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WO2020195903A1 - 成膜方法および成膜装置 - Google Patents

成膜方法および成膜装置 Download PDF

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Publication number
WO2020195903A1
WO2020195903A1 PCT/JP2020/010854 JP2020010854W WO2020195903A1 WO 2020195903 A1 WO2020195903 A1 WO 2020195903A1 JP 2020010854 W JP2020010854 W JP 2020010854W WO 2020195903 A1 WO2020195903 A1 WO 2020195903A1
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Prior art keywords
region
gas
film
substrate
boron
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PCT/JP2020/010854
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English (en)
French (fr)
Inventor
河野　有美子
秀司 東雲
進一 池
Original Assignee
東京エレクトロン株式会社
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Application filed by 東京エレクトロン株式会社 filed Critical 東京エレクトロン株式会社
Priority to KR1020217033044A priority Critical patent/KR102650949B1/ko
Priority to US17/598,175 priority patent/US20220181144A1/en
Publication of WO2020195903A1 publication Critical patent/WO2020195903A1/ja

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    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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    • H01L21/32—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 using masks
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    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
    • H01L21/31122—Etching inorganic layers by chemical means by dry-etching of layers not containing Si, e.g. PZT, Al2O3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
    • H01L21/76826—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by contacting the layer with gases, liquids or plasmas
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H01L21/76885—By forming conductive members before deposition of protective insulating material, e.g. pillars, studs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B05D1/322—Removable films used as masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H01L21/67103—Apparatus for thermal treatment mainly by conduction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H01L21/67109—Apparatus for thermal treatment mainly by convection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
    • H01L21/76883—Post-treatment or after-treatment of the conductive material

Definitions

  • the present disclosure relates to a film forming method and a film forming apparatus.
  • Patent Document 1 discloses a technique for selectively forming a target film in a specific region of a substrate without using a photolithography technique. Specifically, there is a technique of forming a self-assembled monolayer (SAM) that inhibits the formation of a target film in a part of the substrate and forming the target film in the remaining region of the substrate. It is disclosed.
  • SAM self-assembled monolayer
  • SAM can be selectively formed in the second region of the first region where the oxide formed by the surface oxidation of the conductive material is exposed and the second region where the insulating material is exposed.
  • the film forming method of one aspect of the present disclosure is A step of preparing a substrate having a first region where the oxide formed by surface oxidation of the conductive material is exposed and a second region where the insulating material is exposed, and A step of replacing the oxide film of the conductive material with a boron oxide film by supplying a boron halide gas to the substrate.
  • a conductive target film is selectively applied to the first region of the first region and the second region where the conductive material is exposed. Including the step of forming.
  • SAM is selectively formed in the second region of the first region where the oxide formed by the surface oxidation of the conductive material is exposed and the second region where the insulating material is exposed. it can.
  • FIG. 1 is a flowchart showing a film forming method according to an embodiment.
  • FIG. 2 is a side view showing an example of the state of the substrate in the steps S101 to S104 shown in FIG.
  • FIG. 3 is a side view showing an example of the state of the substrate in the steps S105 to S108 shown in FIG.
  • FIG. 4 is a cross-sectional view showing an example of a film forming apparatus for carrying out steps S101 to S107 shown in FIG.
  • FIG. 5 is a cross-sectional view showing an example of a polishing apparatus for carrying out the step S108 shown in FIG.
  • FIG. 1 is a flowchart showing a film forming method according to an embodiment.
  • FIG. 2 is a side view showing an example of the state of the substrate in the steps S101 to S104 shown in FIG.
  • FIG. 2A shows the state of the substrate prepared in step S101
  • FIG. 2B shows the state of the substrate obtained in step S102
  • FIG. 2C shows the state of the substrate obtained in step S103.
  • FIG. 2D shows the state of the substrate obtained in step S104.
  • FIG. 3 is a side view showing an example of the state of the substrate in the steps S105 to S108 shown in FIG.
  • FIG. 3A shows the state of the substrate obtained in step S105
  • FIG. 3B shows the state of the substrate obtained in step S106
  • FIG. 3C shows the state of the substrate obtained in step S107.
  • FIG. 3D shows the state of the substrate obtained in step S108.
  • the film forming method includes a step S101 for preparing the substrate 10 as shown in FIG. 2A.
  • the preparation includes, for example, carrying the substrate 10 into the processing container 120 (see FIG. 4) described later.
  • the substrate 10 has a first region A1 in which the first material is exposed and a second region A2 in which a second material different from the first material is exposed.
  • the first region A1 and the second region A2 are provided on one side of the substrate 10 in the plate thickness direction.
  • the number of the first region A1 is one in FIG. 2A, but it may be plural.
  • two first regions A1 may be arranged so as to sandwich the second region A2.
  • the number of the second region A2 is one in FIG. 2A, but may be plural.
  • two second regions A2 may be arranged so as to sandwich the first region A1.
  • the third region is a region where a third material different from the first material and the second material is exposed.
  • the third region may be arranged between the first region A1 and the second region A2, or may be arranged outside the first region A1 and the second region A2.
  • the first material is, for example, an oxide formed by surface oxidation of a conductive material.
  • the conductive material is, for example, tungsten (W), and the oxide of the conductive material is, for example, tungsten oxide (WO).
  • W tungsten
  • WO tungsten oxide
  • the conductive material is tungsten in this embodiment, molybdenum (Mo), titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), vanadium (V), or vanadium nitride. (VN) or the like may be used.
  • Mo molybdenum
  • Ti titanium
  • TiN titanium nitride
  • TaN tantalum nitride
  • V vanadium nitride
  • VN vanadium nitride.
  • the surfaces of these conductive materials are naturally oxidized over time in the atmosphere.
  • the oxide is the first material.
  • Tungsten oxide is also referred to as "WO” regardless of the composition ratio of oxygen and tungsten.
  • Titanium nitride is also referred to as “TiN” regardless of the composition ratio of nitrogen and titanium.
  • tantalum nitride is also referred to as “TaN” and vanadium nitride is also referred to as "VN”.
  • the second material is, for example, an insulating material.
  • the insulating material is, for example, silicon oxide.
  • silicon oxide is also referred to as “SiO” regardless of the composition ratio of oxygen and silicon.
  • the second material is silicon oxide in this embodiment, it may be silicon nitride, silicon oxynitride, silicon carbide, aluminum oxide, or the like.
  • the second material may be a material that is hardly replaced with another material (for example, boron oxide) in step S102 described later. That is, in step S102 described later, the replacement rate from the second material to the other material is slower than the replacement rate from the first material to boron oxide.
  • the substrate 10 has, for example, a conductive film 11 formed of the above conductive material and an insulating film 12 formed of the above insulating material. On the surface of the conductive film 11, an oxide film 13 is naturally formed over time in the atmosphere.
  • the conductive film 11 is, for example, a tungsten film
  • the oxide film 13 is, for example, a tungsten oxide film.
  • the substrate 10 has a base substrate 14 on which the conductive film 11 and the insulating film 12 are formed.
  • the base substrate 14 is a semiconductor substrate such as a silicon wafer.
  • the base substrate 14 may be a glass substrate or the like.
  • the substrate 10 may further have a base film formed of a material different from that of the base substrate 14 and the conductive film 11 between the base substrate 14 and the conductive film 11. Similarly, the substrate 10 may further have a base film formed of a material different from the base substrate 14 and the insulating film 12 between the base substrate 14 and the insulating film 12.
  • the film forming method includes a step S102 of replacing the oxide film 13 with the boron oxide film 20 as shown in FIG. 2B by supplying boron halide gas to the substrate 10.
  • the metal halide and boron oxide are produced by the chemical reaction between the boron halide gas and the oxide film 13.
  • the substrate 10 is heated to a predetermined temperature, and the metal halide volatilizes, so that the boron oxide film 20 is formed.
  • the substrate 10 is heated to a temperature at which the vapor pressure of the metal halide is higher than the vapor pressure of boron oxide and the vaporization rate of the metal halide is higher than the vaporization rate of boron oxide.
  • boron halide gas boron trichloride (BCl 3 ) gas is used in this embodiment.
  • BCl 3 boron trichloride
  • the chemical reaction between the BCl 3 gas and WO produces, for example, WCl x and B 2 O 3 .
  • Substrate 10 is heated to a predetermined temperature, because WCl x is volatilized, B 2 O 3 film is formed.
  • the boron halide gas may be any gas containing boron and halogen, and is not limited to boron trichloride gas.
  • the boron halide gas may be boron trifluoride (BF 3 ) gas, boron triiodide (BI 3 ) gas, boron tribromide (BBr 3 ) gas, or the like.
  • the boron oxide film 20 is etched in the first region A1 by supplying a gas of a silane compound containing fluorine to the substrate 10, and the second The step S103 for forming the SAM (self-assembled monolayer) 30 in the region A2 is included.
  • the SAM 30 is formed by chemically adsorbing a silane compound to the second region A2, and inhibits the formation of the conductive target film 40 described later.
  • the SAM 30 may or may not be formed in the third region.
  • R and R' are functional groups such as a group in which at least a part of hydrogen of the alkyl group is replaced with fluorine.
  • the terminal group of the functional group is CF-based.
  • OR is a hydrolyzable functional group such as a methoxy group or an ethoxy group.
  • the silane-based compound containing fluorine is not particularly limited, but is, for example, CF 3 (CF 2 ) X CH 2 CH 2 SiCl 3 , CF 3 (CF 2 ) X CH 2 CH 2 Si (OMe) 3 , or CF 3 ( CF 2 ) X CH 2 CH 2 Si (OEt) 3 and the like.
  • X is an integer of 0 or more and 7 or less.
  • the boron oxide film 20 can be etched.
  • the formation of the SAM 30 and the etching of the boron oxide film 20 proceed at the same time, so that the formation of the SAM 30 can be suppressed.
  • SAM30 is hardly formed in the first region A1 as compared with the second region A2.
  • the gas can chemically react with the boron oxide film 20 while avoiding the SAM 30 in the step S104 described later. By this chemical reaction, the boron oxide film 20 can be removed and the conductive film 11 can be exposed.
  • step S104 which will be described later, is unnecessary. Since the silane compound is chemically adsorbed on the surface having an OH group, it is more easily chemically adsorbed on the metal compound than the metal. Therefore, when the conductive film 11 is a metal film, after the conductive film 11 is exposed, the silane compound is selectively chemisorbed on the second region A2 of the first region A1 and the second region A2.
  • the film forming method includes substitution of the oxide film 13 with the boron oxide film 20 (step S102), etching of the boron oxide film 20 and formation of the SAM 30 (step S103).
  • step S102 substitution of the oxide film 13 with the boron oxide film 20
  • step S103 formation of the SAM 30
  • the formation of the SAM 30 and the etching of the boron oxide film 20 proceed at the same time, so that the formation of the SAM 30 can be suppressed.
  • the film forming method is as shown in FIG. 2D by supplying gas to the substrate 10 after the formation of the SAM 30 (step S103) and before the formation of the conductive target film 40 (step S105). It has a step S104 of etching and removing the boron oxide film 20 remaining in the first region A1.
  • the gas used in this step S104 is not particularly limited, but is, for example, hydrogen fluoride (HF) gas.
  • HF hydrogen fluoride
  • chlorine trifluoride (ClF 3 ) gas and nitrogen trifluoride (NF 3 ) gas can also be used.
  • SAM30 Since SAM30 is resistant to the gas used in step S104, it remains in the second region A2.
  • the gas chemically reacts with the boron oxide film 20 while avoiding the SAM 30.
  • the boron oxide film 20 can be removed and the conductive film 11 can be exposed.
  • the SAM 30 on the boron oxide film 20 can also be removed, and the SAM 30 can be left only in the second region A2. That is, the lift-off of the SAM 30 can be carried out by removing the boron oxide film 20.
  • the film forming method is selected in the first region A1 in which the conductive material is exposed from the first region A1 and the second region A2 by using the SAM 30 formed in the second region A2.
  • the step S105 for forming the target film 40 which is conductive is included.
  • the target film 40 is formed of a material different from that of the SAM 30, such as a metal, a metal compound, or a semiconductor. Since the SAM 30 inhibits the formation of the conductive target film 40, the conductive target film 40 is selectively formed in the first region A1. When a third region exists in addition to the first region A1 and the second region A2, the conductive target film 40 may or may not be formed in the third region.
  • the conductive target film 40 is formed by, for example, a CVD (Chemical Vapor Deposition) method or an ALD (Atomic Layer Deposition) method.
  • the conductive target film 40 can be further laminated on the conductive film 11 originally existing in the first region A1.
  • the material of the conductive target film 40 and the material of the conductive film 11 are the same material (for example, W) in this embodiment, but may be different materials.
  • the material of the conductive target film 40 is molybdenum (Mo), titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), vanadium (V), in addition to tungsten (W). ), Vanadium nitride (VN), or the like.
  • a W-containing gas such as tungsten hexachloride (WCl 6 ) gas and a reducing gas such as hydrogen (H 2 ) gas are used as the processing gas on the substrate. It is supplied alternately with respect to 10.
  • These treatment gases may be heated to accelerate the chemical reaction.
  • these processing gases may be turned into plasma in order to promote a chemical reaction.
  • the film forming method is a step S106 of etching and removing the SAM 30 as shown in FIG. 3 (b) by supplying an oxygen-containing gas to the substrate 10 after the formation of the conductive target film 40 (step S105). including.
  • the oxygen-containing gas decomposes the SAM 30 and gasifies it.
  • the gasified SAM 30 is removed, and the insulating film 12 is exposed in the second region A2.
  • the oxygen-containing gas that etches the SAM 30 is not particularly limited, and is, for example, oxygen (O 2 ) gas, ozone (O 3 ) gas, water vapor, or the like. These oxygen-containing gases may be heated to a high temperature in order to promote a chemical reaction. In addition, these oxygen-containing gases may be turned into plasma in order to promote a chemical reaction.
  • the film forming method includes a step S107 of forming an insulating target film 50 in the first region A1 and the second region A2 as shown in FIG. 3C after the removal of the SAM 30 (step S106).
  • the insulating target film 50 is formed by, for example, a CVD method or an ALD method.
  • the insulating target film 50 can be further laminated on the insulating film 12 originally existing in the second region A2.
  • the material of the insulating target film 50 and the material of the insulating film 12 are the same material (for example, SiO) in this embodiment, but may be different materials.
  • the material of the conductive film 11 may be silicon nitride, silicon oxynitride, silicon carbide, aluminum oxide, or the like, in addition to silicon oxide.
  • Si-containing gas such as dichlorosilane (SiH 2 Cl 2 ) gas and oxidation gas such as ozone (O 3 ) gas are used as processing gases. It is supplied alternately to the substrate 10.
  • a reforming gas such as hydrogen (H 2 ) gas may be supplied to the substrate 10.
  • These treatment gases may be plasmatized to facilitate the chemical reaction.
  • these processing gases may be heated in order to promote a chemical reaction.
  • the conductive target film 40 is exposed in the first region A1, the insulating target film 50 is exposed in the second region A2, and the first region A1 is formed.
  • the step S108 is included in which the insulating target film 50 is polished so that the and the second region A2 are flat. Polishing of the insulating target film 50 is, for example, CMP (Chemical Mechanical Polishing). By polishing the insulating target film 50, the conductive target film 40 can be exposed in the first region A1. Further, the first region A1 and the second region A2 can be flattened.
  • FIG. 4 is a cross-sectional view showing an example of a film forming apparatus for carrying out steps S101 to S107 shown in FIG.
  • the film forming apparatus 100 may carry out at least steps S101 to S103 and S105 of the steps S101 to S108 shown in FIG. Of the remaining steps S104 and S106 to S108, step S104 may not be carried out as described above, and steps S106 to S108 may be carried out by another device.
  • the film forming apparatus 100 includes a processing unit 110, a conveying apparatus 170, and a control apparatus 180.
  • the processing unit 110 includes a processing container 120, a substrate holding unit 130, a heater 140, a gas supply device 150, and a gas discharge device 160.
  • the plurality of processing units 110 form a so-called multi-chamber system.
  • the plurality of processing units 110 are arranged so as to surround the vacuum transfer chamber 101.
  • the vacuum transfer chamber 101 is exhausted by a vacuum pump and maintained at a preset degree of vacuum.
  • the transfer device 170 is arranged so as to be movable in the vertical direction and the horizontal direction and rotatably around the vertical axis.
  • the transport device 170 transports the substrate 10 to the plurality of processing containers 120.
  • the processing chamber 121 inside the processing container 120 and the vacuum transfer chamber 101 communicate with each other when the atmospheric pressure is lower than the atmospheric pressure, and the substrate 10 is carried in and out.
  • the air transport chamber is provided instead of the vacuum transport chamber 101, it is possible to prevent the air from flowing from the air transport chamber into the inside of the processing chamber 121 when the substrate 10 is carried in and out.
  • the waiting time for lowering the air pressure in the processing chamber 121 can be reduced, and the processing speed of the substrate 10 can be improved.
  • the processing container 120 has a carry-in outlet 122 through which the substrate 10 passes.
  • the carry-in outlet 122 is provided with a gate G that opens and closes the carry-in outlet 122.
  • the gate G basically closes the carry-in outlet 122, and opens the carry-in outlet 122 when the substrate 10 passes through the carry-in outlet 122.
  • the substrate holding unit 130 holds the substrate 10 inside the processing container 120.
  • the substrate holding portion 130 holds the substrate 10 horizontally from below with the surface of the substrate 10 exposed to the processing gas facing upward.
  • the substrate holding portion 130 is a single-wafer type and holds one substrate 10.
  • the substrate holding unit 130 may be a batch type, or may hold a plurality of substrates 10 at the same time.
  • the batch-type substrate holding unit 130 may hold a plurality of substrates 10 at intervals in the vertical direction or at intervals in the horizontal direction.
  • the heater 140 heats the substrate 10 held by the substrate holding portion 130.
  • the heater 140 is, for example, an electric heater, and generates heat by supplying electric power.
  • the heater 140 is embedded in the substrate holding portion 130, for example, and heats the substrate holding portion 130 to heat the substrate 10 to a desired temperature.
  • the heater 140 may include a lamp that heats the substrate holding portion 130 through the quartz window. In this case, an inert gas such as argon gas may be supplied between the substrate holding portion 130 and the quartz window in order to prevent the quartz window from becoming opaque due to deposits. Further, the heater 140 may heat the substrate 10 arranged inside the processing container 120 from the outside of the processing container 120.
  • the processing unit 110 may further include not only a heater 140 that heats the substrate 10 but also a cooler that cools the substrate 10. Not only can the temperature of the substrate 10 be raised at high speed, but the temperature of the substrate 10 can be lowered at high speed. On the other hand, when the processing of the substrate 10 is performed at room temperature, the processing unit 110 does not have to have a heater 140 and a cooler.
  • the gas supply device 150 supplies a preset processing gas to the substrate 10.
  • the processing gas is prepared for each of steps S102 to S107, for example.
  • the steps S102 to S107 may be carried out inside different processing containers 120, or two or more of any combinations may be carried out continuously inside the same processing container 120. In the latter case, the gas supply device 150 supplies a plurality of types of processing gases to the substrate 10 in a preset order according to the order of the steps.
  • the gas supply device 150 is connected to the processing container 120 via, for example, the gas supply pipe 151.
  • the gas supply device 150 includes a supply source of processing gas, an individual pipe extending individually from each supply source to the gas supply pipe 151, an on-off valve provided in the middle of the individual pipe, and a flow rate controller provided in the middle of the individual pipe. And have.
  • the on-off valve opens the individual pipe, the processing gas is supplied from the supply source to the gas supply pipe 151.
  • the supply amount is controlled by the flow controller.
  • the on-off valve closes the individual pipes, the supply of the processing gas from the supply source to the gas supply pipe 151 is stopped.
  • the gas supply pipe 151 supplies the processing gas supplied from the gas supply device 150 to the inside of the processing container 120, for example, the shower head 152.
  • the shower head 152 is provided above the substrate holding portion 130.
  • the shower head 152 has a space 153 inside, and discharges the processing gas stored in the space 153 vertically downward from a large number of gas discharge holes 154.
  • a shower-like processing gas is supplied to the substrate 10.
  • the gas discharge device 160 discharges gas from the inside of the processing container 120.
  • the gas discharge device 160 is connected to the processing container 120 via the exhaust pipe 161.
  • the gas discharge device 160 has an exhaust source such as a vacuum pump and a pressure controller. When the exhaust source is operated, gas is discharged from the inside of the processing container 120.
  • the air pressure inside the processing container 120 is controlled by a pressure controller.
  • the control device 180 is composed of, for example, a computer, and includes a CPU (Central Processing Unit) 181 and a storage medium 182 such as a memory.
  • the storage medium 182 stores programs that control various processes executed by the film forming apparatus 100.
  • the control device 180 controls the operation of the film forming apparatus 100 by causing the CPU 181 to execute the program stored in the storage medium 182.
  • the control device 180 includes an input interface 183 and an output interface 184.
  • the control device 180 receives a signal from the outside through the input interface 183 and transmits the signal to the outside through the output interface 184.
  • the control device 180 controls the heater 140, the gas supply device 150, the gas discharge device 160, and the transfer device 170 so as to carry out the steps S101 to S107 shown in FIG.
  • the control device 180 also controls the gate G.
  • FIG. 5 is a cross-sectional view showing an example of a polishing apparatus for carrying out the step S108 shown in FIG.
  • the film forming apparatus 100 further includes, for example, a polishing apparatus 210, a load lock apparatus 220, and a conveying apparatus 230.
  • the load lock device 220 forms a load lock chamber 221 that switches the air pressure in the middle of the transport path for transporting the substrate 10 from the vacuum transport chamber 101 to the atmosphere transport chamber 201.
  • the pressure in the load lock chamber 221 is switched between atmospheric pressure lower than atmospheric pressure and atmospheric pressure.
  • the load lock device 220 has a first transport port 222 and a second transport port 223.
  • the first transport port 222 is formed between the vacuum transport chamber 101 and the load lock chamber 221 and is opened and closed by the gate G1.
  • the second transport port 223 is formed between the load lock chamber 221 and the air transport chamber 201, and is opened and closed by the gate G2.
  • the air transport chamber 201 is filled with air
  • the transport device 230 is arranged in the air transport chamber 201 so as to be movable in the vertical direction and the horizontal direction and to be rotatable around the vertical axis.
  • the transfer device 170 transfers the substrate 10 from the vacuum transfer chamber 101 to the load lock chamber 221.
  • the first transport port 222 is opened, the second transport port 223 is closed, and the air pressure in the load lock chamber 221 is maintained at the same level as the air pressure in the vacuum transport chamber 101. Since it is possible to prevent gas from flowing from the load lock chamber 221 into the vacuum transport chamber 101, it is possible to prevent fluctuations in the air pressure in the vacuum transport chamber 101.
  • the transfer device 170 exits from the load lock chamber 221 to the vacuum transfer chamber 101 after arranging the substrate 10 in the load lock chamber 221.
  • the first transport port 222 is closed, then the second transport port 223 is opened, and the pressure in the load lock chamber 221 becomes atmospheric pressure.
  • gas may be supplied to the load lock chamber 221 so that the pressure in the load lock chamber 221 becomes atmospheric pressure.
  • the transport device 230 receives the substrate 10 from the load lock chamber 221 and transports it to the polishing device 210.
  • the polishing device 210 has, for example, a lower surface plate 211, an upper surface plate 213, and a nozzle 214.
  • the lower platen 211 is arranged horizontally, and a polishing pad 212 is attached to the upper surface of the lower platen 211.
  • the upper surface plate 213 is arranged horizontally, and the substrate 10 is fixed to the lower surface of the upper surface plate 213.
  • the upper surface plate 213 holds the substrate 10 horizontally and presses the insulating target film 50 against the polishing pad 212.
  • the diameter of the upper surface plate 213 is smaller than the radius of the lower surface plate 211, and the upper surface plate 213 is arranged radially outside the rotation center line C1 of the lower surface plate 211.
  • the rotation center line C2 of the upper surface plate 213 is arranged so as to be offset in parallel with the rotation center line C1 of the lower surface plate 211.
  • the lower platen 211 is rotated about its vertical rotation center line C1.
  • the upper surface plate 213 passively rotates with the rotation of the lower surface plate 211.
  • the upper surface plate 213 and the lower surface plate 211 may be rotated independently or may be rotated by separate rotary motors.
  • the nozzle 214 supplies the polishing slurry to the polishing pad 212 from above.
  • the polishing slurry is supplied between the substrate 10 and the polishing pad 212, and the lower surface of the substrate 10 is polished flat.
  • the control device 180 controls the polishing device 210 so as to carry out the above step S108.
  • the control device 180 also controls the transfer device 230 and the load lock device 220 in addition to the polishing device 210.
  • Substrate 11 Conductive film 12 Insulation film 14 Substrate substrate 20 Boron oxide film 30 SAM (Self-assembled monolayer) 40 Conductive target film 50 Insulating target film 100 Film forming device 110 Processing unit 120 Processing container 130 Substrate holder 150 Gas supply device 160 Gas discharge device 170 Conveyor device 180 Control device 210 Polishing device

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Abstract

導電材料の表面酸化によって形成される酸化物が露出する第１領域、および絶縁材料が露出する第２領域を有する基板を準備する工程と、ハロゲン化ホウ素ガスを前記基板に対して供給することにより、前記酸化物の膜を酸化ホウ素の膜に置換する工程と、フッ素を含むシラン系化合物のガスを前記基板に対して供給することにより、前記第１領域で前記酸化ホウ素の膜をエッチングすると共に、前記第２領域に自己組織化単分子膜を形成する工程と、前記第２領域に形成した前記自己組織化単分子膜を用いて、前記第１領域および前記第２領域のうちの前記導電材料が露出した前記第１領域に選択的に導電性の対象膜を形成する工程とを含む、成膜方法。

Description

成膜方法および成膜装置
　本開示は、成膜方法および成膜装置に関する。
　特許文献１には、フォトリソグラフィ技術を用いずに、基板の特定の領域に選択的に対象膜を形成する技術が開示されている。具体的には、対象膜の形成を阻害する自己組織化単分子膜（Ｓｅｌｆ－Ａｓｓｅｍｂｌｅｄ　Ｍｏｎｏｌａｙｅｒ：ＳＡＭ）を基板の一部の領域に形成し、基板の残りの領域に対象膜を形成する技術が開示されている。
日本国特表２００７－５０１９０２号公報
　本開示の一態様は、導電材料の表面酸化によって形成される酸化物が露出する第１領域と絶縁材料が露出する第２領域とのうちの、第２領域にＳＡＭを選択的に形成できる、技術を提供する。
　本開示の一態様の成膜方法は、
　導電材料の表面酸化によって形成される酸化物が露出する第１領域、および絶縁材料が露出する第２領域を有する基板を準備する工程と、
　ハロゲン化ホウ素ガスを前記基板に対して供給することにより、前記導電材料の前記酸化物の膜を酸化ホウ素の膜に置換する工程と、
　フッ素を含むシラン系化合物のガスを前記基板に対して供給することにより、前記第１領域で前記酸化ホウ素の膜をエッチングすると共に、前記第２領域に自己組織化単分子膜を形成する工程と、
　前記第２領域に形成した前記自己組織化単分子膜を用いて、前記第１領域および前記第２領域のうちの前記導電材料が露出した前記第１領域に選択的に導電性の対象膜を形成する工程とを含む。
　本開示の一態様によれば、導電材料の表面酸化によって形成される酸化物が露出する第１領域と絶縁材料が露出する第２領域とのうちの、第２領域にＳＡＭを選択的に形成できる。
図１は、一実施形態に係る成膜方法を示すフローチャートである。 図２は、図１に示す工程Ｓ１０１～Ｓ１０４での基板の状態の一例を示す側面図である。 図３は、図１に示す工程Ｓ１０５～Ｓ１０８での基板の状態の一例を示す側面図である。 図４は、図１に示す工程Ｓ１０１～Ｓ１０７を実施する成膜装置の一例を示す断面図である。 図５は、図１に示す工程Ｓ１０８を実施する研磨装置の一例を示す断面図である。
　以下、本開示の実施形態について図面を参照して説明する。なお、各図面において同一の又は対応する構成には同一の符号を付し、説明を省略することがある。
　図１は、一実施形態に係る成膜方法を示すフローチャートである。図２は、図１に示す工程Ｓ１０１～Ｓ１０４での基板の状態の一例を示す側面図である。図２（ａ）は工程Ｓ１０１で準備される基板の状態を示し、図２（ｂ）は工程Ｓ１０２で得られる基板の状態を示し、図２（ｃ）は工程Ｓ１０３で得られる基板の状態を示し、図２（ｄ）は工程Ｓ１０４で得られる基板の状態を示す。図３は、図１に示す工程Ｓ１０５～Ｓ１０８での基板の状態の一例を示す側面図である。図３（ａ）は工程Ｓ１０５で得られる基板の状態を示し、図３（ｂ）は工程Ｓ１０６で得られる基板の状態を示し、図３（ｃ）は工程Ｓ１０７で得られる基板の状態を示し、図３（ｄ）は工程Ｓ１０８で得られる基板の状態を示す。
　成膜方法は、図２（ａ）に示すように基板１０を準備する工程Ｓ１０１を含む。準備することは、例えば、後述する処理容器１２０（図４参照）の内部に基板１０を搬入することを含む。基板１０は、第１材料が露出する第１領域Ａ１と、第１材料とは異なる第２材料が露出する第２領域Ａ２とを有する。第１領域Ａ１と第２領域Ａ２とは、基板１０の板厚方向片側に設けられる。
　第１領域Ａ１の数は、図２（ａ）では１つであるが、複数でもよい。例えば２つの第１領域Ａ１が第２領域Ａ２を挟むように配置されてもよい。同様に、第２領域Ａ２の数は、図２（ａ）では１つであるが、複数でもよい。例えば２つの第２領域Ａ２が第１領域Ａ１を挟むように配置されてもよい。
　なお、図２（ａ）では第１領域Ａ１および第２領域Ａ２のみが存在するが、第３領域がさらに存在してもよい。第３領域は、第１材料および第２材料とは異なる第３材料が露出する領域である。第３領域は、第１領域Ａ１と第２領域Ａ２との間に配置されてもよいし、第１領域Ａ１および第２領域Ａ２の外に配置されてもよい。
　第１材料は、例えば導電材料の表面酸化によって形成される酸化物である。導電材料は例えばタングステン（Ｗ）であり、導電材料の酸化物は例えば酸化タングステン（ＷＯ）である。なお、導電材料は、本実施形態ではタングステンであるが、モリブデン（Ｍｏ）、チタン（Ｔｉ）、窒化チタン（ＴｉＮ）、タンタル（Ｔａ）、窒化タンタル（ＴａＮ）、バナジウム（Ｖ）、または窒化バナジウム（ＶＮ）などでもよい。これらの導電材料の表面は、大気中で時間の経過と共に自然に酸化される。その酸化物が第１材料である。第１材料である酸化物は、酸窒化物であってもよく、後述する工程Ｓ１０２で酸化ホウ素に置換されるものであればよい。
　なお、酸化タングステンを、酸素とタングステンとの組成比に関係なく「ＷＯ」とも表記する。また、窒化チタンを、窒素とチタンとの組成比に関係なく「ＴｉＮ」とも表記する。同様に、窒化タンタルを「ＴａＮ」とも表記し、窒化バナジウムを「ＶＮ」とも表記する。
　第２材料は、例えば絶縁材料である。絶縁材料は、例えば酸化ケイ素である。以下、酸化ケイ素を、酸素とケイ素の組成比に関係なく「ＳｉＯ」とも表記する。なお、第２材料は、本実施形態では酸化ケイ素であるが、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、または酸化アルミニウムなどでもよい。第２材料は、第１材料とは異なり、後述する工程Ｓ１０２で別の材料（例えば酸化ホウ素）にほとんど置換されないものであればよい。つまり、後述する工程Ｓ１０２において、第２材料から前記別の材料への置換速度は、第１材料から酸化ホウ素への置換速度よりも遅い。
　基板１０は、例えば、上記の導電材料で形成される導電膜１１と、上記の絶縁材料で形成される絶縁膜１２とを有する。導電膜１１の表面には、大気中で、酸化物膜１３が時間の経過と共に自然に形成される。導電膜１１は例えばタングステン膜であり、酸化物膜１３は例えば酸化タングステン膜である。
　また、基板１０は、導電膜１１と絶縁膜１２が形成される下地基板１４を有する。下地基板１４は、例えばシリコンウェハなどの半導体基板である。なお、下地基板１４は、ガラス基板などであってもよい。
　なお、基板１０は、下地基板１４と導電膜１１との間に、下地基板１４および導電膜１１とは異なる材料で形成される下地膜をさらに有してもよい。同様に、基板１０は、下地基板１４と絶縁膜１２との間に、下地基板１４および絶縁膜１２とは異なる材料で形成される下地膜をさらに有してもよい。
　成膜方法は、ハロゲン化ホウ素ガスを基板１０に対して供給することにより、図２（ｂ）に示すように酸化物膜１３を酸化ホウ素膜２０に置換する工程Ｓ１０２を含む。ハロゲン化ホウ素ガスと酸化物膜１３とが化学反応することにより、ハロゲン化金属と酸化ホウ素とが生成される。基板１０は予め定められた温度に加熱されており、ハロゲン化金属が揮発するので、酸化ホウ素膜２０が形成される。ハロゲン化金属の蒸気圧が酸化ホウ素の蒸気圧よりも高く、ハロゲン化金属の気化速度が酸化ホウ素の気化速度よりも高くなる温度に基板１０が加熱される。
　ハロゲン化ホウ素ガスとして、本実施形態では三塩化ホウ素（ＢＣｌ３）ガスが用いられる。ＢＣｌ３ガスとＷＯとが化学反応することにより、例えばＷＣｌｘとＢ２Ｏ３が生成する。基板１０は予め定められた温度に加熱されており、ＷＣｌｘが揮発するので、Ｂ２Ｏ３膜が形成される。
　なお、ハロゲン化ホウ素ガスは、ホウ素とハロゲンを含有するガスであればよく、三塩化ホウ素ガスには限定されない。例えば、ハロゲン化ホウ素ガスは、三フッ化ホウ素（ＢＦ３）ガス、三ヨウ化ホウ素（ＢＩ３）ガス、または三臭化ホウ素（ＢＢｒ３）ガスなどでもよい。
　成膜方法は、フッ素を含むシラン系化合物のガスを基板１０に対して供給することにより、図２（ｃ）に示すように、第１領域Ａ１で酸化ホウ素膜２０をエッチングすると共に、第２領域Ａ２にＳＡＭ（自己組織化単分子膜）３０を形成する工程Ｓ１０３を含む。ＳＡＭ３０は、シラン系化合物が第２領域Ａ２に化学吸着することにより形成され、後述する導電性の対象膜４０の形成を阻害する。なお、第１領域Ａ１および第２領域Ａ２に加えて第３領域が存在する場合、第３領域にはＳＡＭ３０が形成されてもよいし、形成されなくてもよい。
　フッ素を含むシラン系化合物は、例えば、一般式Ｒ－ＳｉＨ３－ｘＣｌｘ（ｘ＝１、２、３）で表される化合物、またはＲ´－Ｓｉ（Ｏ－Ｒ）３で表される化合物（シランカップリング剤）である。ここで、Ｒ、Ｒ´は、アルキル基の水素の少なくとも一部をフッ素に置換した基等の官能基である。その官能基の末端基は、ＣＦ系である。また、Ｏ－Ｒは、加水分解可能な官能基、例えばメトキシ基、エトキシ基である。フッ素を含むシラン系化合物は、特に限定されないが、例えば、ＣＦ３（ＣＦ２）ＸＣＨ２ＣＨ２ＳｉＣｌ３、ＣＦ３（ＣＦ２）ＸＣＨ２ＣＨ２Ｓｉ（ＯＭｅ）３、またはＣＦ３（ＣＦ２）ＸＣＨ２ＣＨ２Ｓｉ（ＯＥｔ）３などである。ここで、Ｘは、０以上７以下の整数である。
　シラン系化合物は、フッ素を含むので、酸化ホウ素膜２０をエッチングできる。第１領域Ａ１では、ＳＡＭ３０の形成と、酸化ホウ素膜２０のエッチングとが同時に進行するので、ＳＡＭ３０の形成を抑制できる。第１領域Ａ１には、第２領域Ａ２に比べてＳＡＭ３０がほとんど形成されない。第１領域Ａ１では、ＳＡＭ３０の密度が低いので、後述する工程Ｓ１０４でガスがＳＡＭ３０を避けながら酸化ホウ素膜２０と化学反応できる。この化学反応によって酸化ホウ素膜２０を除去でき、導電膜１１を露出できる。
　なお、酸化ホウ素膜２０の厚さが薄く、工程Ｓ１０３の終了までに導電膜１１が露出し、且つ導電膜１１が金属膜である場合には、後述する工程Ｓ１０４は不要である。シラン系化合物は、ＯＨ基を有する表面に化学吸着するので、金属よりも金属化合物に化学吸着しやすい。従って、導電膜１１が金属膜である場合、導電膜１１が露出した後は、シラン系化合物は、第１領域Ａ１および第２領域Ａ２のうちの第２領域Ａ２に選択的に化学吸着する。
　上記の通り、成膜方法は、酸化物膜１３から酸化ホウ素膜２０への置換（工程Ｓ１０２）と、酸化ホウ素膜２０のエッチングおよびＳＡＭ３０の形成（工程Ｓ１０３）とを含む。第１領域Ａ１では、ＳＡＭ３０の形成と、酸化ホウ素膜２０のエッチングとが同時に進行するので、ＳＡＭ３０の形成を抑制できる。
　成膜方法は、ＳＡＭ３０の形成（工程Ｓ１０３）後、導電性の対象膜４０の形成（工程Ｓ１０５）前に、基板１０に対してガスを供給することにより、図２（ｄ）に示すように第１領域Ａ１に残る酸化ホウ素膜２０をエッチングし除去する工程Ｓ１０４を有する。この工程Ｓ１０４で使用するガスは、特に限定されないが、例えばフッ化水素（ＨＦ）ガスである。ＨＦガス以外に、例えば三フッ化塩素（ＣｌＦ３）ガスや三フッ化窒素（ＮＦ３）ガスなども使用可能である。
　ＳＡＭ３０は、工程Ｓ１０４で使用するガスに対して耐性を有するので、第２領域Ａ２に残る。一方、第１領域Ａ１では、ＳＡＭ３０の密度が低いので、ガスはＳＡＭ３０を避けながら酸化ホウ素膜２０と化学反応する。その化学反応によって、酸化ホウ素膜２０を除去でき、導電膜１１を露出できる。酸化ホウ素膜２０の除去によって、酸化ホウ素膜２０上のＳＡＭ３０をも除去でき、第２領域Ａ２のみにＳＡＭ３０を残すことができる。つまり、酸化ホウ素膜２０の除去によって、ＳＡＭ３０のリフトオフを実施できる。
　成膜方法は、図３（ａ）に示すように、第２領域Ａ２に形成したＳＡＭ３０を用いて、第１領域Ａ１および第２領域Ａ２のうちの導電材料が露出した第１領域Ａ１に選択的に導電性の対象膜４０を形成する工程Ｓ１０５を含む。対象膜４０は、ＳＡＭ３０とは異なる材料、例えば金属、金属化合物または半導体で形成される。ＳＡＭ３０は導電性の対象膜４０の形成を阻害するので、導電性の対象膜４０は第１領域Ａ１に選択的に形成される。なお、第１領域Ａ１および第２領域Ａ２に加えて第３領域が存在する場合、第３領域には導電性の対象膜４０が形成されてもよいし、形成されなくてもよい。
　導電性の対象膜４０は、例えばＣＶＤ（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法またはＡＬＤ（Ａｔｏｍｉｃ　Ｌａｙｅｒ　Ｄｅｐｏｓｉｔｉｏｎ）法で形成される。第１領域Ａ１に元々存在する導電膜１１に、さらに導電性の対象膜４０を積層できる。導電性の対象膜４０の材料と、導電膜１１の材料とは、本実施形態では同一の材料（例えばＷ）であるが、異なる材料であってもよい。例えば、導電性の対象膜４０の材料は、タングステン（Ｗ）の他に、モリブデン（Ｍｏ）、チタン（Ｔｉ）、窒化チタン（ＴｉＮ）、タンタル（Ｔａ）、窒化タンタル（ＴａＮ）、バナジウム（Ｖ）、または窒化バナジウム（ＶＮ）などであってもよい。
　導電性の対象膜４０としてタングステン膜をＡＬＤ法で形成する場合、処理ガスとして六塩化タングステン（ＷＣｌ６）ガスなどのＷ含有ガスと、水素（Ｈ２）ガスなどの還元性ガスとが、基板１０に対して交互に供給される。これらの処理ガスは、化学反応を促進すべく、加熱されてもよい。また、これらの処理ガスは、化学反応を促進すべく、プラズマ化されてもよい。
　成膜方法は、導電性の対象膜４０の形成（工程Ｓ１０５）後に、基板１０に対して酸素含有ガスを供給することにより、図３（ｂ）に示すようにＳＡＭ３０をエッチングし除去する工程Ｓ１０６を含む。酸素含有ガスは、ＳＡＭ３０を分解し、ガス化する。ガス化したＳＡＭ３０は除去され、絶縁膜１２が第２領域Ａ２に露出する。
　ＳＡＭ３０をエッチングする酸素含有ガスは、特に限定されないが、例えば酸素（Ｏ２）ガス、オゾン（Ｏ３）ガス、または水蒸気などである。これらの酸素含有ガスは、化学反応を促進すべく、高温に加熱されてもよい。また、これらの酸素含有ガスは、化学反応を促進すべく、プラズマ化されてもよい。
　成膜方法は、ＳＡＭ３０の除去（工程Ｓ１０６）後に、図３（ｃ）に示すように第１領域Ａ１および第２領域Ａ２に絶縁性の対象膜５０を形成する工程Ｓ１０７を含む。絶縁性の対象膜５０は、例えばＣＶＤ法またはＡＬＤ法で形成される。第２領域Ａ２に元々存在する絶縁膜１２に、さらに絶縁性の対象膜５０を積層できる。
　絶縁性の対象膜５０の材料と、絶縁膜１２の材料とは、本実施形態では同一の材料（例えばＳｉＯ）であるが、異なる材料であってもよい。例えば、導電膜１１の材料は、酸化ケイ素の他に、窒化ケイ素、酸窒化ケイ素、炭化ケイ素、または酸化アルミニウムなどであってもよい。
　絶縁性の対象膜５０としてＳｉＯ膜をＡＬＤ法で形成する場合、処理ガスとして、ジクロロシラン（ＳｉＨ２Ｃｌ２）ガスなどのＳｉ含有ガスと、オゾン（Ｏ３）ガスなどの酸化ガスとが、基板１０に対して交互に供給される。Ｓｉ含有ガスおよび酸化ガスの他に、水素（Ｈ２）ガスなどの改質ガスが基板１０に対して供給されてもよい。これらの処理ガスは、化学反応を促進すべく、プラズマ化されてもよい。また、これらの処理ガスは、化学反応を促進すべく、加熱されてもよい。
　成膜方法は、図３（ｄ）に示すように、第１領域Ａ１に導電性の対象膜４０が露出し、第２領域Ａ２に絶縁性の対象膜５０が露出し、且つ第１領域Ａ１と第２領域Ａ２とが平坦になるように絶縁性の対象膜５０を研磨する工程Ｓ１０８を含む。絶縁性の対象膜５０の研磨は、例えばＣＭＰ（Ｃｈｅｍｉｃａｌ　Ｍｅｃｈａｎｉｃａｌ　Ｐｏｌｉｓｈｉｎｇ）である。絶縁性の対象膜５０の研磨によって、第１領域Ａ１において導電性の対象膜４０を露出できる。また、第１領域Ａ１と第２領域Ａ２とを平坦化できる。
　図４は、図１に示す工程Ｓ１０１～Ｓ１０７を実施する成膜装置の一例を示す断面図である。成膜装置１００は、図１に示す工程Ｓ１０１～Ｓ１０８のうちの、少なくとも工程Ｓ１０１～Ｓ１０３およびＳ１０５を実施すればよい。残りの工程Ｓ１０４およびＳ１０６～Ｓ１０８のうち、工程Ｓ１０４は上記の通り実施されなくてもよく、工程Ｓ１０６～Ｓ１０８は別の装置で実施されてもよい。成膜装置１００は、処理ユニット１１０と、搬送装置１７０と、制御装置１８０とを備える。処理ユニット１１０は、処理容器１２０と、基板保持部１３０と、加熱器１４０と、ガス供給装置１５０と、ガス排出装置１６０とを有する。
　処理ユニット１１０は、図４には１つのみ図示するが、複数であってもよい。複数の処理ユニット１１０は、いわゆるマルチチャンバーシステムを形成する。複数の処理ユニット１１０は、真空搬送室１０１を囲むように配置される。真空搬送室１０１は、真空ポンプによって排気され、予め設定された真空度に保持される。真空搬送室１０１には、搬送装置１７０が鉛直方向および水平方向に移動可能に、且つ鉛直軸周りに回転可能に配置される。搬送装置１７０は、複数の処理容器１２０に対して基板１０を搬送する。処理容器１２０の内部の処理室１２１と、真空搬送室１０１とは、これらの気圧がいずれも大気圧よりも低い気圧である時に連通し、基板１０の搬入出が行われる。真空搬送室１０１の代わりに大気搬送室が設けられる場合とは異なり、基板１０の搬入出時に大気が大気搬送室から処理室１２１の内部に流れ込むのを防止できる。処理室１２１の気圧を下げるための待ち時間を削減でき、基板１０の処理速度を向上できる。
　処理容器１２０は、基板１０が通過する搬入出口１２２を有する。搬入出口１２２には、搬入出口１２２を開閉するゲートＧが設けられる。ゲートＧは、基本的に搬入出口１２２を閉じており、基板１０が搬入出口１２２を通る時に搬入出口１２２を開く。搬入出口１２２の開放時に、処理容器１２０の内部の処理室１２１と、真空搬送室１０１とが連通する。搬入出口１２２の開放前に、処理室１２１と真空搬送室１０１とは、いずれも、真空ポンプによって排気され、予め設定された気圧に維持される。
　基板保持部１３０は、処理容器１２０の内部で基板１０を保持する。基板保持部１３０は、基板１０の処理ガスに曝される表面を上に向けて、基板１０を下方から水平に保持する。基板保持部１３０は、枚葉式であって、一枚の基板１０を保持する。なお、基板保持部１３０は、バッチ式でもよく、同時に複数枚の基板１０を保持してもよい。バッチ式の基板保持部１３０は、複数枚の基板１０を、鉛直方向に間隔をおいて保持してもよいし、水平方向に間隔をおいて保持してもよい。
　加熱器１４０は、基板保持部１３０で保持されている基板１０を加熱する。加熱器１４０は、例えば電気ヒータであり、電力供給によって発熱する。加熱器１４０は、例えば、基板保持部１３０の内部に埋め込まれ、基板保持部１３０を加熱することにより、基板１０を所望の温度に加熱する。なお、加熱器１４０は、石英窓を介して基板保持部１３０を加熱するランプを含んでもよい。この場合、石英窓が堆積物で不透明になるのを防止すべく、基板保持部１３０と石英窓との間にアルゴンガスなどの不活性ガスが供給されてもよい。また、加熱器１４０は、処理容器１２０の外部から処理容器１２０の内部に配置される基板１０を加熱してもよい。
　なお、処理ユニット１１０は、基板１０を加熱する加熱器１４０だけではなく、基板１０を冷却する冷却器をさらに有してもよい。基板１０の温度を高速で昇温できるだけではなく、基板１０の温度を高速で降温できる。一方、基板１０の処理が室温で行われる場合、処理ユニット１１０は加熱器１４０および冷却器を有しなくてもよい。
　ガス供給装置１５０は、基板１０に対して予め設定された処理ガスを供給する。処理ガスは、例えば、工程Ｓ１０２～Ｓ１０７毎に用意される。工程Ｓ１０２～Ｓ１０７は、それぞれが互いに異なる処理容器１２０の内部で実施されてもよいし、任意の組合せの２つ以上が同じ処理容器１２０の内部で連続的に実施されてもよい。後者の場合、ガス供給装置１５０は、工程の順番に従って、複数種類の処理ガスを、予め設定された順番で基板１０に対して供給する。
　ガス供給装置１５０は、例えば、ガス供給管１５１を介して処理容器１２０と接続される。ガス供給装置１５０は、処理ガスの供給源と、各供給源から個別にガス供給管１５１まで延びる個別配管と、個別配管の途中に設けられる開閉バルブと、個別配管の途中に設けられる流量制御器とを有する。開閉バルブが個別配管を開くと、供給源からガス供給管１５１に処理ガスが供給される。その供給量は流量制御器によって制御される。一方、開閉バルブが個別配管を閉じると、供給源からガス供給管１５１への処理ガスの供給が停止される。
　ガス供給管１５１は、ガス供給装置１５０から供給される処理ガスを、処理容器１２０の内部、例えばシャワーヘッド１５２に供給する。シャワーヘッド１５２は、基板保持部１３０の上方に設けられる。シャワーヘッド１５２は、内部に空間１５３を有し、空間１５３に溜めた処理ガスを多数のガス吐出孔１５４から鉛直下方に向けて吐出する。シャワー状の処理ガスが、基板１０に対して供給される。
　ガス排出装置１６０は、処理容器１２０の内部からガスを排出する。ガス排出装置１６０は、排気管１６１を介して処理容器１２０と接続される。ガス排出装置１６０は、真空ポンプなどの排気源と、圧力制御器とを有する。排気源を作動させると、処理容器１２０の内部からガスが排出される。処理容器１２０の内部の気圧は、圧力制御器によって制御される。
　制御装置１８０は、例えばコンピュータで構成され、ＣＰＵ（Ｃｅｎｔｒａｌ　Ｐｒｏｃｅｓｓｉｎｇ　Ｕｎｉｔ）１８１と、メモリなどの記憶媒体１８２とを備える。記憶媒体１８２には、成膜装置１００において実行される各種の処理を制御するプログラムが格納される。制御装置１８０は、記憶媒体１８２に記憶されたプログラムをＣＰＵ１８１に実行させることにより、成膜装置１００の動作を制御する。また、制御装置１８０は、入力インターフェース１８３と、出力インターフェース１８４とを備える。制御装置１８０は、入力インターフェース１８３で外部からの信号を受信し、出力インターフェース１８４で外部に信号を送信する。
　制御装置１８０は、図１に示す工程Ｓ１０１～Ｓ１０７を実施するように、加熱器１４０、ガス供給装置１５０、ガス排出装置１６０、および搬送装置１７０を制御する。制御装置１８０は、ゲートＧも制御する。
　図５は、図１に示す工程Ｓ１０８を実施する研磨装置の一例を示す断面図である。成膜装置１００は、例えば、研磨装置２１０と、ロードロック装置２２０と、搬送装置２３０とをさらに備える。ロードロック装置２２０は、真空搬送室１０１から大気搬送室２０１に基板１０を搬送する搬送経路の途中に、気圧を切り替えるロードロック室２２１を形成する。ロードロック室２２１の気圧は、大気圧よりも低い気圧と、大気圧とに切り替えられる。ロードロック装置２２０は、第１搬送口２２２と、第２搬送口２２３とを有する。第１搬送口２２２は、真空搬送室１０１とロードロック室２２１との間に形成され、ゲートＧ１によって開閉される。また、第２搬送口２２３は、ロードロック室２２１と大気搬送室２０１との間に形成され、ゲートＧ２によって開閉される。大気搬送室２０１は大気で満たされ、大気搬送室２０１には搬送装置２３０が鉛直方向および水平方向に移動可能に、且つ鉛直軸周りに回転可能に配置される。
　絶縁性の対象膜５０の形成（工程Ｓ１０７）後、搬送装置１７０（図４参照）が真空搬送室１０１からロードロック室２２１に基板１０を搬送する。この時、第１搬送口２２２は開放され、第２搬送口２２３は閉塞され、ロードロック室２２１の気圧は真空搬送室１０１の気圧と同程度に維持される。ロードロック室２２１から真空搬送室１０１へのガスの流れ込みを防止できるので、真空搬送室１０１の気圧の変動を防止できる。
　搬送装置１７０は、ロードロック室２２１に基板１０を配置した後、ロードロック室２２１から真空搬送室１０１に退出する。その後、第１搬送口２２２が閉塞され、続いて、第２搬送口２２３が開放され、ロードロック室２２１の気圧が大気圧になる。なお、第１搬送口２２２の閉塞後、第２搬送口２２３の開放前に、ロードロック室２２１の気圧が大気圧になるようにロードロック室２２１にガスが供給されてもよい。第２搬送口２２３の開放後、搬送装置２３０がロードロック室２２１から基板１０を受け取り、研磨装置２１０に搬送する。
　研磨装置２１０は、例えば、下定盤２１１と、上定盤２１３と、ノズル２１４とを有する。下定盤２１１は水平に配置され、下定盤２１１の上面には研磨パッド２１２が貼付される。上定盤２１３は水平に配置され、上定盤２１３の下面には基板１０が固定される。上定盤２１３は、基板１０を水平に保持し、絶縁性の対象膜５０を研磨パッド２１２に押し付ける。上定盤２１３の直径は下定盤２１１の半径よりも小さく、下定盤２１１の回転中心線Ｃ１よりも径方向外側に上定盤２１３が配置される。上定盤２１３の回転中心線Ｃ２は、下定盤２１１の回転中心線Ｃ１と平行にずらして配置される。下定盤２１１は、その鉛直な回転中心線Ｃ１を中心に回転させられる。上定盤２１３は、下定盤２１１の回転に伴って受動的に回転する。なお、上定盤２１３と下定盤２１１とは、独立に回転してもよく、別々の回転モータによって回転させられてもよい。ノズル２１４は、研磨パッド２１２に対して上方から研磨スラリーを供給する。研磨スラリーは、基板１０と研磨パッド２１２との間に供給され、基板１０の下面を平坦に研磨する。
　制御装置１８０（図４参照）は、上記工程Ｓ１０８を実施するように、研磨装置２１０を制御する。また、制御装置１８０は、研磨装置２１０に加えて、搬送装置２３０およびロードロック装置２２０も制御する。
　以上、本開示に係る成膜方法および成膜装置の実施形態について説明したが、本開示は上記実施形態などに限定されない。特許請求の範囲に記載された範疇内において、各種の変更、修正、置換、付加、削除、および組合わせが可能である。それらについても当然に本開示の技術的範囲に属する。
　本出願は、２０１９年３月２５日に日本国特許庁に出願した特願２０１９－０５７１６４号に基づく優先権を主張するものであり、特願２０１９－０５７１６４号の全内容を本出願に援用する。
１０　　基板
１１　　導電膜
１２　　絶縁膜
１４　　下地基板
２０　　酸化ホウ素膜
３０　　ＳＡＭ（自己組織化単分子膜）
４０　　導電性の対象膜
５０　　絶縁性の対象膜
１００　成膜装置
１１０　処理ユニット
１２０　処理容器
１３０　基板保持部
１５０　ガス供給装置
１６０　ガス排出装置
１７０　搬送装置
１８０　制御装置
２１０　研磨装置

Claims (8)

  1. 　導電材料の表面酸化によって形成される酸化物が露出する第１領域、および絶縁材料が露出する第２領域を有する基板を準備する工程と、
    　ハロゲン化ホウ素ガスを前記基板に対して供給することにより、前記酸化物の膜を酸化ホウ素の膜に置換する工程と、
    　フッ素を含むシラン系化合物のガスを前記基板に対して供給することにより、前記第１領域で前記酸化ホウ素の膜をエッチングすると共に、前記第２領域に自己組織化単分子膜を形成する工程と、
    　前記第２領域に形成した前記自己組織化単分子膜を用いて、前記第１領域および前記第２領域のうちの前記導電材料が露出した前記第１領域に選択的に導電性の対象膜を形成する工程とを含む、成膜方法。
  2. 　前記導電材料は、タングステン（Ｗ）、モリブデン（Ｍｏ）、チタン（Ｔｉ）、窒化チタン（ＴｉＮ）、タンタル（Ｔａ）、窒化タンタル（ＴａＮ）、バナジウム（Ｖ）、または窒化バナジウム（ＶＮ）である、請求項１に記載の成膜方法。
  3. 　前記ハロゲン化ホウ素ガスは、三塩化ホウ素（ＢＣｌ３）、三フッ化ホウ素（ＢＦ３）ガス、三ヨウ化ホウ素（ＢＩ３）ガス、または三臭化ホウ素（ＢＢｒ３）ガスである、請求項１または２に記載の成膜方法。
  4. 　前記自己組織化単分子膜の形成後、前記導電性の対象膜の形成前に、前記基板に対してガスを供給することにより、前記第１領域に残る前記酸化ホウ素の膜をエッチングし除去する工程を含む、請求項１～３のいずれか１項に記載の成膜方法。
  5. 　前記第１領域に残る前記酸化ホウ素の膜をエッチングするガスは、フッ化水素（ＨＦ）ガスである、請求項４に記載の成膜方法。
  6. 　前記導電性の対象膜の形成後に、前記基板に対して酸素含有ガスを供給することにより、前記自己組織化単分子膜をエッチングし除去する工程を含む、請求項１～５のいずれか１項に記載の成膜方法。
  7. 　前記自己組織化単分子膜の除去後に、前記第１領域および前記第２領域に絶縁性の対象膜を形成する工程と、
    　前記第１領域に前記導電性の対象膜が露出し、前記第２領域に前記絶縁性の対象膜が露出し、且つ前記第１領域と前記第２領域とが平坦になるように前記絶縁性の対象膜を研磨する工程とを含む、請求項６に記載の成膜方法。
  8. 　処理容器と、
    　前記処理容器の内部で前記基板を保持する基板保持部と、
    　前記処理容器の内部にガスを供給するガス供給装置と、
    　前記処理容器の内部からガスを排出するガス排出装置と、
    　前記処理容器に対して前記基板を搬入出する搬送装置と、
    　請求項１～７のいずれか１項に記載の成膜方法を実施するように、前記ガス供給装置、前記ガス排出装置および前記搬送装置を制御する制御装置とを備える、成膜装置。
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