WO2020235596A1 - Procédé de formation de film, appareil de formation de film et procédé de nettoyage de cuve de traitement - Google Patents

Procédé de formation de film, appareil de formation de film et procédé de nettoyage de cuve de traitement Download PDF

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Publication number
WO2020235596A1
WO2020235596A1 PCT/JP2020/019952 JP2020019952W WO2020235596A1 WO 2020235596 A1 WO2020235596 A1 WO 2020235596A1 JP 2020019952 W JP2020019952 W JP 2020019952W WO 2020235596 A1 WO2020235596 A1 WO 2020235596A1
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Prior art keywords
gas
processing container
film
ruthenium
cleaning
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PCT/JP2020/019952
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English (en)
Japanese (ja)
Inventor
村上　誠志
泉　浩一
正 荘所
真鍋　俊樹
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東京エレクトロン株式会社
岩谷産業株式会社
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Publication of WO2020235596A1 publication Critical patent/WO2020235596A1/fr

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    • 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
    • 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
    • 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
    • H01L21/02—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

Definitions

  • the present invention relates to a film forming method and a film forming apparatus, and a method for cleaning a processing container.
  • This application claims priority based on Japanese Application No. 2019-95723 filed on May 22, 2019, and incorporates all the contents described in the Japanese application.
  • the ruthenium film is used for a liner layer of copper wiring and the like, and is also attracting attention as a wiring material.
  • the ruthenium oxide film is used for a capacitor electrode layer or the like of a DRAM.
  • a chemical vapor deposition method (CVD method) is generally used as a method for forming a ruthenium-containing film.
  • CVD method chemical vapor deposition method
  • the reaction product containing ruthenium adheres to the inner wall of the processing container, so that it is necessary to clean the inside of the chamber at a predetermined timing.
  • Patent Document 1 proposes a technique of forming a ruthenium oxide film as a ruthenium-containing film by a CVD method and then cleaning the inside of a processing container with ClF 3 gas or the like.
  • the present invention provides a film forming method and a film forming apparatus capable of cleaning the inside of a processing container at a lower temperature when forming a ruthenium-containing film or an osmium-containing film, and a method for cleaning the processing container.
  • the film forming method includes a step of accommodating a substrate to be processed in a processing container and forming a ruthenium-containing film or an osmium-containing film on the substrate to be processed by a CVD method in the processing container. After the step of forming the film is carried out once or a plurality of times, a halogen-containing gas and an oxidation gas are supplied into the processing container in a state where the substrate to be processed does not exist in the processing container, and the inside of the processing container. Has a step of dry cleaning.
  • the method for cleaning the processing container according to another aspect of the present invention is a process in which a ruthenium-containing film or an osmium-containing film is formed on a substrate to be processed by a CVD method in the processing container, and then the inside of the processing container is dry-cleaned.
  • a method for cleaning a container that is, a step of making a substrate to be processed not present in the processing container, and a step of supplying a halogen-containing gas and an oxidation gas into the processing container in a state where the substrate to be processed does not exist.
  • a film forming method and a film forming apparatus capable of cleaning the inside of a processing container at a lower temperature when forming a ruthenium-containing film or an osmium-containing film, and a method for cleaning the processing container.
  • FIG. 1 is a flowchart showing a film forming method according to an embodiment.
  • FIG. 2 is a cross-sectional view schematically showing a first example of a film forming apparatus for carrying out the film forming method according to one embodiment.
  • FIG. 3 is a timing chart when the first aspect of dry cleaning is performed by the apparatus of FIG.
  • FIG. 4 is a timing chart when the second aspect of dry cleaning is performed by the apparatus of FIG.
  • FIG. 5 is a cross-sectional view schematically showing a second example of a film forming apparatus for carrying out the film forming method according to one embodiment.
  • FIG. 6 is a diagram showing the results of the examples.
  • FIG. 1 is a flowchart showing a film forming method according to an embodiment.
  • the film forming method according to the present embodiment includes a step of forming a ruthenium-containing film on a substrate to be treated by a CVD method in a processing container (step 1) and a halogen-containing gas in the processing container. And a step (step 2) of dry cleaning with an oxidizing gas.
  • step 1 Film formation process
  • step 1 the substrate to be processed is placed in the processing container, and while the substrate to be processed is heated and the inside of the processing container is in a vacuum atmosphere, only the ruthenium raw material gas and the reaction gas or only the ruthenium raw material gas is contained in the processing container. Supply to.
  • the reaction between the ruthenium raw material gas and the reaction gas or the thermal decomposition of the ruthenium raw material gas occurs on the substrate to be treated, and a ruthenium-containing film is formed.
  • the substrate to be processed is not particularly limited, but a semiconductor substrate (semiconductor wafer) such as silicon is exemplified.
  • the ruthenium-containing film generally refers to a film containing ruthenium, and examples thereof include a metal ruthenium film, a ruthenium oxide (RuOx) film, and a ruthenium film containing an additive component such as Si or N.
  • the film formation by the CVD method at this time is not only a normal CVD method in which the ruthenium raw material gas and the reaction gas are simultaneously supplied and reacted, but also an atomic layer deposition method in which the ruthenium raw material gas and the reaction gas are alternately supplied. ALD method) is also included.
  • Ru 3 (CO) 12 As the ruthenium raw material gas, various organic and inorganic gases can be used.
  • Ru 3 (CO) 12 ruthenium carbonyl
  • Ru 3 (CO) 12 gas becomes Ru by thermal decomposition.
  • CO gas As the carrier gas of Ru 3 (CO) 12 gas.
  • CO the carrier gas
  • a ruthenium-containing film other than the ruthenium film may be formed by reacting the Ru 3 (CO) 12 gas with the reaction gas.
  • Ru 3 (CO) 12 As ruthenium raw material gas, in addition to Ru 3 (CO) 12 , RuO 2 , Ru (EtCp) 2 , Ru (DMDB) (CO) 3 , RuO 4 (HFE), Ru (HDAC), Ru (PF 3 ), Ru (AMD) 2 CO, RuCOT and the like can be mentioned, and at least one of these raw materials including Ru 3 (CO) 12 can be used.
  • the reaction gas is appropriately selected according to the ruthenium raw material gas and the ruthenium-containing membrane to be obtained.
  • Reaction gases include CO 2 , O 2 , H 2 , Si H 4 , Si 2 H 6 , Si 3 H 8 , Si 4 H 10 , NH 3 , CH 3 (NH) NH 2 , C 2 H 8 N 2 , N 2 H 4 and the like can be mentioned, and at least one of these can be used.
  • reaction gas When the reaction gas is CO 2 , O 2 , or H 2 , a ruthenium film or a ruthenium oxide film can be formed.
  • reaction gas When the reaction gas is SiH 4 , Si 2 H 6 , Si 3 H 8 , or Si 4 H 10 , a ruthenium film containing Si can be formed.
  • reaction gas is NH 3 , CH 3 (NH) NH 2 , C 2 H 8 N 2 , N 2 H 4 , a ruthenium film containing N can be formed. It is also possible to form a doped ruthenium film using a gas containing a dopant.
  • the flow rates of the ruthenium raw material gas and the reaction gas are appropriately determined depending on the film forming apparatus and the type of the ruthenium-containing film to be formed.
  • an inert gas such as N 2 gas or a rare gas can be used as the carrier gas for the ruthenium raw material gas other than the purge gas and Ru 3 (CO) 12 .
  • an inert gas such as N 2 gas or a rare gas can be used as the rare gas.
  • Ar, He, Ne, Xe, Kr can be used as the rare gas.
  • the temperature of the substrate to be processed when step 1 is carried out can be in the range of 120 to 250 ° C., depending on the combination of the raw material gas and the reaction gas. More preferably, it is in the range of 170 to 200 ° C. Further, the pressure in the processing container when carrying out step 1 can be in the range of 0.1 to 100 Pa. More preferably, it is in the range of 1 to 10 Pa.
  • Step 2 Dry cleaning process
  • the dry cleaning step in the processing container of step 2 is carried out.
  • the number of film formations (the number of substrates to be filmed) until the dry cleaning step is performed, that is, the cleaning cycle calculates the integrated film thickness of the ruthenium-containing film deposited on the inner wall of the processing container, and the integrated film is calculated. It is preset so that the thickness is equal to or less than a predetermined value.
  • a halogen-containing gas is used as a gas for dry cleaning while the processing container is heated and the inside of the processing container is in a vacuum atmosphere in a state where the substrate to be processed does not exist in the processing container. Oxidizing gas is supplied into the processing container.
  • ClF 3 can be preferably used as a cleaning gas for a processing container that generally performs CVD film formation.
  • examples of the halogen-containing gas include NF 3 , F 2 , Cl 2 , Br 2 , I 2 , HF, HCl, HBr, and HI. These halogen-containing gases may be used alone or in combination of two or more.
  • oxidizing gas examples include O 2 , O 3 , N 2 O, NO 2 , NO, H 2 O, and H 2 O 2 . These oxidizing gases may be used alone or in combination of two or more.
  • the temperature inside the processing container when performing step 2 can be preferably as low as 200 ° C. or lower. More preferably, it is 150 to 200 ° C. Further, it is preferable that the temperature inside the processing container when carrying out step 2 is substantially the same as the temperature inside the processing container at the time of step 1.
  • Plasma may be used depending on the type of halogen-containing gas. When plasma is used, plasma may be generated in the processing container, or may be remote plasma in which plasma generated at another location is introduced into the processing container.
  • the pressure in the processing container when carrying out step 2 can be in the range of 1 to 1000 Pa. More preferably, it is in the range of 10 to 100 Pa.
  • FIG. 4 of Patent Document 1 shows the etching properties of the metal ruthenium (Ru) film and the RuO 2 film which is ruthenium oxide by ClF 3 gas, which is often used in CVD. From this figure, it can be seen that although the Ru film is more easily etched than the RuO 2 film, both require a temperature of about 200 ° C. or higher in order to etch at a high rate.
  • Ru metal ruthenium
  • the present inventors have investigated a method capable of cleaning a ruthenium-containing film at a lower temperature.
  • a halogen-containing gas such as ClF 3 and an oxidizing gas such as O 2 in combination
  • the reactivity with the ruthenium-containing film is enhanced as compared with the case of the halogen-containing gas alone, and the ruthenium-containing film attached to the processing container It was found that it can be cleaned at a lower temperature.
  • the ruthenium-containing film can be cleaned by a reaction similar to this.
  • the halogen-containing gas and the oxidizing gas may be supplied at the same time or alternately. By supplying them alternately, the reactivity can be further enhanced.
  • the one-time supply time of the halogen-containing gas and the oxidation gas is preferably in the range of 1 to 300 sec, the number of repetitions is preferably about 1 to 100 times, and the total time is preferably about 10 to 3600 sec.
  • the cleaning time is preferably about 10 to 3600 sec.
  • the flow rates of these gases may be changed on the way. For example, the flow rates of the halogen-containing gas and the oxidizing gas are reduced with the lapse of the cleaning time.
  • the flow rates of the halogen-containing gas and the oxidizing gas are appropriately set according to the film forming apparatus.
  • the value of [halogen-containing gas / oxidizing gas], which is the flow rate ratio of the halogen-containing gas to the oxidizing gas, is preferably in the range of 1 to 1000.
  • the operation of alternately supplying the halogen-containing gas and the oxidizing gas as described above and / or the operation of supplying the halogen-containing gas and the oxidizing gas at the same time may be performed a plurality of times with the purge of the processing container interposed therebetween.
  • Good Specifically, whether the operation of alternately supplying the halogen-containing gas and the oxidizing gas is performed a plurality of times or the operation of simultaneously supplying the halogen-containing gas and the oxidizing gas is performed a plurality of times, both of these can be performed at arbitrary timings. You may go multiple times with.
  • FIG. 2 is a cross-sectional view schematically showing a first example of a film forming apparatus for carrying out the film forming method according to one embodiment.
  • Ru 3 (CO) 12 gas is used as the ruthenium raw material gas
  • ClF 3 gas is used as the halogen-containing gas of the cleaning gas
  • O 2 gas is used as the oxidation gas.
  • This film forming apparatus 100 is a single-wafer film forming apparatus that deposits a ruthenium-containing film by CVD.
  • the film forming apparatus 100 has a substantially cylindrical processing container (chamber) 11 that is airtightly configured. Inside the processing container 11, a susceptor 12 for horizontally supporting a semiconductor wafer (hereinafter, simply referred to as a wafer) W as a substrate to be processed is provided in a cylindrical support member 13 provided in the center of the bottom wall of the processing container 11. It is supported and arranged by.
  • a heater 15 is embedded in the susceptor 12, and a heater power supply 16 is connected to the heater 15.
  • the wafer W is brought to a predetermined temperature via the susceptor 12. It is designed to be controlled. Further, the susceptor 12 is provided with three wafer elevating pins (not shown) for supporting and elevating the wafer W so as to be recessed from the surface of the susceptor 12.
  • the processing container 11 has an exhaust chamber 31 protruding downward from the bottom wall of the main body.
  • An exhaust pipe 32 is connected to the side surface of the exhaust chamber 31, and an exhaust device 33 having a vacuum pump, a pressure control valve, or the like is connected to the exhaust pipe 32. Then, by operating the exhaust device 33, it is possible to bring the inside of the processing container 11 into a predetermined decompression (vacuum) state. Further, the pressure control valve controls the inside of the processing container 11 to a predetermined pressure.
  • the side wall of the processing container 11 is provided with an carry-in outlet 37 for carrying in and out the wafer W to and from a transport chamber (not shown) in a predetermined decompressed state, and the carry-in outlet 37 is opened and closed by a gate valve G. It is supposed to be done. Further, a heater 26 is provided on the wall portion of the processing container 11, and the temperature of the inner wall of the processing container 11 can be heated to, for example, 200 ° C. or less during the film forming process and the dry cleaning process. ing.
  • a shower head 20 for introducing a processing gas for CVD-depositing a ruthenium-containing film and a cleaning gas for cleaning the inside of the processing container 11 into the processing container in a shower shape is provided as a susceptor. It is provided so as to face the twelve.
  • the shower head 20 is for discharging the gas supplied from the gas supply mechanism 40 described later into the processing container 11, and two gas introduction ports 21a and 21b for introducing the gas are formed above the shower head 20. Has been done. Further, a gas diffusion space 22 is formed inside the shower head 20, and a large number of gas discharge holes 23 communicating with the gas diffusion space 22 are formed on the bottom surface of the shower head 20.
  • the gas supply mechanism 40 is for supplying a processing gas for forming a ruthenium-containing film by CVD and a cleaning gas for cleaning the inside of the processing container 11.
  • the gas supply mechanism 40 has a film forming raw material container 41 accommodating Ru 3 (CO) 12 as a solid film forming raw material S.
  • a heater 42 is provided around the film-forming raw material container 41.
  • a carrier CO gas supply pipe 43 that supplies CO gas as a carrier gas from above is inserted into the film forming raw material container 41.
  • a CO gas supply source 44 for supplying CO gas is connected to the carrier CO gas supply pipe 43. Further, a film-forming raw material gas supply pipe 45 is inserted into the film-forming raw material container 41.
  • the carrier CO gas supply pipe 43 is provided with a mass flow controller 46 for flow rate control and valves 47a and 47b before and after the mass flow controller 46. Further, the film forming raw material gas supply pipe 45 is provided with a flow meter 48 for grasping the amount of Ru 3 (CO) 12 gas and valves 49a and 49b before and after the flow meter 48.
  • the gas supply mechanism 40 has a counter CO gas supply pipe 51 branched from the upstream side of the valve 47a in the carrier CO gas supply pipe 43.
  • the counter CO gas supply pipe 51 is provided with a mass flow controller 52 for controlling the flow rate and valves 53a and 53b before and after the mass flow controller 52.
  • the gas supply mechanism 40 has an additional gas supply source 54 for supplying the additional gas A which is a dilution gas or a reaction gas, and an additional gas supply pipe 55 having one end connected to the additional gas supply source 54.
  • the other end of the additional gas supply pipe 55 is connected to the film forming raw material gas supply pipe 45.
  • the additional gas A is a diluting gas, a rare gas such as Ar or an N 2 gas is used, and when the additional gas A is a reaction gas, an O 2 gas, a SiH 4 gas, an NH 3 gas or the like is used.
  • a ruthenium film is formed as a ruthenium-containing film, and when a reaction gas is used, a ruthenium oxide film or a ruthenium film containing Si or N is formed as a ruthenium-containing film.
  • the additional gas supply pipe 55 is provided with a mass flow controller 56 for controlling the flow rate and valves 57a and 57b before and after the mass flow controller 56.
  • the gas supply mechanism 40 has a ClF 3 gas supply source 61 and an O 2 gas supply source 62 for supplying ClF 3 gas and O 2 gas used as cleaning gas, respectively.
  • One end of the first cleaning gas supply pipe 63 is connected to the ClF 3 gas supply source 61, and the other end of the first cleaning gas supply pipe 63 is connected to the first carrier gas supply pipe 73 described later.
  • one end of the second cleaning gas supply pipe 64 is connected to the O 2 gas supply source 62, and the other end of the second cleaning gas supply pipe 64 is connected to the second carrier gas supply pipe 74 described later. It is connected.
  • a mass flow controller 65 for flow control and valves 66a and 66b before and after the mass flow controller 65 are provided on the ClF 3 gas supply source 61 side of the first cleaning gas supply pipe 63, and valves 67 are provided on the shower head 20 side.
  • a mass flow controller 68 for flow control and valves 69a and 69b before and after the mass flow controller 68 are provided on the O 2 gas supply source 62 side of the second cleaning gas supply pipe 64, and valves 70 are provided on the shower head 20 side. Has been done.
  • the halogen-containing gas ClF 3 gas and the oxidation gas O 2 gas are used as the first carrier gas and the second carrier gas from the first Ar gas supply source 71 and the second Ar gas supply source 72, respectively. It is conveyed by the supplied Ar gas.
  • One end of the first carrier gas supply pipe 73 is connected to the first Ar gas supply source 71, and the other end of the first carrier gas pipe 73 is connected to the gas introduction port 21b of the shower head 20. ..
  • One end of the second carrier gas supply pipe 74 is connected to the second Ar gas supply source 72, and the other end of the second carrier gas supply pipe 74 is connected to the gas introduction port 21a of the shower head 20. There is.
  • a mass flow controller 75 for flow control and valves 76a and 76b before and after the mass flow controller 75 are provided on the first carrier gas supply source 71 side of the first carrier gas supply pipe 73, and valves 79 are provided on the shower head 20 side.
  • a mass flow controller 77 for flow control and valves 78a and 78b before and after the mass flow controller 77 are provided on the second carrier gas supply source 72 side of the second carrier gas supply pipe 74, and valves 80 are provided on the shower head 20 side. Has been done.
  • ClF 3 gas supplied from the ClF 3 gas supply source 61 is a carrier of Ar gas, is supplied into the processing chamber 11 through the first cleaning gas supply pipe 63 and the shower head 20.
  • O 2 gas supplied from the O 2 gas supply source 62 is supplied into the processing vessel 11 through the second cleaning gas supply pipe 64 and the shower head 20 is a carrier of Ar gas. Further, by operating the valve 67 and the valve 70, ClF 3 gas and O 2 gas can be alternately supplied.
  • the first cleaning gas supply pipe 63 and the second cleaning gas supply pipe 64 are connected by a bypass pipe 81 in the vicinity of the gas introduction ports 21a and 21b.
  • a valve 82 is provided in the bypass pipe 81. By opening the valve 82, both ClF 3 gas and O 2 gas can be supplied to the gas inlets 21a and 21b. As a result, the Ru-containing film formed inside the gas introduction ports 21a and 21b can also be cleaned.
  • the film-forming raw material gas supply pipe 45 for supplying the Ru 3 (CO) 12 gas which is the film-forming raw material gas, is connected to the second carrier gas supply pipe 74. Therefore, the CO gas as a carrier gas is blown into the film forming raw material container 41 from the CO gas supply source 44 via the carrier CO gas supply pipe 43, and the Ru 3 (CO) 12 gas sublimated in the film forming raw material container 41. Is transported to CO gas and supplied into the processing container 11 via the film-forming raw material gas supply pipe 45, the second carrier gas supply pipe 74, and the shower head 20. Further, the counter CO gas supply pipe 51 is connected to the first carrier gas supply pipe 73.
  • the CO gas from the CO gas supply source 44 is treated separately from the Ru 3 (CO) 12 gas via the counter CO gas supply pipe 51, the first carrier gas supply pipe 73, and the shower head 20. It is supplied within 11.
  • a valve 58 and a valve 59 are provided in the vicinity of the second carrier gas supply pipe 74 of the film-forming raw material gas supply pipe 45 and in the vicinity of the first carrier gas supply pipe 73 of the counter CO gas pipe 51, respectively. ing.
  • the film forming apparatus 100 has a controller 90 for controlling each component such as a heater power supply 16, an exhaust device 33, and valves of the gas supply mechanism 40. Based on the processing recipe stored in the storage medium, the controller 90 causes each component of the film forming apparatus 100 to perform the predetermined operations shown below so that the film forming method is performed.
  • the gate valve G is opened, the wafer W is carried into the processing container 11 from the carry-in outlet 37, and placed on the susceptor 12.
  • the susceptor 12 is heated to, for example, 120 to 250 ° C. by the heater 15, on which the wafer W is heated.
  • the inner wall of the processing container 11 is also heated by the heater 26.
  • the purge gas for example, Ar gas supplied as a carrier gas
  • the pressure in the processing container 11 is controlled to, for example, 10 to 100 Pa by the pressure control valve of the exhaust device 33.
  • valves 47a and 47b are opened, CO gas as a carrier gas is blown into the film-forming raw material container 41 through the carrier CO gas supply pipe 43, and the gas is sublimated by heating the heater 42 in the film-forming raw material container 41 to generate the gas.
  • the resulting Ru 3 (CO) 12 gas is introduced into the processing container 11 via the film-forming raw material gas supply pipe 45 and the shower head 20 in a state of being carried by the CO gas.
  • the reaction gas may be supplied as the additional gas A from the additional gas supply source 54.
  • the surface of the wafer W, the ruthenium Ru 3 (CO) 12 gas is generated by thermal decomposition or by ruthenium and the reaction gas, a ruthenium-containing film is formed to have a predetermined thickness.
  • dry cleaning is performed.
  • the number of wafers W until dry cleaning, that is, the cleaning cycle, is preset by calculating the integrated film thickness of the ruthenium-containing film deposited on the inner wall of the processing container 11.
  • the inside of the processing container 11 is heated to a predetermined temperature, preferably 200 ° C. or lower, more preferably 170 to 200 ° C. by the heater 15 and the heater 26 in a state where the wafer W does not exist in the processing container 11. .. Then, with the valve 58 and the valve 59 closed and the valve 79 and the valve 80 open, Ar gas is supplied from the first and second carrier gas supply sources 71 and 72 into the processing container 11, and the processing container 11 is used. The inside is purged, and the pressure inside the processing vessel 11 is adjusted to 10 to 1000 Pa. Dry cleaning is performed in this state.
  • a predetermined temperature preferably 200 ° C. or lower, more preferably 170 to 200 ° C.
  • the valves 79 and 80 are opened to keep Ar gas, which is a carrier gas, flowing, and the valves 67 and 70 are alternately operated. It opens and closes and supplies ClF 3 gas and O 2 gas alternately.
  • these flow rates may be in the range of ClF 3 gas: 10 to 1000 sccm and O 2 gas: 1 to 1000 sccm.
  • the value of the flow rate ratio [ClF 3 / O 2 ] of ClF 3 gas and O 2 gas is preferably in the range of 1 to 100.
  • the time for supplying ClF 3 gas and O 2 gas at one time is preferably in the range of 1 to 60 sec, and the number of repetitions is preferably about 1 to 100 times.
  • the valve 79 and the valve 80 are opened, and the valve 67 and the valve 70 are opened at the same time with the Ar gas as the carrier gas flowing.
  • ClF 3 gas and O 2 gas are supplied at the same time.
  • these flow rates may be in the range of ClF 3 gas: 10 to 1000 sccm and O 2 gas: 1 to 1000 sccm.
  • the value of the flow rate ratio [ClF 3 / O 2 ] of ClF 3 gas and O 2 gas is preferably in the range of 1 to 100.
  • the cleaning time is preferably about 60 to 3600 sec.
  • the flow rates of ClF 3 gas and O 2 gas may be changed on the way.
  • the valves 67 and 70 are closed, the flow rate of Ar gas, which is a carrier gas, is increased, and the inside of the processing container 11 is purged.
  • the operation of the first aspect and / or the operation of the second aspect may be performed a plurality of times with the purge of the processing container 11 interposed therebetween. Specifically, only the operation of the first aspect may be performed a plurality of times, only the second aspect may be performed a plurality of times, or both of these may be performed a plurality of times at an arbitrary timing.
  • FIG. 5 is a cross-sectional view schematically showing a second example of a film forming apparatus for carrying out the film forming method according to one embodiment.
  • This film forming apparatus 200 is a batch type film forming apparatus for forming a ruthenium-containing film by CVD.
  • the film forming apparatus 200 includes a heating furnace 102 having a tubular heat insulating body 103 having a ceiling portion and a heater 104 provided on the inner peripheral surface of the heat insulating body 103.
  • the heating furnace 102 is installed on the base plate 105.
  • the heating furnace 102 has a double-tube structure having an outer tube 111 made of, for example, quartz and having a closed upper end, and an inner tube 112 made of, for example, quartz, which are concentrically installed in the outer tube 111.
  • the processing container 110 is inserted.
  • the heater 104 is provided so as to surround the outside of the processing container 110.
  • the outer pipe 111 and the inner pipe 112 are each held at the lower ends of the tubular manifold 113 made of stainless steel or the like, and the lower end opening of the manifold 113 is for airtightly sealing the opening.
  • the cap portion 114 is provided so as to be openable and closable.
  • a rotating shaft 115 that can rotate in an airtight state is inserted through the center of the cap portion 114, for example, the lower end of the rotating shaft 115 is connected to the rotating mechanism 117 of the elevator table 116, and the upper end is a turntable. It is fixed at 118.
  • a wafer boat 120 made of quartz, which is a substrate holder for holding the wafer W which is a substrate to be processed, is placed on the turntable 118 via a heat insulating cylinder 119.
  • the wafer boat 120 is configured so that, for example, 50 to 150 wafers W can be stacked and accommodated at a pitch of predetermined intervals.
  • the wafer boat 120 can be carried in and out of the processing container 110 by raising and lowering the elevating table 116 by an elevating mechanism (not shown).
  • the cap portion 114 comes into close contact with the manifold 113, and the space between them is hermetically sealed.
  • the film forming apparatus 200 is for supplying a processing gas for forming a CVD film on a ruthenium-containing film and a cleaning gas for cleaning the inside of the processing container 110, which are configured in the same manner as the gas supply mechanism 40 of the film forming apparatus 100. It has a gas supply mechanism 130 of. The gas from the gas supply mechanism 130 is supplied into the processing container 110 via two quartz nozzles 121 and 122 provided so as to penetrate the lower side wall of the manifold 113.
  • An exhaust pipe 141 for discharging the processing gas from the gap between the outer pipe 111 and the inner pipe 112 is connected to the upper part of the side wall of the manifold 113.
  • An exhaust device 142 having a vacuum pump, a pressure control valve, or the like is connected to the exhaust pipe 141. Then, by operating the exhaust device 142, it is possible to bring the inside of the processing container 110 into a predetermined decompression (vacuum) state. Further, the pressure control valve controls the inside of the processing container 110 to a predetermined pressure.
  • the film forming apparatus 200 has a controller 150 for controlling each component such as a power supply for the heater 104, a drive mechanism such as an elevating mechanism, and a heater power supply. Based on the processing recipe stored in the storage medium, the controller 150 causes each component of the film forming apparatus 200 to perform a predetermined operation so that the film forming method is performed.
  • the wafer boat 120 In the film forming apparatus 200 configured as described above, for example, 50 to 150 wafers W are mounted on the wafer boat 120, and the wafer boat 120 on which the wafer W is mounted is placed on the turntable 118 via the heat insulating cylinder 119. To do. By raising the elevating table 160 in this state, the wafer boat 120 is carried into the processing container 110 from the lower opening.
  • the lower end opening of the manifold 113 is closed by the cap portion 114 to seal the inside of the processing container 110, and the pressure inside the processing container 110 while supplying purge gas (for example, Ar gas supplied as a carrier gas) into the processing container 110. Is controlled to, for example, 10 to 1000 Pa.
  • purge gas for example, Ar gas supplied as a carrier gas
  • the heater 104 heats the temperature inside the processing container 110 to, for example, 100 to 300 ° C.
  • a ruthenium-containing film having a predetermined film thickness is formed on the wafer W by the same procedure as that of the film forming apparatus 100 of the first example.
  • the flow rate of the CO gas as the carrier gas and the flow rate of the counter CO gas are appropriately set according to the size of the processing container 110 and the number of wafers W mounted on the wafer boat 120.
  • dry cleaning is performed.
  • the number of film formations until dry cleaning, that is, the cleaning cycle, is preset by calculating the integrated film thickness of the ruthenium-containing film deposited on the inner wall of the processing container 110.
  • the inside of the processing container 110 is sealed in a state where the wafer boat 120 does not exist in the processing container 110, and the inside of the processing container 110 is kept at a predetermined temperature, preferably 200 ° C. or less, more preferably by the heater 104. Heat to 150-200 ° C. Then, the inside of the processing container 110 is purged with Ar gas, and the pressure inside the processing container 110 is adjusted to 10 to 1000 Pa. Dry cleaning is performed in this state.
  • the first aspect is supplied alternately and ClF 3 gas and O 2 gas, any of the second aspect supplying simultaneously ClF 3 gas and O 2 gas You may go with.
  • the flow rates of the Cl F 3 gas and the O 2 gas may be changed on the way.
  • the flow rates of ClF 3 gas, O 2 gas, and Ar gas as a purge gas are appropriately set according to the capacity of the processing container 110.
  • the operation of the first aspect and / or the operation of the second aspect may be performed a plurality of times with the purge of the processing container 11 interposed therebetween. Specifically, only the operation of the first aspect may be performed a plurality of times, only the second aspect may be performed a plurality of times, or both of these may be performed a plurality of times at an arbitrary timing.
  • the film formation of the ruthenium-containing film and the cleaning of the processing container after the film formation of the ruthenium-containing film have been described, but the present invention is not limited to this, and the film formation of the osmium-containing film and the formation of the osmium-containing film are not limited to this. Cleaning of the processing container after the membrane may be performed.
  • the osmium-containing film can be formed by reacting the osmium raw material gas with the reaction gas or thermally decomposing the osmium raw material gas on the substrate to be treated.
  • osmium-containing film a metal osmium film, an osmium oxide film, an osmium film containing an additive component such as Si or N, and the like can be mentioned. Furthermore, osmium exhibits chemical properties similar to ruthenium, and the osmium-containing film undergoes an etching reaction by the same mechanism as the ruthenium-containing film, so that film formation and cleaning can be performed in the same manner as the ruthenium-containing film.
  • the film forming apparatus is not limited thereto.
  • the shower head may not be provided and the supply may be performed through a nozzle or the like.
  • the gas supply mechanism is merely an example, and various forms can be used.
  • Ru 3 (CO) 12 is used as the ruthenium raw material gas as the film forming apparatus
  • ClF 3 gas is used as the halogen-containing gas of the cleaning gas
  • O 2 gas is used as the oxidation gas.
  • the device configuration can be made according to this.
  • a ruthenium film was formed with Ru 3 (CO) 12 gas and CO gas using the single-wafer film forming apparatus shown in FIG.
  • the thickness of the ruthenium film deposited on the wall of the processing container was calculated to be 10 ⁇ m (1000 sheets), and then dry cleaning was performed.
  • Example 1 dry cleaning was carried out using ClF 3 gas and O 2 gas at different temperatures in the range of 150 to 300 ° C.
  • the pressure was 100 Pa
  • the ClF 3 gas flow rate was 100 sccm
  • the O 2 gas flow rate was 100 sccm.
  • Comparative Example 1 dry cleaning was carried out using only ClF 3 gas at different temperatures in the range of 150 to 300 ° C.
  • the pressure and ClF 3 gas flow rate were the same as in Example 1.
  • FIG. 6 is a diagram showing the relationship between the temperature and the etching amount of the ruthenium film in Example 1 and Comparative Example 1. As shown in this figure, in Example 1, a high etching amount was obtained at a low temperature of 150 ° C., whereas in Comparative Example 1, the etching amount remained low at a temperature lower than 200 ° C.
  • Processing container 12 Suceptor 15,26,104; Heater 20; shower head 40,130; Gas supply mechanism 33,142; Exhaust mechanism 90,150; Controller 100,200; Film formation device 120; Wafer boat W Wafer (substrate to be processed)

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Abstract

Le but de la présente invention est de nettoyer une cuve de traitement à une température inférieure lorsqu'un film contenant du ruthénium ou un film contenant de l'osmium est formé. Ce procédé de formation de film comprend : une étape (étape 1) consistant à recevoir un substrat à traiter dans une cuve de traitement et à former un film contenant du ruthénium ou un film contenant de l'osmium sur le substrat à traiter dans la cuve de traitement au moyen d'un dépôt chimique en phase vapeur ; et, après exécution de l'étape de formation de film une ou plusieurs fois, une étape (étape 2) consistant à fournir un gaz contenant un/des halogène(s) et un gaz oxydant dans la cuve de traitement dans un état dans lequel le substrat à traiter n'est pas présent dans la cuve de traitement et à nettoyer à sec l'intérieur de la cuve de traitement.
PCT/JP2020/019952 2019-05-22 2020-05-20 Procédé de formation de film, appareil de formation de film et procédé de nettoyage de cuve de traitement WO2020235596A1 (fr)

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JP2019095723A JP2020190014A (ja) 2019-05-22 2019-05-22 成膜方法および成膜装置、ならびに処理容器のクリーニング方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08153707A (ja) * 1994-11-29 1996-06-11 Nec Corp 半導体装置の製造方法
JP2003027240A (ja) * 2001-07-23 2003-01-29 Hitachi Ltd 半導体製造装置及びそのクリーニング方法
KR20090104258A (ko) * 2008-03-31 2009-10-06 주식회사 아이피에스 박막 증착 장비의 챔버 세정 방법
JP2015037134A (ja) * 2013-08-14 2015-02-23 大陽日酸株式会社 炭化珪素除去装置、及び炭化珪素除去方法
WO2016140166A1 (fr) * 2015-03-02 2016-09-09 株式会社日立国際電気 Procédé de nettoyage, procédé de fabrication de dispositif à semi-conducteur, dispositif de traitement de substrat, et support d'enregistrement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08153707A (ja) * 1994-11-29 1996-06-11 Nec Corp 半導体装置の製造方法
JP2003027240A (ja) * 2001-07-23 2003-01-29 Hitachi Ltd 半導体製造装置及びそのクリーニング方法
KR20090104258A (ko) * 2008-03-31 2009-10-06 주식회사 아이피에스 박막 증착 장비의 챔버 세정 방법
JP2015037134A (ja) * 2013-08-14 2015-02-23 大陽日酸株式会社 炭化珪素除去装置、及び炭化珪素除去方法
WO2016140166A1 (fr) * 2015-03-02 2016-09-09 株式会社日立国際電気 Procédé de nettoyage, procédé de fabrication de dispositif à semi-conducteur, dispositif de traitement de substrat, et support d'enregistrement

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