a seed film 6 is first formed on the surface of the semiconductor wafer W in such a state as shown in FIG.
• the seed film 6 may be a CuMn alloy film (S1 in FIG. 3 (A)), or an Mn film (SI_1 in FIG. 3 (B)).
• the seed film 6 can be formed by a CVD method or an ALD method.
• the ALD method is a film forming method in which different film forming gases are alternately supplied to repeatedly form an atomic level or molecular level thin film layer by layer.
• a Cu film 8 is formed as a metal film in the loading process to fill the recess 2 (S2 in FIG. 3 (A) and FIG. 3 (B) ) S2).
• This embedding process may be performed by a CVD method, an ALD method, or a PVD method (sputter deposition) or a plating method as in the conventional method.
• the wafer W is subjected to an annealing process by exposing it to a high temperature, and as shown in FIG. Self-aligned reaction at the boundary with the insulating layer 1 made of SiO film
• the barrier layer 112 made of the MnSixOy (x, y: any integer) film is surely formed (S3 in FIG. 3A and S3 in FIG. 3B).
• This annealing process may not be performed if the barrier layer 112 has already been formed in the previous process involving a high temperature process. However, in order to sufficiently form the barrier film 112, this annealing process is not necessary. Is preferably performed.
• the first film formation method is to form a CuMn alloy film by the CVD method by flowing all of the Cu-containing source gas, the Mn-containing source gas, and the reducing gas H gas simultaneously.
• the second film-forming method employs the ALD method to supply the Cu-containing source gas and the Mn-containing source gas in synchronism with each other. Alternately between
• the intermittent period T1 between the two gases and H gas is the purge period.
• the residual gas in the processing container 14 may be removed only by evacuation, N gas etc.
• ALD method for example, there is a force cycle from the supply of one Mn-containing source gas to the supply of the next Mn-containing source gas, and this is a very thin layer, for example, 0.4 to 0.
• a CuMn alloy film of about 6 nm is formed.
• the required thickness of the seed film 6 is, for example, about 2 nm in terms of the film thickness of the Mn pure metal in the CuMn film, and the film forming process is performed, for example, about 10 to 100 cycles.
• the controllability of the film thickness can be increased, and a thinner film can be formed with better controllability than the CVD method.
• the process conditions at this time are a process temperature of about 70 to 450 ° C and a process pressure force of about SlPa to 13kPa.
• the flow rate of the Mn-containing source gas is about 0.1 to:! Osccm, and the flow rate of the Cu-containing source gas is about 1 to 100 sccm.
• the amount of Cu is about 10 times higher than that of Mn.
• the flow rate of H gas is about 5 to 500 sccm.
• the flow rate ratio of the Mn-containing source gas to the gas may be increased so that the resulting alloy film components become Mn-rich.
• the supply period tl of the Mn-containing source gas is about 10 to 15 seconds
• the supply period of the Cu-containing source gas t2 is about 10 sec
• the supply period of H gas t3 is about 10 sec
• the intermittent period T1 is 20 to 20 sec.
• Cu has good adhesion to insulating films such as SiO.
• the supply period tl of the Mn-containing source gas with respect to the supply period t2 of the Cu-containing source gas may be increased at the initial stage of film formation, for example, 15 sec (indicated by the dotted line 121 in FIG. 4 (A)).
• the process recipe is such that the supply ratio of the Mn-containing source gas and the Cu-containing source gas changes sequentially according to the transition of the deposition time or according to the deposited film thickness. Can be assembled.
• the adhesion between the insulating layer 1 and the seed film 6 and between the seed film 6 and the Cu film 8 can be increased, and film peeling during film formation can be prevented.
• the seed is in an alloy state in which a very thin Mn film with a film thickness of about 0.2 to 0.3 nm and a very thin layer with a film thickness of about 0.2 to 0.3 nm are stacked alternately. It becomes membrane 6.
• the Mn-containing material is supplied prior to the supply of the Cu-containing source gas in consideration of the adhesion and barrier properties between the seed film 6 and the insulating layer 1. It is desirable to arrange steps so that the source gas is supplied. Since both films are very thin, Mn and Cu diffuse into each other and become alloyed.
• Such film formation by the ALD method can sufficiently improve the step coverage since the film adheres sufficiently to the inner wall of the fine recess as compared with the film formation by the CVD method.
• the ALD method is more effective as the size of the recess becomes finer.
• Fig. 4 (A) and Fig. 4 (B) show the Cu-containing source gas and H gas.
• the flow may be repeated alternately.
• metal film 8 made of Cu film is formed by simple thermal decomposition reaction without flowing H gas.
• the process conditions at this time are a process temperature of about 70 to 450 ° C and a process pressure of about 1 Pa to 13 kPa.
• the flow rate of Cu-containing source gas is about 1 to lOOsccm, and the flow rate of H gas is about 5 to 500 sccm.
• a conventional PVD method sputter deposition
• a plating method is used to form and fill the metal film 8 made of the Cu film. Good.
• a thin film can be easily deposited on the inner wall of a fine recess as compared with the plating method. Therefore, even if the recess is further miniaturized, a void or the like is generated inside. It is possible to fill the recess without any problem.
• the wafer W after the above-described embedding process is brought to a predetermined process temperature, for example, about 100 to 450 ° C. By heating, the boundary between the seed film 6 and the insulating layer 1 made of the SiO film as the base film
• the barrier layer 112 made of the MnSixOy film is surely formed in a self-aligning manner.
• oxygen may be supplied from the enzyme supply means 76a into the processing container to control the oxygen partial pressure.
• This annealing treatment is intended to surely form the barrier layer 112. Therefore, the seed film forming process and the Cu film forming process, which are the previous processes, are performed at a sufficiently high temperature, for example, 150 ° C or higher. If the process temperature is high, the barrier layer 112 has already been formed with a sufficient thickness, so that the annealing process can be dispensed with. Of course, when the plating process is performed at S2 in FIG. 3 (A), the annealing process is performed.
• the seed film formation process, the Cu film formation process by CVD or ALD, and the annealing process can all be performed continuously in the same processing apparatus 12.
• the Cu-containing source gas containing copper the Mn-containing source gas containing manganese as a transition metal, and the H gas as a reducing gas.
• Fig. 5 is a graph showing an example of changes in the supply amounts of Mn-containing source gas and Cu-containing source gas as the film formation time (heat treatment) changes. Note that the graph only shows the trend of changes in supply volume, not the absolute value of supply volume.
• the copper-containing source gas and / or the transition metal-containing source gas is used to change the composition ratio of copper Cu in the thin film and a transition metal such as Mn in the film thickness direction of the thin film.
• the supply amount is changed during the heat treatment. Specifically, the supply amount of each raw material gas is controlled so that the composition ratio of the transition metal in the thin film of the CuMn film, which is a thin film, becomes smaller as the lower layer side in the thin film increases toward the upper layer side.
• the Mn-containing source gas is flowed at a large flow rate at the initial stage of film formation, and after a while, the flow rate is decreased sequentially, for example, linearly as the film formation time elapses. Set the flow rate to approximately zero.
• the Cu-containing source gas hardly flows for a while at the initial stage of film formation, and a pure Mn metal film is formed, and the Cu-containing source gas corresponding to the decrease in the Mn-containing source gas is formed.
• the gas flow rate is increased, for example, linearly as the film formation time elapses.
• the flow rate of the Cu-containing source gas is maximized while the supply amount of the Mn-containing source gas is maintained at zero, and the film is formed for a while.
• a pure Cu metal film is formed.
• the thin film in this case becomes a pure Mn metal film at the initial stage of film formation, then becomes a CuMn alloy and continues in a Mn rich state, reverses to a Cu rich state in the middle, and finally becomes a pure Cu metal film. It has become.
• Fig. 5 (B) the Mn source gas is gradually reduced from a certain supply amount from the start of film formation, and conversely, the Cu-containing source gas is gradually increased from zero supply amount.
• the entire thickness direction of the thin film is a CuMn film, and no pure Mn metal film or pure Cu metal film is formed as shown in Fig. 5 (A).
• Fig. 5 (A) and Fig. 5 (B) the linear increase is shown. Force that is an additive characteristic or a decreasing characteristic Instead of this, the supply amount of each source gas may be adjusted so as to have a curve-like increasing characteristic or a decreasing characteristic.
• Fig. 5 (A) and Fig. 5 (B) above in the CuMn alloy film portion, the composition ratio of Cu and Mn increases from the bottom to the top of the film thickness and from the Mn rich state to the Cu rich state. It will change continuously to the state of.
• Fig. 5 (C) shows a case where the Mn-containing source gas is decreased in steps (steps), while the Cu-containing source gas is increased in steps (steps). .
• the composition ratio of Cu and Mn in the CuMn alloy film changes stepwise. Of course, the number of steps is not particularly limited. In the case shown in FIGS.
• the lower layer in the film is a pure Mn metal film or Mn-rich CuMn alloy
• the upper layer is a pure Cu metal film or Cu-rich CuMn alloy. Since it is gold, as described above, it is possible to further improve the adhesion between the base film Si02 and the Cu film 8.
• the case where a CuMn alloy film is formed as the seed film 6 has been described as an example (S1 in FIG. 3A).
• the Mn film (see FIG. B1-1 S1-1) may be formed.
• the Mn-containing source gas and the reducing gas H gas are simultaneously flown and formed by the CVD method, and the above Mn-containing film is formed.
• source gas and H gas are alternately flowed repeatedly and formed by the ALD method.
• any of the methods can be used.
• the process conditions in this case such as the process pressure, process temperature, and flow rate of each gas, are the same as those described with reference to FIGS. 4 (A) and 4 (B).
• S2 and S3 in FIG. 3 (B) are processes having the same contents as S2 and S3 in FIG. 3 (A).
• the annealing process of S3 in Fig. 3 (B) can be omitted.
• the adhesion between these metals can be improved by treating these films in-situ.
• the upper Cu wiring layer 8 has a lower resistance at the bottom of the recess 2 than the Cu film via the Mn film having a higher resistance than the Cu film. Will be connected.
• This seed film is much thinner than the conventional sputtering Mn film, so most of the Mn element is Cu wiring layer 3 and Cu distribution by annealing treatment. By diffusing into the line layer 8, it does not exist as an Mn layer, so the contact resistance of this part will not increase.
• the amount of Mn metal in the thin film CuMn film (including the case of having a pure Mn metal film or pure Cu metal film) or in the Mn film has an optimum value, and the value is the pure metal film of Mn. It is preferable to form the thin film so as to be within a range of 0.7 to 2.6 nm in terms of thickness and to be within the range of the converted value of the Mn metal film. That is, in the annealing process, as described above, Mn is combined into an MnSixOy film, and excessive Mn is diffused to some extent in the Cu film by diffusion, but is discharged to the surface, but the amount of Mn is excessive. If contained in the film, the Mn component that could not be exhausted will remain in the Cu film that contains the recess, and this remaining Mn component will cause an increase in the resistance value of the Cu wiring. Reliability will be reduced.
• a necessary and sufficient amount of Mn is obtained by setting the Mn content in the thin film within the range of 0.7 to 2.6 nm in terms of the Mn pure metal film thickness as described above. Can be held in the barrier layer that forms the interface between the Cu wiring and the insulating layer.
• the Mn amount is smaller than 0.7 nm, a barrier layer having good characteristics cannot be formed.
• the Mn amount is larger than 2.6 nm, as described above, an excess amount is not obtained. The Mn component remains in the Cu wiring and degrades the film quality.
• FIG. 6 is a partial configuration diagram showing a modified example of the source gas supply means of the film forming apparatus configured as described above.
• the shower head unit 16 and the raw material gas supply means 72 connected thereto are shown, and the same components as those shown in FIG. 1 are given the same reference numerals.
• source gas flow paths 120 and 122 extend from the first source source 86 containing Mn and the second source source 94 containing Cu, respectively.
• the raw material gas flow paths 120 and 122 are connected to the common gas inlet 76 of the shower head unit 16 without being joined in the middle, and both are mixed with each other during the raw material gas transfer. It is designed to be introduced into the shower head 16 without matching.
• each of the source gas channels 120 122 is provided with a channel heating means 96a 96b made of, for example, a tape heater so that each source gas flowing therethrough is provided. Heated to prevent liquefaction.
• the power S can be heated and maintained at the optimum temperature corresponding to the flowing raw material gas.
• the raw material gas flow path 96a is, for example,
• the raw material gas flow path 96b is set to a range of 55 70 ° C, for example. In this case, the same effects as those described above can be exhibited.
• the organometallic material is not limited to those described above, and any material composed of a transition metal, C (carbon), and H (hydrogen) may be used.
• M (R_Cp) x (x is a natural number) can be used as the organometallic material, or M (R_Cp) x (CO) y (xy is a natural number) can be used.
• M represents a transition metal
• R represents an aralkyl group, and is one selected from the group consisting of H CH C H C H C H and C
• P is a cyclopentane genyl group (C H), and CO is a carbonyl group.
• a metal complex material can be used.
• the present invention is not limited to this, and it is also possible to use a SiOC film, a SiCOH film, or the like, which is a Low_k (low relative dielectric constant) material used as an interlayer insulating layer.
• Si ⁇ film including thermal oxide film and plasma TEOS film
• SiOC film SiCOH film
• SiCN film porous film
• a lath silica film a porous methyl cinresesquioxane film
• a polyarylene film a polyarylene film
• SiLK registered trademark
• fluorocarbon film fluorocarbon film
• Agents such as ethanol, isopropyl alcohol, acetone, hexane, octane, butyl acetate and the like can also be used.
• Mn As the transition metal is not limited to this, and other transition metals such as Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh
• Mn, Nb, Zr, Cr, V, Y, Pd, Ni, Pt, Rh One or more metals selected from the group consisting of Tc, Al, Mg, Sn, Ge, Ti, and Re can be used.
• the film forming apparatus described here is merely an example.
• a heating lamp such as a halogen lamp may be used as a heating unit instead of a resistance heater, or the processing apparatus may be a single wafer. Not only a formula but also a batch type may be used.
• the present invention is not limited to film formation by heat treatment.
• the shower head unit 16 is used as an upper electrode
• the mounting table 44 is used as a lower electrode
• high frequency power is applied between both electrodes as necessary to raise a plasma.
• plasma assistance may be applied during film formation.
• the force described using a semiconductor wafer as an example of the object to be processed is not limited to this, and the present invention can be applied to a glass substrate, an LCD substrate, a ceramic substrate, and the like.

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• 2007
  • 2007-06-05 JP JP2007148856A patent/JP2008013848A/ja not_active Withdrawn
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