WO2017046921A1 - 半導体装置の製造方法、基板処理装置および記録媒体 - Google Patents
半導体装置の製造方法、基板処理装置および記録媒体 Download PDFInfo
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- WO2017046921A1 WO2017046921A1 PCT/JP2015/076526 JP2015076526W WO2017046921A1 WO 2017046921 A1 WO2017046921 A1 WO 2017046921A1 JP 2015076526 W JP2015076526 W JP 2015076526W WO 2017046921 A1 WO2017046921 A1 WO 2017046921A1
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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- 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
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Definitions
- the present invention relates to a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium.
- a film forming process for forming a film on a substrate may be performed.
- An object of the present invention is to provide a technique capable of improving the film quality of a film formed on a substrate.
- the film quality of the film formed on the substrate can be improved.
- FIG. 2 is a schematic configuration diagram of a part of a vertical processing furnace of a substrate processing apparatus suitably used in an embodiment of the present invention, and is a diagram showing a part of the processing furnace as a cross-sectional view taken along line AA of FIG.
- the controller of the substrate processing apparatus used suitably by embodiment of this invention, and is a figure which shows the control system of a controller with a block diagram.
- (A) is a film-forming sequence of 1st Embodiment of this invention
- (b) is a figure which shows the film-forming sequence of other embodiment of this invention.
- (A) is a film-forming sequence of 2nd Embodiment of this invention
- (b) is a figure which shows the film-forming sequence of other embodiment of this invention. It is a figure which shows the film-forming sequence of other embodiment of this invention.
- the processing furnace 202 has a heater 207 as heating means (heating mechanism).
- the heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.
- the heater 207 functions as an activation mechanism (excitation unit) that activates (excites) gas with heat.
- a reaction tube 203 is disposed inside the heater 207 concentrically with the heater 207.
- the reaction tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end opened.
- a manifold (inlet flange) 209 is disposed below the reaction tube 203 concentrically with the reaction tube 203.
- the manifold 209 is made of a metal such as stainless steel (SUS), for example, and is formed in a cylindrical shape with an upper end and a lower end opened. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203 and is configured to support the reaction tube 203.
- An O-ring 220a as a seal member is provided between the manifold 209 and the reaction tube 203.
- the reaction tube 203 As the manifold 209 is supported by the heater base, the reaction tube 203 is installed vertically.
- a processing vessel (reaction vessel) is mainly constituted by the reaction tube 203 and the manifold 209.
- a processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to accommodate a plurality of wafers 200 as substrates in a state where they are arranged in multiple stages in a vertical posture in a horizontal posture by a boat 217 described later.
- nozzles 249a to 249c are provided so as to penetrate the manifold 209.
- the nozzles 249a to 249c are made of a heat resistant material such as quartz or SiC.
- Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.
- the processing container manifold 209 is provided with the three nozzles 249a to 249c and the three gas supply pipes 232a to 232c, and supplies a plurality of types of gases into the processing chamber 201. It is possible.
- the gas supply pipes 232a to 232c are provided with mass flow controllers (MFC) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as opening / closing valves, respectively, in order from the upstream direction.
- MFC mass flow controllers
- Gas supply pipes 232d to 232f for supplying an inert gas are connected to the gas supply pipes 232a to 232c on the downstream side of the valves 243a to 243c, respectively.
- the gas supply pipes 232d to 232f are provided with MFCs 241d to 241f as flow rate controllers (flow rate control units) and valves 243d to 243f as opening / closing valves, respectively, in order from the upstream direction.
- Nozzles 249a to 249c are connected to the distal ends of the gas supply pipes 232a to 232c, respectively. As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part from the lower part of the inner wall of the reaction tube 203. Each is provided so as to rise upward in the stacking direction. That is, the nozzles 249a to 249c are provided along the wafer arrangement area in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged.
- the nozzles 249a to 249c are respectively provided perpendicular to the surface (flat surface) of the wafer 200 on the side of the end (periphery) of the wafer 200 carried into the processing chamber 201.
- Each of the nozzles 249a to 249c is configured as an L-shaped long nozzle, and each horizontal portion thereof is provided so as to penetrate the side wall of the manifold 209, and each vertical portion thereof is at least in the wafer arrangement region. It is provided so as to rise from one end side toward the other end side.
- Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively.
- the gas supply holes 250 a to 250 c are each opened so as to face the center of the reaction tube 203, and can supply gas toward the wafer 200.
- a plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided with the same opening pitch.
- an annular vertically long space in a plan view defined by the inner wall of the reaction tube 203 and the ends of a plurality of stacked wafers 200 that is, a cylindrical space.
- Gas is conveyed through nozzles 249a to 249c arranged inside. Then, gas is first ejected into the reaction tube 203 from the gas supply holes 250a to 250c opened in the nozzles 249a to 249c, respectively, in the vicinity of the wafer 200.
- the main flow of gas in the reaction tube 203 is a direction parallel to the surface of the wafer 200, that is, a horizontal direction.
- the gas flowing on the surface of the wafer 200 that is, the residual gas after the reaction, flows toward the exhaust port, that is, the direction of the exhaust pipe 231 described later.
- the direction of the remaining gas flow is appropriately specified depending on the position of the exhaust port, and is not limited to the vertical direction.
- a halosilane source gas containing Si and a halogen element as the predetermined element is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a as the source gas containing the predetermined element.
- the raw material gas is a raw material in a gaseous state, for example, a gas obtained by vaporizing a liquid raw material that is in a liquid state under normal temperature and normal pressure, a gaseous raw material that is in a gaseous state under normal temperature and normal pressure, or the like.
- the halosilane raw material is a silane raw material having a halogen group.
- the halogen group includes chloro group, fluoro group, bromo group, iodo group and the like. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and the like. It can be said that the halosilane raw material is a kind of halide.
- the term “raw material” when used, it means “a raw material in a liquid state”, “a raw material in a gas state (raw material gas)”, or both of them. There is a case.
- halosilane source gas for example, a source gas containing Si, Cl and an alkylene group and having a Si—C bond, that is, an alkylene chlorosilane source gas which is an organic chlorosilane source gas can be used.
- the alkylene group includes a methylene group, an ethylene group, a propylene group, a butylene group and the like.
- the alkylene chlorosilane source gas can also be referred to as an alkylene halosilane source gas.
- alkylene chlorosilane source gas examples include bis (trichlorosilyl) methane ((SiCl 3 ) 2 CH 2 , abbreviation: BTCSM) gas, ethylene bis (trichlorosilane) gas, that is, 1,2-bis (trichlorosilyl) ethane. ((SiCl 3 ) 2 C 2 H 4 , abbreviation: BTCSE) gas or the like can be used. It can be said that these gases are source gases containing at least two Si in one molecule, further containing C and Cl, and having a Si—C bond. These gases act as a Si source and also as a C source in a film forming process to be described later.
- halosilane source gas for example, a source gas containing Si, Cl and an alkyl group and having a Si—C bond, that is, an alkylchlorosilane source gas which is an organic chlorosilane source gas can be used.
- Alkyl groups include methyl, ethyl, propyl, butyl and the like.
- the alkylchlorosilane source gas can also be referred to as an alkylhalosilane source gas.
- alkylchlorosilane source gas examples include 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH 3 ) 2 Si 2 Cl 4 , abbreviation: TCMDDS) gas, 1,2-dichloro-1 , 1,2,2-tetramethyldisilane ((CH 3 ) 4 Si 2 Cl 2 , abbreviation: DCTMDS) gas, 1-monochloro-1,1,2,2,2-pentamethyldisilane ((CH 3 ) 5 Si 2 Cl (abbreviation: MCPMDS) gas or the like can be used. It can be said that these gases are source gases containing at least two Si in one molecule, further containing C and Cl, and having a Si—C bond. Note that these gases also have Si—Si bonds. These gases act as a Si source and also as a C source in a film forming process to be described later.
- a C-free source gas containing Si and Cl that is, an inorganic chlorosilane source gas
- an inorganic chlorosilane source gas for example, hexachlorodisilane (Si 2 Cl 6 , abbreviation: HCDS) gas, octachlorotrisilane (Si 3 Cl 8 , abbreviation: OCTS) gas, or the like can be used. It can be said that these gases are source gases containing at least two Si in one molecule, further containing Cl, and having a Si—Si bond. These gases act as Si sources in the film forming process described later.
- the liquid source When using a liquid source that is in a liquid state at normal temperature and pressure, such as BTCSM, TCMDDS, and HCDS, the liquid source is vaporized by a vaporization system such as a vaporizer or bubbler and supplied as a source gas. .
- a vaporization system such as a vaporizer or bubbler
- a gas containing an OH group (hydroxy group) is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b as a reaction gas (reactant) having a chemical structure different from that of the source gas.
- the gas containing an OH group acts as an oxidizing agent (oxidizing gas), that is, an O source in a film forming process described later.
- oxidizing gas oxidizing gas
- water vapor H 2 O gas
- RO Reverse Osmosis
- deionized water from which impurities have been removed by applying deionization treatment or distillation from which impurities have been removed by distillation using a distiller Pure water (or ultrapure water) such as water is vaporized by a vaporization system such as a vaporizer, bubbler, or boiler, and supplied as a gas containing OH groups (H 2 O gas).
- a vaporization system such as a vaporizer, bubbler, or boiler
- a catalyst gas that promotes the film forming reaction using the above-described raw material gas and reaction gas is supplied into the processing chamber 201 through the MFC 241c, the valve 243c, and the nozzle 249c.
- the catalyst gas for example, an amine-based gas containing C, N, and H can be used.
- the amine-based gas is a gas containing an amine in which at least one of H in ammonia (NH 3 ) is substituted with a hydrocarbon group such as an alkyl group.
- a hydrocarbon group such as an alkyl group.
- An amine containing N having a lone pair and having an acid dissociation constant (hereinafter also referred to as pKa) of, for example, about 5 to 11 can be suitably used as a catalyst.
- the acid dissociation constant (pKa) is one of the indexes that quantitatively express the strength of the acid, and is an equilibrium constant Ka in the dissociation reaction in which H ions are released from the acid, expressed as a negative common logarithm.
- a cyclic amine-based gas in which a hydrocarbon group is cyclic or a chain amine-based gas in which a hydrocarbon group is chained can be used as the amine-based gas.
- the cyclic amine-based gas is a heterocyclic compound (heterocyclic compound) having a cyclic structure composed of a plurality of kinds of elements of C and N, that is, a nitrogen-containing heterocyclic compound.
- the amine-based gas that acts as a catalyst can also be referred to as an amine-based catalyst or an amine-based catalyst gas.
- the catalyst illustrated here may decompose
- Such a substance that partially changes before and after a chemical reaction is not strictly a “catalyst”.
- Catalyst Even when a part of the chemical reaction is decomposed in the course of the chemical reaction, most of the substance is not decomposed, and the substance that changes the rate of the reaction and substantially acts as a catalyst, This is referred to as “catalyst”.
- fluorine (F) -based gas as a reformed gas is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a.
- the fluorine-based gas acts as a fluorinated gas, that is, an F source by appropriately controlling the conditions of the reforming process described later.
- nitrogen fluoride (NF 3 ) gas or fluorine (F 2 ) gas can be used as the fluorine-based gas.
- NF 3 gas and F 2 gas are F-containing gases not containing C.
- nitrogen (N 2 ) gas as an inert gas passes through the MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. Supplied into 201.
- a source gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a.
- the nozzle 249a may be included in the source gas supply system.
- the source gas supply system can also be referred to as a source supply system.
- the source gas supply system may be referred to as a halosilane source gas supply system or a halosilane source supply system.
- a reaction gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b.
- the nozzle 249b may be included in the reaction gas supply system.
- the reaction gas supply system can also be referred to as a reactant supply system.
- the reaction gas supply system can also be referred to as an OH group-containing gas supply system, an O-containing gas supply system, an oxidant supply system, or an oxidizing gas supply system. .
- a catalyst gas supply system is mainly configured by the gas supply pipe 232c, the MFC 241c, and the valve 243c.
- the nozzle 249c may be included in the catalyst gas supply system.
- the catalyst gas supply system can also be referred to as a catalyst supply system.
- the catalyst gas supply system may be referred to as an amine catalyst gas supply system, an amine gas supply system, or an amine supply system.
- a reformed gas supply system When supplying the above-described reformed gas from the gas supply pipe 232a, a reformed gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a.
- the nozzle 249a may be included in the reformed gas supply system.
- the reformed gas supply system When supplying the above-mentioned fluorine-based gas from the gas supply pipe 232a, the reformed gas supply system may be referred to as a fluorine-based gas supply system, a fluoride gas supply system, or an F-containing gas supply system.
- an inert gas supply system is mainly configured by the gas supply pipes 232d to 232f, the MFCs 241d to 241f, and the valves 243d to 243f.
- the reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201.
- the exhaust pipe 231 is connected to a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit).
- a vacuum pump 246 as a vacuum exhaust device is connected.
- the APC valve 244 can perform vacuum evacuation and vacuum evacuation stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 activated, and further, with the vacuum pump 246 activated,
- the valve is configured such that the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening based on the pressure information detected by the pressure sensor 245.
- An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245.
- the vacuum pump 246 may be included in the exhaust system.
- a seal cap 219 is provided as a furnace opening lid capable of airtightly closing the lower end opening of the manifold 209.
- the seal cap 219 is configured to contact the lower end of the manifold 209 from the lower side in the vertical direction.
- the seal cap 219 is made of a metal such as SUS and is formed in a disk shape.
- an O-ring 220b is provided as a seal member that comes into contact with the lower end of the manifold 209.
- a rotation mechanism 267 for rotating a boat 217 described later is installed on the opposite side of the seal cap 219 from the processing chamber 201.
- a rotation shaft 255 of the rotation mechanism 267 passes through the seal cap 219 and is connected to the boat 217.
- the rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217.
- the seal cap 219 is configured to be lifted and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism vertically installed outside the reaction tube 203.
- the boat elevator 115 is configured so that the boat 217 can be carried in and out of the processing chamber 201 by moving the seal cap 219 up and down.
- the boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217, that is, the wafers 200 into and out of the processing chamber 201.
- a shutter 219s is provided below the manifold 209 as a furnace port lid that can airtightly close the lower end opening of the manifold 209 while the seal cap 219 is lowered by the boat elevator 115.
- the shutter 219s is made of a metal such as SUS and is formed in a disk shape.
- an O-ring 220c is provided on the upper surface of the shutter 219s.
- the opening / closing operation (elevating operation, rotating operation, etc.) of the shutter 219s is controlled by the shutter opening / closing mechanism 115s.
- the boat 217 as a substrate support is configured to support a plurality of, for example, 25 to 200, wafers 200 in a multi-stage manner by aligning them vertically in a horizontal posture and with their centers aligned. It is configured to arrange at intervals.
- the boat 217 is made of a heat-resistant material such as quartz or SiC.
- heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages. With this configuration, heat from the heater 207 is not easily transmitted to the seal cap 219 side.
- this embodiment is not limited to the above-mentioned form.
- a heat insulating cylinder configured as a cylindrical member made of a heat resistant material such as quartz or SiC may be provided.
- a temperature sensor 263 is installed as a temperature detector. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 becomes a desired temperature distribution.
- the temperature sensor 263 is configured in an L shape similarly to the nozzles 249a to 249c, and is provided along the inner wall of the reaction tube 203.
- the controller 121 which is a control unit (control means), is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d.
- the RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via the internal bus 121e.
- an input / output device 122 configured as a touch panel or the like is connected to the controller 121.
- the storage device 121c includes, for example, a flash memory, a HDD (Hard Disk Drive), and the like.
- a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner.
- the process recipe is a combination of the controller 121 that allows the controller 121 to execute each procedure in the substrate processing process described later and obtain a predetermined result, and functions as a program.
- the process recipe, the control program, and the like are collectively referred to simply as a program.
- a process recipe is also simply called a recipe.
- the RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily stored.
- the I / O port 121d includes the above-described MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc. It is connected to the.
- the CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a process recipe from the storage device 121c in response to an operation command input from the input / output device 122 or the like.
- the CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241f, the opening and closing operations of the valves 243a to 243f, the opening and closing operations of the APC valve 244, and the pressure by the APC valve 244 based on the pressure sensor 245 so as to match the contents of the read process recipe.
- the controller 121 is stored in an external storage device 123 (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, or a semiconductor memory such as a USB memory or a memory card).
- the above-mentioned program can be configured by installing it in a computer.
- the storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as a recording medium.
- recording medium When the term “recording medium” is used in this specification, it may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them.
- the program may be provided to the computer using a communication means such as the Internet or a dedicated line without using the external storage device 123.
- a film forming step for forming a film on the wafer 200 and a modification step for modifying the film formed on the wafer 200 are performed.
- SiOC film silicon oxycarbide film
- At least the surface of the SiOC film is modified by supplying NF 3 gas as a C-free fluorine-based gas to the wafer 200 under the condition that etching of the SiOC film formed on the wafer 200 does not occur.
- F is added (doped) to the entire area of the SiOC film formed on the wafer 200, and the entire SiOC film is a film containing Si, O, C, and F. That is, an example of modifying to a silicon oxycarbon fluoride film (SiOCF film) is shown.
- the SiOCF film can also be referred to as an F-containing SiOC film or an SiOC film to which F is added (doped).
- FIG. 4A a series of sequences shown in FIG. 4A may be shown as follows for convenience. The same notation is used in the description of other embodiments described below.
- wafer when the term “wafer” is used, it means “wafer itself” or “a laminate (aggregate) of a wafer and a predetermined layer or film formed on the surface”. In other words, it may be called a wafer including a predetermined layer or film formed on the surface.
- wafer surface when the term “wafer surface” is used in this specification, it means “the surface of the wafer itself (exposed surface)” or “the surface of a predetermined layer or film formed on the wafer”. That is, it may mean “the outermost surface of the wafer as a laminated body”.
- the phrase “supplying a predetermined gas to the wafer” means “supplying a predetermined gas directly to the surface (exposed surface) of the wafer itself”. , It may mean that “a predetermined gas is supplied to a layer, a film, or the like formed on the wafer, that is, to the outermost surface of the wafer as a laminated body”. Further, in this specification, when “describe a predetermined layer (or film) on the wafer” is described, “determine a predetermined layer (or film) directly on the surface (exposed surface) of the wafer itself”. This means that a predetermined layer (or film) is formed on a layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminate. There is a case.
- substrate is synonymous with the term “wafer”.
- Vacuum exhaust (reduced pressure) is performed by the vacuum pump 246 so that the processing chamber 201, that is, the space where the wafer 200 exists, has a desired pressure (degree of vacuum).
- the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information.
- the vacuum pump 246 maintains a state in which it is always operated until at least the processing on the wafer 200 is completed. Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired temperature.
- the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed. Further, the rotation of the boat 217 and the wafers 200 by the rotation mechanism 267 is started. The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continuously performed at least until the processing on the wafer 200 is completed.
- Step 1 BTCSM gas and pyridine gas are supplied to the wafer 200 in the processing chamber 201.
- the valves 243a and 243c are opened, and BTCSM gas and pyridine gas are allowed to flow into the gas supply pipes 232a and 232c, respectively.
- the flow rates of the BTCSM gas and the pyridine gas are adjusted by the MFCs 241a and 241c, supplied into the processing chamber 201 through the nozzles 249a and 249c, mixed into the processing chamber 201, and then mixed (Post-mix) and exhausted. Exhaust from the tube 231.
- the valves 243d and 243f are opened, and N 2 gas is allowed to flow into the gas supply pipes 232d and 232f.
- the N 2 gas flowing through the gas supply pipes 232d and 232f is adjusted in flow rate by the MFCs 241d and 241f, supplied into the processing chamber 201 together with the BTCSM gas and pyridine gas, and exhausted from the exhaust pipe 231. Further, in order to prevent BTCSM gas and pyridine gas from entering the nozzle 249b, the valve 243e is opened, and N 2 gas is allowed to flow into the gas supply pipe 232e. The N 2 gas is supplied into the processing chamber 201 through the gas supply pipe 232b and the nozzle 249b, and is exhausted from the exhaust pipe 231.
- the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 1 to 3000 Pa, preferably 133 to 2666 Pa.
- the supply flow rate of the BTCSM gas controlled by the MFC 241a is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm.
- the supply flow rate of the pyridine gas controlled by the MFC 241c is, for example, a flow rate in the range of 1 to 2000 sccm, preferably 10 to 1000 sccm.
- the supply flow rate of the N 2 gas controlled by the MFCs 241d to 241f is, for example, a flow rate in the range of 100 to 10,000 sccm.
- the time for supplying the BTCSM gas and the pyridine gas to the wafer 200 is, for example, 1 to 100 seconds, preferably 5 to 60 seconds.
- the temperature of the heater 207 is the temperature in the processing chamber 201, that is, the temperature of the wafer 200 is, for example, 10 ° C. or higher and 90 ° C. or lower, preferably room temperature (25 ° C.) or higher and 70 ° C. or lower, more preferably 50 ° C. or higher.
- the temperature is set to a temperature (film forming temperature) within a range of 70 ° C. or lower.
- the pressure in the processing chamber 201 is set to a predetermined pressure (for example, 1333 Pa) within the above-described range, when the temperature of the wafer 200 in the film forming step is less than 10 ° C., the gas supplied into the processing chamber 201 (step 1 , 2, at least one of BTCSM gas, H 2 O gas, and pyridine gas) tends to aggregate, and these gases may be liquefied.
- the etching resistance also referred to as HF resistance or acid resistance
- the temperature of the wafer 200 in the film forming step By setting the temperature of the wafer 200 in the film forming step to be room temperature or higher, it becomes easy to suppress the aggregation reaction of the gas supplied into the processing chamber 201. As a result, the etching resistance of the film formed on the wafer 200 can be increased, and the in-plane film thickness uniformity and in-plane film quality uniformity of the film can be improved.
- the temperature of the wafer 200 in the film forming step to 50 ° C. or higher, the aggregation reaction of the gas supplied into the processing chamber 201 can be reliably suppressed, and the etching resistance of the film formed on the wafer 200 can be reduced. Further, the in-plane film thickness uniformity and the in-plane film quality uniformity of the film can be further improved.
- the pressure in the processing chamber 201 is set to a predetermined pressure (for example, 1333 Pa) within the above-described range, if the temperature of the wafer 200 in the film formation step exceeds 90 ° C., a film formation reaction (step in the wafer 200) The reaction of forming the first layer and the second layer described later in 1 and 2 is difficult to proceed, and the thickness of the layer formed per cycle may decrease (the cycle rate decreases). As a result, the film formation rate of the film formed on the wafer 200 may decrease.
- This can be solved by setting the temperature of the wafer 200 in the film formation step to 90 ° C. or lower.
- the temperature of the wafer 200 in the film forming step By setting the temperature of the wafer 200 in the film forming step to 70 ° C. or lower, it is possible to reliably ensure (maintain) a practical level cycle rate, that is, a practical level film forming rate.
- the temperature in the processing chamber 201 in the film formation step that is, the temperature of the wafer 200 (film formation temperature) is 10 ° C. or higher and 90 ° C. or lower, preferably room temperature or higher and 70 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. or lower. It is good to set the temperature within the range.
- a C layer having a thickness of, for example, less than one atomic layer to several atomic layers is formed as a first layer on the wafer 200 (surface underlayer film).
- a Si-containing layer containing Cl is formed.
- the Si-containing layer containing C and Cl becomes a layer containing a Si—C bond.
- the Si-containing layer containing C and Cl may be a Si layer containing C and Cl, an adsorption layer of BTCSM, or both of them. In this specification, the Si-containing layer containing C and Cl may be simply referred to as a Si-containing layer containing C for convenience.
- the Si layer containing C and Cl is a generic name including a continuous layer composed of Si and containing C and Cl, as well as a discontinuous layer and a Si thin film containing C and Cl formed by overlapping them. .
- a continuous layer made of Si and containing C and Cl may be referred to as a Si thin film containing C and Cl.
- Si constituting the Si layer containing C and Cl includes not only completely broken bonds with C and Cl but also completely broken bonds with C and Cl.
- the BTCSM adsorption layer includes a discontinuous adsorption layer in addition to a continuous adsorption layer composed of BTCSM molecules. That is, the adsorption layer of BTCSM includes an adsorption layer having a thickness of less than one molecular layer composed of BTCSM molecules or less than one molecule layer.
- the BTCSM molecules constituting the BTCSM adsorption layer include those in which the bond between Si and C is partially broken and those in which the bond between Si and Cl is partially broken. That is, the BTCSM adsorption layer may be a BTCSM physical adsorption layer, a BTCSM chemical adsorption layer, or both of them.
- a layer having a thickness of less than one atomic layer means an atomic layer formed discontinuously, and a layer having a thickness of one atomic layer means an atomic layer formed continuously.
- a layer having a thickness of less than one molecular layer means a molecular layer formed discontinuously, and a layer having a thickness of one molecular layer means a molecular layer formed continuously.
- the Si-containing layer containing C and Cl can include both an Si layer containing C and Cl and an adsorption layer of BTCSM. However, as described above, expressions such as “one atomic layer” and “several atomic layer” are used for the Si-containing layer containing C and Cl.
- the action of oxidation in step 2 described later does not reach the entire first layer.
- the minimum thickness of the first layer that can be formed on the wafer 200 is less than one atomic layer. Therefore, it is preferable that the thickness of the first layer be less than one atomic layer to several atomic layers.
- the thickness of the first layer By setting the thickness of the first layer to 1 atomic layer or less, that is, 1 atomic layer or less than 1 atomic layer, the action of the oxidation reaction in Step 2 described later can be relatively enhanced.
- the time required for the oxidation reaction can also be shortened.
- the time required for forming the first layer in step 1 can also be shortened.
- the processing time per cycle can be shortened, and the total processing time can be shortened. That is, the film forming rate can be increased. Moreover, the controllability of the film thickness uniformity can be improved by setting the thickness of the first layer to 1 atomic layer or less.
- Si is deposited on the wafer 200 to form a Si layer containing C and Cl.
- the BTCSM adsorption layer is formed by adsorbing the BTCSM on the wafer 200.
- at least a part of the Si—C bond in the BTCSM gas is retained (maintained) without being broken, and is directly taken into the Si-containing layer containing C and Cl. It is preferable to form a Si layer containing C and Cl on the wafer 200 rather than forming a BTCSM adsorption layer on the wafer 200 because the film formation rate can be increased.
- the temperature of the wafer 200 is set to a low temperature of 90 ° C. or less, for example, the BTCSM adsorption layer is more easily formed on the wafer 200 instead of the Si layer containing C and Cl.
- the BTCSM adsorption layer is easily constituted by the BTCSM physical adsorption layer, not the BTCSM chemical adsorption layer.
- the pyridine gas acts as a catalyst gas that weakens the bonding force of O—H bonds existing on the surface of the wafer 200, promotes decomposition of BTCSM, and promotes formation of the first layer by chemical adsorption of BTCSM molecules. That is, when pyridine gas is supplied to the wafer 200, the pyridine gas acts on the O—H bonds existing on the surface of the wafer 200, and acts to weaken the bonding force.
- the reaction between the weakened bonding force H and the BTCSM gas Cl produces a gaseous substance containing Cl and H, desorbs H from the surface of the wafer 200, and desorbs Cl from the BTCSM molecules. Will be separated.
- BTCSM molecules (halides) that have lost Cl are chemically adsorbed on the surface of the wafer 200 or the like. As a result, a BTCSM chemical adsorption layer is formed on the wafer 200 as the first layer.
- the reason why the bonding force of the O—H bond existing on the surface of the wafer 200 is weakened by the catalytic action of the pyridine gas is that N having a lone electron pair in the pyridine molecule acts to attract H.
- a compound having a large pKa has a stronger ability to attract H.
- a compound having a pKa of 5 or more as a catalyst gas, it is possible to promote the decomposition of BTCSM and promote the formation of the first layer by chemical adsorption.
- Cl extracted from the BTCSM molecule reacts with the catalyst gas, thereby generating a salt (particle source) such as ammonium chloride (NH 4 Cl).
- a compound having a pKa of, for example, 11 or less, preferably 7 or less is preferable to use as the catalyst gas.
- Pyridine gas has a relatively large pKa of about 5.67 and is 7 or less, so it can be suitably used as a catalyst gas.
- the valves 243a and 243c are closed, and the supply of BTCSM gas and pyridine gas into the processing chamber 201 is stopped.
- the APC valve 244 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and BTCSM gas and pyridine gas after remaining in the processing chamber 201 or contributing to the formation of the first layer , Reaction by-products and the like are removed from the processing chamber 201.
- the supply of N 2 gas into the processing chamber 201 is maintained while the valves 243d to 243f are kept open.
- the N 2 gas acts as a purge gas, thereby enhancing the effect of removing unreacted BTCSM gas, pyridine gas, etc. remaining in the processing chamber 201 or contributing to the formation of the first layer from the processing chamber 201. Can do.
- the gas remaining in the processing chamber 201 may not be completely removed, and the inside of the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is very small, there will be no adverse effect in the subsequent step 2.
- the flow rate of the N 2 gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount equivalent to the volume of the reaction tube 203 (processing chamber 201), an adverse effect occurs in step 2. There can be no purging. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. It is also possible to minimize the consumption of N 2 gas.
- a silane source gas having a Si—C bond such as BTCSE gas, TCMDDS gas, DCTMDS gas, MCPMDS gas, or the like can be used.
- the catalyst gas examples include pyridine gas, cyclic amine gases such as aminopyridine gas, picoline gas, lutidine gas, piperazine gas, and piperidine gas, and chains such as TEA gas, DEA gas, MEA gas, TMA gas, and MMA gas.
- a non-amine gas such as a gaseous amine gas or NH 3 gas can be used.
- the inert gas for example, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to N 2 gas.
- a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to N 2 gas.
- Step 2 H 2 O gas and pyridine gas are supplied to the wafer 200 in the processing chamber 201.
- the opening / closing control of the valves 243b, 243c, 243d to 243f is performed in the same procedure as the opening / closing control of the valves 243a, 243c, 243d to 243f in Step 1.
- the flow rates of the H 2 O gas and the pyridine gas are adjusted by the MFCs 241b and 241c, respectively, are supplied into the processing chamber 201 through the nozzles 249b and 249c, are mixed into the processing chamber 201, and then are mixed (Post-mix).
- the exhaust pipe 231 is exhausted. Further, N 2 gas for preventing intrusion of H 2 O gas or the like into the nozzle 249a is supplied into the processing chamber 201 through the gas supply pipe 232a and the nozzle 249a and is exhausted from the exhaust pipe 231.
- the supply flow rate of the H 2 O gas controlled by the MFC 241b is, for example, 10 to 10,000 sccm, preferably 100 to 1000 sccm.
- the supply flow rate of the pyridine gas controlled by the MFC 241c is, for example, a flow rate in the range of 1 to 2000 sccm, preferably 10 to 1000 sccm.
- the time for supplying H 2 O gas and pyridine gas to the wafer 200 is, for example, 1 to 100 seconds, preferably 5 to 60 seconds.
- the other processing conditions are, for example, the same processing conditions as in Step 1.
- the second layer By supplying H 2 O gas to the wafer 200 under the above-described conditions, at least a part of the first layer formed on the wafer 200 in Step 1 is oxidized (modified).
- a second layer containing Si, O, and C that is, a silicon oxycarbide layer (SiOC layer) is formed.
- SiOC layer silicon oxycarbide layer
- impurities such as Cl contained in the first layer in the course of the reforming reaction by the H 2 O gas, constitutes a gaseous material containing at least Cl, from the process chamber 201 Discharged. That is, impurities such as Cl in the first layer are separated from the first layer by being extracted from or desorbed from the first layer.
- the second layer is a layer having less impurities such as Cl than the first layer.
- Pyridine gas weakens the bonding force of O-H bond the H 2 O gas has, promote decomposition of the H 2 O gas, the catalyst for promoting the formation of the second layer by reaction with the H 2 O gas and the first layer Acts as a gas. That is, when supplying the pyridine gas to the wafer 200, the pyridine gas acts on O-H bonds with the the H 2 O gas, acts to weaken the bonding strength. A reaction between H having a weak bonding force and Cl in the first layer formed on the wafer 200 generates a gaseous substance containing Cl and H, and H is desorbed from H 2 O molecules. At the same time, Cl is desorbed from the first layer. O in the H 2 O gas that has lost H is bonded to Si in the first layer in which Cl is desorbed and at least a part of C remains. As a result, the oxidized first layer, that is, the second layer is formed on the wafer 200.
- the binding force of O-H bond the H 2 O gas has weakens, N having a lone electron pair in the pyridine molecule, in order to act to attract H.
- a compound having a large pKa has a stronger ability to attract H.
- the bonding force of the O—H bond of the H 2 O gas can be appropriately weakened, and the above-described oxidation reaction can be promoted.
- the salt extracted from the first layer may react with the catalyst gas to generate a salt such as NH 4 Cl.
- a compound having a pKa of, for example, 11 or less, preferably 7 or less is preferable to use as the catalyst gas.
- Pyridine gas has a relatively large pKa of about 5.67 and is 7 or less, so it can be suitably used as a catalyst gas. This is the same as step 1.
- the valves 243b and 243c are closed, and the supply of H 2 O gas and pyridine gas into the processing chamber 201 is stopped. Then, H 2 O gas, pyridine gas, reaction by-products, etc. remaining in the processing chamber 201 or contributed to the formation of the second layer are removed from the processing chamber 201 by the same processing procedure as in Step 1. Exclude. At this time, it is the same as in step 1 that the gas remaining in the processing chamber 201 does not have to be completely removed.
- an O-containing gas containing an O—H bond such as hydrogen peroxide (H 2 O 2 ) gas
- the reaction gas may be an O-containing gas not containing an OH bond, such as oxygen (O 2 ) gas, ozone (O 3 ) gas, hydrogen (H 2 ) gas + O 2 gas, H 2 gas + O 3 gas. Etc. can also be used.
- the above-described various amine-based gases and non-amine-based gases can be used in addition to the pyridine gas. That is, as the catalyst gas used in Step 2, a gas having the same molecular structure (chemical structure) as the catalyst gas used in Step 1, that is, a gas having the same material can be used. Further, as the catalyst gas used in Step 2, a gas having a molecular structure different from that of the catalyst gas used in Step 1, that is, a gas having a different material can be used.
- the inert gas for example, the above-described various rare gases can be used in addition to the N 2 gas.
- a SiOC film having a predetermined composition and a predetermined film thickness is formed on the wafer 200 by performing the above steps 1 and 2 non-simultaneously, that is, by performing a cycle in which the steps 1 and 2 are alternately performed at least once (a predetermined number of times). Can do.
- the above cycle is preferably repeated multiple times. That is, the thickness of the second layer (SiOC layer) formed per cycle is made smaller than the desired film thickness, and the thickness of the SiOC film formed by laminating the second layer becomes the desired film thickness. It is preferable to repeat the above-described cycle a plurality of times until it becomes.
- the opening / closing control of the valves 243a, 243d to 243f is performed in the same procedure as the opening / closing control of the valves 243a, 243d to 243f in Step 1 of the film forming step described above.
- the flow rate of the NF 3 gas is adjusted by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, NF 3 gas is supplied to the SiOC film formed on the wafer 200.
- the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 50 to 300 Torr (6650 to 39900 Pa), preferably 50 to 100 Torr (6650 to 13300 Pa). Pressure).
- the SiOC film formed on the wafer 200 and the NF 3 gas are difficult to react, and it may be difficult to dope F into the SiOC film.
- the SiOC film and the NF 3 gas can be reacted to dope F into the SiOC film.
- etching of the SiOC film formed on the wafer 200 with NF 3 gas may progress, and it may be difficult to dope F into the SiOC film.
- etching of the SiOC film can be suppressed, and F can be doped into the SiOC film without desorbing Si and C from the SiOC film.
- pressure in the processing chamber 201 to 100 Torr or less, the etching of the SiOC film can be reliably suppressed, and a larger amount of F can be doped into the SiOC film.
- the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 is, for example, in the range of 300 ° C. to 500 ° C., preferably 350 ° C. to 400 ° C. To do.
- the SiOC film formed on the wafer 200 and the NF 3 gas are difficult to react, and it may be difficult to dope F into the SiOC film.
- the SiOC film and the NF 3 gas can be reacted to dope F into the SiOC film.
- the temperature of the wafer 200 to 350 ° C. or higher, the reaction between the SiOC film and the NF 3 gas is promoted, and it becomes possible to dope a larger amount of F into the SiOC film.
- the supply flow rate of the NF 3 gas controlled by the MFC 241a is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm.
- the time for supplying the NF 3 gas to the wafer 200 is, for example, 10 to 1200 seconds, preferably 5 to 600 seconds.
- the other conditions are the same as the processing conditions of Step 1 in the film forming step described above.
- the SiOC film formed on the wafer 200 can be doped with F.
- the SiOC film is modified (fluorinated) into a film containing Si, O, C and F, that is, a SiOCF film.
- the doping of F is performed not only in the vicinity of the surface of the SiOC film but also in the entire region including the region deeper than the surface (deeply).
- the SiOCF film can also be referred to as an F-doped SiOC film.
- the inert gas for example, the above-described various rare gases can be used in addition to the N 2 gas.
- Step 243a When the formation of the SiOCF film is completed, the valve 243a is closed and the supply of NF 3 gas into the processing chamber 201 is stopped. Then, NF 3 gas and reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing procedure as Step 1 of the film forming step. At this time, it is the same as Step 1 of the film forming step that the gas remaining in the processing chamber 201 does not have to be completely removed.
- N 2 gas is supplied into the processing chamber 201 from each of the gas supply pipes 232d to 232f and exhausted from the exhaust pipe 231.
- N 2 gas acts as a purge gas.
- the inside of the processing chamber 201 is purged, and the gas and reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201 (after purge).
- the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).
- the SiOC film is doped with F by performing a modification step of supplying NF 3 gas to the wafer 200 under the condition that the etching of the SiOC film does not occur. It becomes possible to do. As a result, this film can be modified into a SiOCF film having higher etching resistance than the F-free SiOC film. In addition, by doping F into the SiOC film, this film can be modified into a low-k film having a lower dielectric constant than the F-free SiOC film that is a low-k film. Become.
- the temperature of the wafer 200 is modified to a temperature higher than the film formation temperature (a temperature in the range of 300 ° C. to 500 ° C., preferably 350 ° C. to 400 ° C.). It is possible to desorb impurities such as moisture (H 2 O) and C x H y contained in the film during the film formation process by performing a modification step that heats the film. It becomes.
- the quality of the SiOCF film formed by modifying the SiOC film can be improved. That is, by performing the modification step, the SiOC film can be annealed simultaneously with the doping of F into the SiOC film. Thereby, the etching resistance of the SiOCF film formed by modifying the SiOC film can be further improved.
- this film can be a porous film, and the dielectric constant of this film can be further reduced.
- the film forming method of this embodiment is particularly effective when embedding in a recess such as a trench or a hole formed on the surface of the wafer 200.
- a recess such as a trench or a hole formed on the surface of the wafer 200.
- the SOG (Spin On Glass) method using a coating raw material and the plasma CVD method are known as a film formation method for the SiOCF film.
- the SOG method it may be difficult to form a film with good coverage at a stepped portion such as a trench.
- the plasma CVD method not only the step coverage may be lowered as in the SOG method, but the surface of the wafer 200 may be damaged by the plasma.
- the film forming method of this embodiment since the source gas and the reactive gas are alternately supplied, a high step coverage can be obtained as compared with the SOG method and the plasma CVD method. Further, according to the film forming method of the present embodiment, since the film forming step and the modifying step are performed in a non-plasma atmosphere, plasma damage to the wafer 200 can be avoided.
- the SiOCF film formed in this embodiment has good suitability in etching resistance, step coverage, film thickness uniformity, and film thickness controllability, so that a semiconductor device (device) is manufactured. This is particularly effective when performing fine shape control required in the process.
- the SiOCF film formed in this embodiment can be suitably applied to applications such as sidewall spacers, etching stoppers, and hard masks.
- SADP Self-Aligned Double Patterning
- SAQP Self-Aligned
- the present invention can also be suitably applied to a patterning process that requires etching selectivity with other film types such as Quadruple Patterning.
- the SiOCF film formed in this embodiment is a Low-k film having a lower dielectric constant than the F-free SiOC film, it is particularly effective in reducing the parasitic capacitance of the semiconductor device.
- the SiOCF film formed in this embodiment can be suitably applied to uses such as a buried insulating film.
- Second Embodiment As shown in FIG. 5A and the film forming sequence shown below, after an SiOC film is formed on the wafer 200, F 2 gas is supplied to the wafer 200 under the condition that etching of the SiOC film does not occur.
- the surface of the SiOC film may be modified to a layer containing C and F and containing no Si and O, that is, a fluorocarbon layer (CF layer).
- an SiOC film is formed on the wafer 200 by the same processing procedure and processing conditions as the film forming step of the first embodiment. Thereafter, the reforming step is performed by the same processing procedure as the reforming step of the first embodiment.
- F 2 gas is used as the fluorine-based gas containing no C.
- the flow rate of the F 2 gas is adjusted by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, F 2 gas is supplied to the SiOC film formed on the wafer 200.
- the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 0.1 to 10 Torr (13.3 to 1330 Pa), preferably 0.5 to 1 Torr (66.5 to 133 Pa).
- the pressure is within the range (reforming pressure).
- the SiOC film formed on the wafer 200 and the F 2 gas are less likely to react with each other, and formation of C—F bonds on the surface of the SiOC film, Desorption of Si and O from the surface may be difficult.
- the SiOC film reacts with the F 2 gas to form a C—F bond on the surface of the SiOC film, and Si and O from the surface of the SiOC film. Desorption can proceed, which makes it possible to modify the surface of the SiOC film into a CF layer.
- the pressure in the processing chamber 201 By setting the pressure in the processing chamber 201 to 0.5 Torr or more, it is possible to reliably react the SiOC film with the F 2 gas and to reliably modify the surface of the SiOC film to the CF layer.
- the temperature of the heater 207 is set to a temperature (reforming temperature) in which the temperature of the wafer 200 is, for example, in the range of room temperature to 100 ° C., preferably in the range of room temperature to 50 ° C.
- the SiOC film formed on the wafer 200 and the F 2 gas are less likely to react with each other, forming a CF bond on the surface of the SiOC film, or from the surface of the SiOC film. It may be difficult to desorb Si and O.
- the SiOC film reacts with the F 2 gas to progress the formation of C—F bonds on the surface of the SiOC film and the desorption of Si and O from the surface of the SiOC film.
- the surface of the SiOC film can be modified to the CF layer.
- the supply flow rate of the F 2 gas controlled by the MFC 241a is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm.
- the time for supplying the F 2 gas to the wafer 200 is, for example, 10 to 1200 seconds, preferably 30 to 600 seconds.
- Other conditions are the same as the processing conditions of step 1 in the film forming step of the first embodiment.
- the surface of the SiOC film formed on the wafer 200 can be doped with F to form a C—F bond. It is also possible to desorb Si and O from the surface of the film while leaving C on the surface of the SiOC film. As a result, the surface of the SiOC film is modified into a layer containing C and F and containing no Si and O, that is, a CF layer. Note that when the CF layer is formed, Si constitutes a by-product such as SiF 4 and is discharged from the processing chamber 201.
- the CF layer is formed by F entering (doped) into the surface of the SiOC film.
- the CF layer acts to suppress the entry of F.
- F does not enter the SiOC film. That is, the doping of F in the present embodiment tends to proceed mainly in the vicinity of the surface of the SiOC film and hardly proceed in a region deeper than the surface. Further, the desorption of Si and O from the SiOC film also proceeds mainly in the vicinity of the surface of the SiOC film, and tends not to proceed in a region deeper than the surface. That is, according to the present embodiment, the composition and film quality can be maintained without modifying the region except the surface of the SiOC film.
- the CF layer formed by modifying the surface of the SiOC film suppresses intrusion of oxygen (O) or the like into the SiOC film when the wafer 200 is exposed to the atmosphere.
- the CF layer can also be referred to as a diffusion suppression layer (block layer) for F or O, a barrier layer, a cap layer, and the like.
- fluorine-based gas in addition to F 2 gas, iodine fluoride (IF 7 ) gas, chlorine fluoride (ClF 3 ) gas, HF gas, or a gas obtained by mixing these in any combination can be used.
- IF 7 iodine fluoride
- ClF 3 chlorine fluoride
- HF gas a gas obtained by mixing these in any combination
- the valve 243a is closed and the supply of F 2 gas into the processing chamber 201 is stopped. Then, F 2 gas, reaction byproducts, and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing procedure as in step 1 of the film forming step. At this time, it is the same as Step 1 of the film forming step that the gas remaining in the processing chamber 201 does not have to be completely removed.
- an after purge step, an atmospheric pressure return step, and an unloading step are performed according to the same processing procedure and processing conditions as in the first embodiment, and the processed wafers 200 are taken out from the boat 217, and the substrate processing step of this embodiment is performed. Ends.
- the reforming step of supplying F 2 gas to the wafer 200 under a condition in which the etching of the SiOC film does not occur is performed.
- the surface can be modified to the CF layer.
- the CF layer functions as a protective film against a chemical solution (etchant) such as an HF solution. Therefore, by modifying the surface of the SiOC film to a CF layer, this film can be made a film having higher etching resistance than an F-free SiOC film having no CF layer on the surface. A film having a low dielectric constant can be obtained.
- the temperature of the wafer 200 is heated to a modification temperature higher than the film formation temperature in the modification step, impurities can be desorbed from the film, and the surface It is possible to improve the quality of the SiOC film that has been modified into the CF layer.
- the supply of BTCSM gas and pyridine gas to the wafer 200 and the supply of H 2 O gas and pyridine gas to the wafer 200 are alternately performed without synchronization, so that the surface is changed to the CF layer. It is possible to improve the step coverage, film thickness uniformity, and film thickness controllability of the formed SiOC film.
- the CF layer formed on the surface of the SiOC film acts to suppress the entry of O or the like into the SiOC film when the wafer 200 is exposed to the atmosphere.
- the film formed on the wafer 200 can be a stable film that is strong against exposure to the atmosphere.
- each of the above effects is obtained when a halosilane source gas other than BTCSM gas is used as the source gas, when an oxidizing gas other than H 2 O gas is used as the reaction gas, or when an amine-based gas other than pyridine gas is used as the catalyst gas Can also be obtained similarly.
- the above-described effects can be obtained in the same manner when a fluorine-based gas other than F 2 gas is used as the reformed gas.
- FIG. 4B shows an example in which the number of set executions (n 1 ) in the layer formation step is two.
- the processing procedure and processing conditions of the layer formation step and the modification step can be the same as the processing procedure and processing conditions of the film forming step and the modification step of the first embodiment.
- the thickness of the SiOC layer formed per layer formation step is set to such a thickness that the entire region of the layer can be uniformly modified in the modification step, so that the entire region in the thickness direction of the SiOCF film is covered. , F can be reliably doped, and the F concentration in the film thickness direction can be made uniform.
- n 1 By performing a predetermined number of times (n 1 ) of performing a step of supplying BTCSM gas and pyridine gas to the wafer and a step of supplying H 2 O gas and pyridine gas to the wafer at the same time.
- FIG. 5B shows an example in which the number of set executions (n 1 ) in the layer formation step is two.
- the processing procedure and processing conditions of the layer formation step and the modification step can be the same as the processing procedure and processing conditions of the film forming step and the modification step of the second embodiment.
- the finally formed stacked film is a film having a uniform characteristic in the stacking direction, that is, a film As a whole, a nanolaminate film having inseparable characteristics can be obtained.
- the second modification step for modifying the surface of the SiOCF film into a CF layer may be performed in this order. In this case, it is possible to form a SiOCF film whose surface is modified to a CF layer on the wafer.
- the processing procedure and processing conditions of the film forming step and the first reforming step can be the same as the processing procedure and processing conditions of the film forming step and the reforming step of the first embodiment.
- the processing procedure and processing conditions of the second reforming step can be the same as the processing procedure and processing conditions of the reforming step of the second embodiment. In this case, the effects described in the first and second embodiments can be obtained simultaneously.
- the film formation step and the modification step are performed in-situ, that is, in the same processing chamber.
- the present invention is not limited to such an embodiment, and the film formation step and the modification step may be performed ex-situ, that is, in different processing chambers. If both steps are performed in-situ, the wafer can be consistently processed while being kept under vacuum without exposing the wafer to the atmosphere, and a stable film forming process can be performed. . If both steps are performed ex-situ, the temperature in each processing chamber can be preset, for example, to the processing temperature in each step or a temperature close thereto, reducing the time required for temperature adjustment and improving production efficiency. Can be increased.
- a SiOC film or a SiOCN film (hereinafter also referred to as a SiOC (N) film) may be formed on the wafer.
- the SiOC film is formed by oxidizing the SiCN layer until N is sufficiently desorbed from the SiCN layer formed so far, and in the step of supplying O 2 gas, The SiOCN film is formed by stopping the oxidation of the SiCN layer before N is sufficiently desorbed from the SiCN layer formed in (1). Also for the film formed by this procedure, the same effect as that of the above-described embodiment can be obtained by performing the modification step in the same manner as in the above-described embodiment.
- the processing conditions when supplying HCDS gas are set as follows, for example. Wafer temperature: 250 to 700 ° C., preferably 300 to 650 ° C., more preferably 350 to 600 ° C. Processing chamber pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa HCDS gas supply flow rate: 1 to 2000 sccm, preferably 10 to 1000 sccm N 2 gas supply flow rate: 100 to 10000 sccm Gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds
- the processing conditions when supplying the TEA gas are set as follows, for example. Processing chamber pressure: 1 to 5000 Pa, preferably 1 to 4000 Pa TEA gas supply flow rate: 100-10000sccm Gas supply time: 1 to 200 seconds, preferably 1 to 120 seconds, more preferably 1 to 60 seconds Other processing conditions: Same as when supplying HCDS gas
- Processing conditions when supplying O 2 gas are set as follows, for example. Processing chamber pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa O 2 gas supply flow rate: 100 to 10000 sccm Gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Other processing conditions: Same as when supplying HCDS gas
- HCDS gas HCDS gas
- OCTS gas OCTS gas
- amine gases such as DEA gas, MEA gas, TMA gas, and MMA gas
- trimethylhydrazine ((CH 3 ) 2 N 2 (CH 3 ) H, abbreviation:
- organic hydrazine-based gas such as TMH) gas, dimethylhydrazine ((CH 3 ) 2 N 2 H 2 , abbreviation: DMH) gas, monomethyl hydrazine ((CH 3 ) HN 2 H 2 , abbreviation: MMH) gas, etc.
- TMH trimethylhydrazine
- DMH dimethylhydrazine
- MMH monomethyl hydrazine
- These gases can be supplied from, for example, the gas supply pipe 232b.
- the O-containing gas other O 2 gas, O 3 gas, H 2 O gas, H 2 O 2 gas, H 2 + O 2 gas, it is possible to use H 2 + O 3 gas.
- the film forming step into the processing chamber accommodating the wafer, 1,4 disilabutane (Si 2 C 2 H 10, abbreviated: DSB) organic silane such as a gas
- DSB 1,4 disilabutane
- a catalytic substance such as trichloroborane (BCl 3 ) gas
- the steps of containing them in the processing chamber and the step of exhausting the processing chamber are performed a predetermined number of times (one or more times) on the wafer.
- the SiOC film may be formed on the wafer by oxidizing the SiC film with a reactive gas (O-containing gas) such as H 2 O gas.
- O-containing gas such as H 2 O gas.
- the processing conditions at this time are set as follows, for example. Wafer temperature: 200 to 400 ° C., preferably 250 to 400 ° C., more preferably 300 to 400 ° C. Processing chamber pressure: 100-5000Pa DSB gas supply flow rate: 100 sccm to 2000 sccm BCl 3 gas supply flow rate: 0.1 sccm to 500 sccm H 2 O gas supply flow rate: 1 to 1000 sccm N 2 gas supply flow rate: 100 to 10000 sccm Containment time: 0.5 to 30 minutes, preferably 0.5 to 20 minutes, more preferably 0.5 to 10 minutes
- Examples of the organic silane raw material include DSB gas, SiC 2 H 8 , Si 2 CH 8 , SiC 3 H 10 , Si 3 CH 10 , SiC 4 H 12 , Si 2 C 3 H 12 , and Si 3 C 2.
- H 12, Si 4 CH 12 it is possible to use SiC 2 H 6, SiC 3 H 8, Si 2 C 2 H 8, SiC 4 H 10, Si 2 C 3 H 10, and Si 3 C 2 H 10, etc. .
- These gases can be supplied from, for example, a gas supply pipe 232a.
- BCl 3 gas BClH 2 , BCl 2 H, BOCl 3 , BF 3 , BBr 3 , BI 3 , B 2 H 6 , NF 3 and the like can be used.
- gases can be supplied from, for example, a gas supply pipe 232c.
- O-containing gas in addition to H 2 O gas, O 2 gas, O 3 gas, H 2 O 2 gas, H 2 + O 2 gas, H 2 + O 3 gas, or the like can be used.
- a step of supplying DSB gas, BCl 3 gas and H 2 O gas into the processing chamber containing the wafer to contain them and a step of exhausting the processing chamber are performed a predetermined number of times. It is also possible to form it.
- the processing conditions at this time can be the same as the processing conditions described above.
- the present invention provides titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), molybdenum (Mo), tungsten (W), and yttrium (Y) on a wafer. , Strontium (Sr), lanthanum (La), oxycarbide film containing a metal element such as aluminum (Al), that is, suitable for the case where a metal oxycarbide film is formed and at least the surface of the film is doped with F It is applicable to.
- the present invention forms a TiOC film, ZrOC film, HfOC film, TaOC film, NbOC film, MoOC film, WOC film, YOC film, SrOC film, LaOC film, and AlOC film on the wafer, and into these films.
- doping F these films are modified into TiOCF films, ZrOCF films, HfOCF films, TaOCF films, NbOCF films, MoOCF films, WOCF films, YOCF films, SrOCF films, LaOCF films, AlOCF films. Is also preferably applicable.
- the present invention forms a TiOC film, a ZrOC film, an HfOC film, a TaOC film, an NbOC film, a MoOC film, a WOC film, a YOC film, an SrOC film, an LaOC film, an AlOC film on the wafer, and the surface of these films.
- the present invention can also be suitably applied to the case of modifying CF into a CF layer.
- a metal element such as titanium tetrachloride (TiCl 4 ) or hafnium tetrachloride (HfCl 4 ) as a raw material and a metal compound containing Cl are used, and a TiOCF film or an HfOCF film is formed on the wafer by the following film forming sequence. Or a TiOC film or HfOC film whose surface is modified to a CF layer can be formed.
- the processing procedure and processing conditions of the film forming process at this time can be the same as the processing procedure and processing conditions of the above-described embodiment. In these cases, the same effects as those of the above-described embodiment can be obtained. That is, the present invention is used when forming a semi-metal oxycarbon fluoride film or metal oxycarbon fluoride film, or when forming a semi-metal oxycarbide film or metal oxycarbide film whose surface is modified to a CF layer. , Can be suitably applied.
- the above-described process recipe is not limited to a case of newly creating, and may be prepared by changing an existing recipe that has already been installed in the substrate processing apparatus, for example.
- the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe is recorded.
- an existing recipe that has already been installed in the substrate processing apparatus may be directly changed by operating the input / output device 122 provided in the existing substrate processing apparatus.
- the processing furnace 302 includes a processing vessel 303 that forms the processing chamber 301, a shower head 303s that supplies gas into the processing chamber 301 in a shower shape, and a support base 317 that supports one or several wafers 200 in a horizontal posture. And a rotating shaft 355 that supports the support base 317 from below, and a heater 307 provided on the support base 317. Gas supply ports 332a to 332c are connected to the inlet (gas inlet) of the shower head 303s.
- the gas supply port 332a is connected to a gas supply system similar to the source gas supply system and the reformed gas supply system of the above-described embodiment.
- a gas supply system similar to the reaction gas supply system of the above-described embodiment is connected to the gas supply port 332b.
- a gas supply system similar to the catalyst gas supply system of the above-described embodiment is connected to the gas supply port 332c.
- a gas dispersion plate that supplies gas into the processing chamber 301 in a shower shape is provided at the outlet (gas outlet) of the shower head 303s.
- the processing vessel 303 is provided with an exhaust port 331 for exhausting the inside of the processing chamber 301.
- An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 331.
- the processing furnace 402 includes a processing container 403 that forms a processing chamber 401, a support base 417 that supports one or several wafers 200 in a horizontal position, a rotating shaft 455 that supports the support base 417 from below, and a processing container.
- a lamp heater 407 that irradiates light toward the wafer 200 in the 403 and a quartz window 403w that transmits light from the lamp heater 407 are provided.
- Gas supply ports 432 a to 432 c are connected to the processing container 403.
- the gas supply port 432a is connected to a gas supply system similar to the source gas supply system and the reformed gas supply system of the above-described embodiment.
- a gas supply system similar to the reaction gas supply system of the above-described embodiment is connected to the gas supply port 432b.
- a gas supply system similar to the catalyst gas supply system of the above-described embodiment is connected to the gas supply port 432c.
- the processing container 403 is provided with an exhaust port 431 for exhausting the inside of the processing chamber 401.
- An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 431.
- the film forming process can be performed by the same processing procedure and processing conditions as those of the above-described embodiment, and the same effects as those of the above-described embodiment can be obtained.
- a plurality of samples 1 each having a SiOC film formed on the surface of a wafer were produced.
- the film forming process for forming the SiOC film on the surface of the wafer includes the steps of supplying DSB gas and BCl 3 gas into the processing chamber containing the wafer and enclosing them in the processing chamber, and evacuating the processing chamber a predetermined number of times. This was performed by forming a SiC film on the wafer and then oxidizing the SiC film with H 2 O gas.
- the processing conditions of the film forming process were set within the processing condition range described in the above embodiment.
- Sample 2 was fabricated by performing a process of supplying NF 3 gas into the processing chamber containing the sample 1 wafer under predetermined processing conditions.
- the temperature of the wafer was set to a predetermined temperature in the range of 350 to 400 ° C.
- the pressure in the processing chamber was set to a predetermined pressure in the range of 80 to 120 Torr.
- the other processing conditions were those within the processing condition range described in the first embodiment.
- Sample 3 was fabricated by performing a process of supplying F 2 gas into the processing chamber containing the sample 1 wafer under predetermined processing conditions.
- the wafer temperature was set to a predetermined temperature within a range of 40 to 60 ° C.
- the pressure inside the processing chamber was set to a predetermined pressure within a range of 0.50 to 1.5 Torr.
- the other processing conditions were those within the processing condition range described in the second embodiment.
- Sample 4 was fabricated by performing a process of supplying NF 3 gas into the processing chamber containing the sample 1 wafer under predetermined processing conditions.
- the pressure in the processing chamber was set to a predetermined pressure within the range of 10 to 20 Torr.
- the other processing conditions were the same as the processing conditions for producing Sample 2 described above.
- FIGS. 7 to 10 are diagrams showing XPS analysis results of the films formed from Samples 1 to 4, respectively.
- the horizontal axis of FIGS. 7 to 10 shows the sputtering time (minutes), which is synonymous with the depth from the surface of the film formed on the wafer.
- the vertical axes in FIGS. 7 to 10 indicate atomic concentrations (at%) of various elements (Si, O, C, F, etc.) contained in the film formed on the wafer.
- the film formed by sample 1, that is, the film before performing the process of supplying NF 3 gas or F 2 gas is an F-free film containing Si, O, C, that is, a SiOC film. It turns out that it is. Note that B and Cl contained in the film are considered to have been contained in the BCl 3 gas used in the film formation process, but both are at the impurity level.
- the entire film formed from Sample 2 is modified from the SiOC film to the SiOCF film. That is, it can be seen that F is widely doped not only on the surface but also in other regions (regions excluding the surface of the film) in the film. It can also be seen that Si and C remain in the film with almost no desorption.
- FIG. 9 shows that only the surface of the film formed from Sample 3 is modified into a CF layer. That is, the surface of the film is doped with F at a relatively high concentration, and Si and O are desorbed from the surface of the film, thereby increasing the C concentration on the surface of the film. It can be seen that the layer contains no Si and O. It can also be seen that in the region excluding the surface of the film, the composition does not change significantly from the SiOC film formed in Sample 1.
- the F concentration in the film formed of Sample 4 is an impurity level, specifically, 5% or less on the surface and 1% or less in other regions.
- the film formed in Sample 4 is not significantly different in composition from the film formed in Sample 1. Therefore, it can be seen that in the process of supplying NF 3 gas, it is difficult to modify the SiOC film when the pressure in the process chamber is lowered to 10 to 20 Torr.
- the processing conditions for preparing the sample 2 and the processing conditions for generating the sample 4 are the same except for the pressure in the processing chamber when supplying the NF 3 gas.
- the reason why a large difference in the effect of the modification treatment occurred in these samples is considered as follows.
- the pressure in the processing chamber i.e., increases the concentration of NF 3 gas by increasing the partial pressure of the NF 3 gas, thereby, the number of collisions to the surface of the SiOC film NF 3 molecules (collision probability), i.e., increased reaction probability between NF 3 and SiOC films, diffusion of F into the film is considered to have occurred actively.
- collision probability i.e., increased reaction probability between NF 3 and SiOC films
- diffusion of F into the film is considered to have occurred actively.
- the pressure in the processing chamber that is, the partial pressure of the NF 3 gas is low, so that the concentration of the NF 3 gas is reduced, and thereby the surface of the SiOC film of NF 3 molecules is reduced.
- the number of collisions that is, the reaction probability between the NF 3 and the SiOC film is reduced, and it is considered that diffusion of F into the film is less likely to occur.
- the pressure in the processing chamber i.e., by increasing the partial pressure of the NF 3 gas, it is possible to increase the reaction energy of the NF 3 gas molecules, thereby, in the film C- It is thought that formation of F bond is promoted.
- the reaction energy of the NF 3 gas molecules is insufficient. It is considered that the formation of bonds is difficult to proceed.
- the inventors have confirmed that the films formed in Samples 2 and 3 have higher etching resistance and lower dielectric constant than the films formed in Samples 1 and 4.
- Appendix 2 The method according to appendix 1, preferably, At least in the step of modifying the surface of the film, fluorine is doped in the entire area of the film, and the film (entire film) is formed into a film (oxycarbon fluoride) containing the predetermined element, oxygen, carbon and fluorine. Film).
- the temperature of the substrate is set to a temperature in the range of 300 ° C. to 500 ° C. (more preferably 350 ° C. to 400 ° C.).
- the pressure in the space in which the substrate exists is set to a pressure in the range of 50 Torr to 300 Torr (more preferably 50 Torr to 100 Torr).
- appendix 6 The method according to appendix 1, preferably, At least in the step of modifying the surface of the film, the surface of the film is modified into a layer containing carbon and fluorine and not containing the predetermined element and oxygen (fluorinated carbon layer, CF layer).
- appendix 7 The method according to appendix 6, preferably, At least in the step of modifying the surface of the film, as the fluorine-based gas, fluorine (F 2 ) gas, iodine fluoride (IF 7 ) gas, chlorine fluoride (ClF 3 ) gas, and hydrogen fluoride (HF) gas are used. At least one selected from the group consisting of:
- the temperature of the substrate is set to a temperature in the range of room temperature (25 ° C.) to 100 ° C. (more preferably, room temperature to 50 ° C.).
- Appendix 10 The method according to any one of appendices 1 to 9, preferably, A recess (trench, hole) is provided on the surface of the substrate, and the film is formed at least in the recess.
- the method according to any one of appendices 1 to 10, preferably, The method further includes the step of forming the film on the substrate by supplying a plurality of types of processing gases to the substrate non-simultaneously.
- the film is formed by supplying a plurality of types of processing gases to the substrate at the same time.
- Appendix 12 The method according to appendix 11, preferably, The step of forming the film on the substrate and the step of modifying at least the surface of the film are performed in-situ (in the same processing chamber).
- Appendix 13 The method according to appendix 11, preferably, The step of forming the film on the substrate and the step of modifying at least the surface of the film are performed ex-situ (in different processing chambers).
- Appendix 14 The method according to any one of appendices 1 to 13, preferably: At least the step of modifying the surface of the film is performed in a non-plasma atmosphere.
- a processing chamber for accommodating the substrate;
- a supply system for supplying a carbon-free fluorine-based gas to the substrate in the processing chamber;
- a temperature adjusting unit for adjusting the temperature of the substrate in the processing chamber;
- a control unit configured to control the supply system and the temperature adjustment unit so that at least a process of modifying the surface of the film is performed;
- a substrate processing apparatus is provided.
- Controller 200 wafer (substrate) 201 processing chamber 202 processing furnace 203 reaction tube 207 heater 231 exhaust pipe 232a to 232f gas supply pipe
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Abstract
Description
表面に所定元素、酸素および炭素を含む膜が形成された基板を準備する工程と、
前記膜のエッチングが生じない条件下で前記基板に対して炭素非含有のフッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる工程と、
を有する技術が提供される。
以下、本発明の第1実施形態について、図1~図3を用いて説明する。
図1に示すように、処理炉202は加熱手段(加熱機構)としてのヒータ207を有する。ヒータ207は円筒形状であり、保持板としてのヒータベース(図示せず)に支持されることにより垂直に据え付けられている。ヒータ207は、後述するようにガスを熱で活性化(励起)させる活性化機構(励起部)として機能する。
上述の基板処理装置を用い、半導体装置(デバイス)の製造工程の一工程として、基板上に膜を形成するシーケンス例について、図4(a)を用いて説明する。以下の説明において、基板処理装置を構成する各部の動作はコントローラ121により制御される。
ウエハ200に対して、原料ガスとしてのBTCSMガスと、触媒ガスとしてのピジリンガスと、を供給するステップ1と、
ウエハ200に対して、反応ガスとしてのH2Oガスと、触媒ガスとしてのピリジンガスと、を供給するステップ2と、
を非同時に、すなわち、同期させることなく交互に行うサイクルを所定回数(1回以上)行うことで、ウエハ200上に、Si、OおよびCを含む膜として、シリコン酸炭化膜(SiOC膜)を形成する。
ウエハ200上に形成したSiOC膜のエッチングが生じない条件下で、ウエハ200に対してC非含有のフッ素系ガスとしてNF3ガスを供給することで、少なくともSiOC膜の表面を改質させる。なお、図4(a)に示す改質ステップでは、ウエハ200上に形成されたSiOC膜中の全域にFを添加(ドープ)し、SiOC膜全体を、Si、O、CおよびFを含む膜、すなわち、シリコン酸炭フッ化膜(SiOCF膜)へ改質させる例を示している。SiOCF膜を、F含有SiOC膜や、Fが添加(ドープ)されたSiOC膜と称することもできる。
複数枚のウエハ200がボート217に装填(ウエハチャージ)されると、シャッタ開閉機構115sによりシャッタ219sが移動させられて、マニホールド209の下端開口が開放される(シャッタオープン)。その後、図1に示すように、複数枚のウエハ200を支持したボート217は、ボートエレベータ115によって持ち上げられて処理室201内へ搬入(ボートロード)される。この状態で、シールキャップ219は、Oリング220bを介してマニホールド209の下端をシールした状態となる。
処理室201内、すなわち、ウエハ200が存在する空間が所望の圧力(真空度)となるように、真空ポンプ246によって真空排気(減圧排気)される。この際、処理室201内の圧力は圧力センサ245で測定され、この測定された圧力情報に基づきAPCバルブ244がフィードバック制御される。真空ポンプ246は、少なくともウエハ200に対する処理が終了するまでの間は常時作動させた状態を維持する。また、処理室201内のウエハ200が所望の温度となるようにヒータ207によって加熱される。この際、処理室201内が所望の温度分布となるように、温度センサ263が検出した温度情報に基づきヒータ207への通電具合がフィードバック制御される。ヒータ207による処理室201内の加熱は、少なくともウエハ200に対する処理が終了するまでの間は継続して行われる。また、回転機構267によるボート217およびウエハ200の回転を開始する。回転機構267によるボート217およびウエハ200の回転は、少なくとも、ウエハ200に対する処理が終了するまでの間は継続して行われる。
その後、後述する2つのステップ、すなわち、ステップ1,2を順次実行する。
このステップでは、処理室201内のウエハ200に対してBTCSMガスとピリジンガスとを供給する。
このステップでは、処理室201内のウエハ200に対してH2Oガスとピリジンガスとを供給する。
上述したステップ1,2を非同時に、すなわち、同期させることなく交互に行うサイクルを1回以上(所定回数)行うことにより、ウエハ200上に、所定組成および所定膜厚のSiOC膜を形成することができる。上述のサイクルは、複数回繰り返すのが好ましい。すなわち、1サイクルあたりに形成する第2層(SiOC層)の厚さを所望の膜厚よりも小さくし、第2層を積層することで形成されるSiOC膜の膜厚が所望の膜厚になるまで、上述のサイクルを複数回繰り返すのが好ましい。
ウエハ200上にSiOC膜が形成されたら、ウエハ200の温度が所望の温度となるように、ヒータ207によって加熱される。ウエハ200の温度が所望の温度となったら、処理室201内のウエハ200に対してNF3ガスを供給する。
改質ステップが終了したら、ガス供給管232d~232fのそれぞれからN2ガスを処理室201内へ供給し、排気管231から排気する。N2ガスはパージガスとして作用する。これにより、処理室201内がパージされ、処理室201内に残留するガスや反応副生成物が処理室201内から除去される(アフターパージ)。その後、処理室201内の雰囲気が不活性ガスに置換され(不活性ガス置換)、処理室201内の圧力が常圧に復帰される(大気圧復帰)。
その後、ボートエレベータ115によりシールキャップ219が下降され、マニホールド209の下端が開口されるとともに、処理済のウエハ200が、ボート217に支持された状態でマニホールド209の下端から反応管203の外部に搬出(ボートアンロード)される。ボートアンロードの後は、シャッタ219sが移動させられ、マニホールド209の下端開口がOリング220cを介してシャッタ219sによりシールされる(シャッタクローズ)。処理済のウエハ200は、反応管203の外部に搬出された後、ボート217より取り出されることとなる(ウエハディスチャージ)。
本実施形態によれば、以下に示す1つ又は複数の効果が得られる。
図5(a)や以下に示す成膜シーケンスのように、ウエハ200上にSiOC膜を形成した後、SiOC膜のエッチングが生じない条件下でウエハ200に対してF2ガスを供給することで、SiOC膜の表面を、CおよびFを含みSiおよびO非含有の層、すなわち、フッ化炭素層(CF層)へ改質させてもよい。
以上、本発明の実施形態を具体的に説明した。しかしながら、本発明は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能である。
ウエハに対してBTCSMガスとピリジンガスとを供給するステップと、ウエハに対してH2Oガスとピリジンガスとを供給するステップと、を非同時に行うセットを所定回数(n1回)行うことで、ウエハ上に、SiOC層を形成する層形成ステップと、
ウエハ上に形成したSiOC層のエッチングが生じない条件下で、ウエハに対してNF3ガスを供給することで、SiOC層をSiOCF層へ改質させる改質ステップと、
を交互に行うサイクルを複数回(n2回)行うようにしてもよい(n1、n2はそれぞれ1以上の整数)。この場合も、ウエハ上に、SiOCF膜を形成することができる。図4(b)は、層形成ステップにおけるセットの実施回数(n1)を2回とした例を示している。
ウエハに対してBTCSMガスとピリジンガスとを供給するステップと、ウエハに対してH2Oガスとピリジンガスとを供給するステップと、を非同時に行うセットを所定回数(n1回)行うことで、ウエハ上に、SiOC層を形成する層形成ステップと、
ウエハ上に形成したSiOC層のエッチングが生じない条件下で、ウエハに対してF2ガスを供給することで、SiOC層の表面をCF層へ改質させる改質ステップと、
を交互に行うサイクルを複数回(n2回)行うようにしてもよい(n1、n2はそれぞれ1以上の整数)。この場合、ウエハ上に、SiOC層とCF層とが交互に複数積層されてなる積層膜を形成することが可能となる。図5(b)は、層形成ステップにおけるセットの実施回数(n1)を2回とした例を示している。
ウエハ温度:250~700℃、好ましくは300~650℃、より好ましくは350~600℃
処理室内圧力:1~2666Pa、好ましくは67~1333Pa
HCDSガス供給流量:1~2000sccm、好ましくは10~1000sccm
N2ガス供給流量:100~10000sccm
ガス供給時間:1~120秒、好ましくは1~60秒
処理室内圧力:1~5000Pa、好ましくは1~4000Pa
TEAガス供給流量:100~10000sccm
ガス供給時間:1~200秒、好ましくは1~120秒、より好ましくは1~60秒
その他の処理条件:HCDSガス供給時と同じ
処理室内圧力:1~4000Pa、好ましくは1~3000Pa
O2ガス供給流量:100~10000sccm
ガス供給時間:1~120秒、好ましくは1~60秒
その他の処理条件:HCDSガス供給時と同じ
ウエハ温度:200~400℃、好ましくは250~400℃、より好ましくは300~400℃
処理室内圧力:100~5000Pa
DSBガス供給流量:100sccm~2000sccm
BCl3ガス供給流量:0.1sccm~500sccm
H2Oガス供給流量:1~1000sccm
N2ガス供給流量:100~10000sccm
封じ込め時間:0.5~30分、好ましくは0.5~20分、より好ましくは0.5~10分
上述の実施形態の基板処理装置を用い、ウエハの表面にSiOC膜が形成されてなるサンプル1を複数作製した。ウエハの表面にSiOC膜を形成する成膜処理は、ウエハを収容した処理室内へDSBガスおよびBCl3ガスを供給しこれらを処理室内に封じ込めるステップと、処理室内を排気するステップと、を所定回数実施してウエハ上にSiC膜を形成した後、このSiC膜をH2Oガスにより酸化させることで行った。成膜処理の処理条件は、上述の実施形態に記載の処理条件範囲内の条件とした。
サンプル1のウエハを収容した処理室内へ所定の処理条件下でNF3ガスを供給する処理を実施してサンプル2を作製した。NF3ガスを供給する処理においては、ウエハの温度を350~400℃の範囲内の所定の温度とし、処理室内の圧力を80~120Torrの範囲内の所定の圧力とした。他の処理条件は、上述の第1実施形態に記載の処理条件範囲内の条件とした。
サンプル1のウエハを収容した処理室内へ所定の処理条件下でF2ガスを供給する処理を実施してサンプル3を作製した。F2ガスを供給する処理においては、ウエハの温度を40~60℃の範囲内の所定の温度とし、処理室内の圧力を0.50~1.5Torrの範囲内の所定の圧力とした。他の処理条件は、上述の第2実施形態に記載の処理条件範囲内の条件とした。
サンプル1のウエハを収容した処理室内へ所定の処理条件下でNF3ガスを供給する処理を実施してサンプル4を作製した。NF3ガスを供給する処理においては、処理室内の圧力を10~20Torrの範囲内の所定の圧力とした。他の処理条件は、上述のサンプル2を作製する際の処理条件と同様とした。
以下、本発明の好ましい態様について付記する。
本発明の一態様によれば、
表面に所定元素、酸素および炭素を含む膜(酸炭化膜)が形成された基板を準備する工程と、
前記膜のエッチングが生じない条件下で前記基板に対して炭素非含有のフッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる工程と、
を有する半導体装置の製造方法、または、基板処理方法が提供される。
付記1に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記膜中(の全域)にフッ素をドープし、前記膜(膜全体)を、前記所定元素、酸素、炭素およびフッ素を含む膜(酸炭フッ化膜)へ改質させる。
付記2に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記フッ素系ガスとしてフッ化窒素(NF3)ガスを用いる。
付記2又は3に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記基板の温度を300℃以上500℃以下(より好ましくは350℃以上400℃以下)の範囲内の温度とする。
付記2乃至4のいずれかに記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記基板が存在する空間の圧力を50Torr以上300Torr以下(より好ましくは50Torr以上100Torr以下)の範囲内の圧力とする。
付記1に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記膜の表面を、炭素およびフッ素を含み前記所定元素および酸素非含有の層(フッ化炭素層、CF層)へ改質させる。
付記6に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記フッ素系ガスとして、フッ素(F2)ガス、フッ化ヨウ素(IF7)ガス、フッ化塩素(ClF3)ガスおよびフッ化水素(HF)ガスからなる群より選択される少なくとも1つを用いる。
付記6又は7に記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記基板の温度を室温(25℃)以上100℃以下(より好ましくは室温以上50℃以下)の範囲内の温度とする。
付記6乃至8のいずれかに記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程では、前記基板が存在する空間の圧力を0.1Torr以上10Torr以下(より好ましくは0.5Torr以上1Torr以下)の範囲内の圧力とする。
付記1乃至9のいずれかに記載の方法であって、好ましくは、
前記基板の表面には凹部(トレンチ、ホール)が設けられており、前記膜は少なくとも前記凹部内に形成されている。
付記1乃至10のいずれかに記載の方法であって、好ましくは、
前記基板に対して複数種類の処理ガスを非同時に供給することで前記基板上に前記膜を形成する工程をさらに有する。また好ましくは、前記膜は、前記基板に対して複数種類の処理ガスを非同時に供給することで形成されている。
付記11に記載の方法であって、好ましくは、
前記基板上に前記膜を形成する工程と、少なくとも前記膜の表面を改質させる工程と、をin-situで(同一の処理室内で)行う。
付記11に記載の方法であって、好ましくは、
前記基板上に前記膜を形成する工程と、少なくとも前記膜の表面を改質させる工程と、をex-situで(異なる処理室内で)行う。
付記1乃至13のいずれかに記載の方法であって、好ましくは、
少なくとも前記膜の表面を改質させる工程は、ノンプラズマの雰囲気下で行われる。
本発明の他の態様によれば、
基板を収容する処理室と、
前記処理室内の基板に対し炭素非含有のフッ素系ガスを供給する供給系と、
前記処理室内の基板の温度を調整する温度調整部と、
前記処理室内に、表面に所定元素、酸素および炭素を含む膜が形成された基板を準備(収容)した後、前記膜のエッチングが生じない条件下で前記基板に対して前記フッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる処理を行わせるように、前記供給系および前記温度調整部を制御するよう構成される制御部と、
を有する基板処理装置が提供される。
本発明のさらに他の態様によれば、
表面に所定元素、酸素および炭素を含む膜が形成された基板を準備する手順と、
前記膜のエッチングが生じない条件下で前記基板に対して炭素非含有のフッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる手順と、
をコンピュータに実行させるプログラム、または、該プログラムを記録したコンピュータ読み取り可能な記録媒体が提供される。
200 ウエハ(基板)
201 処理室
202 処理炉
203 反応管
207 ヒータ
231 排気管
232a~232f ガス供給管
Claims (16)
- 表面に所定元素、酸素および炭素を含む膜が形成された基板を準備する工程と、
前記膜のエッチングが生じない条件下で前記基板に対して炭素非含有のフッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる工程と、
を有する半導体装置の製造方法。 - 少なくとも前記膜の表面を改質させる工程では、前記膜中にフッ素をドープし、前記膜を、前記所定元素、酸素、炭素およびフッ素を含む膜へ改質させる請求項1に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記フッ素系ガスとしてフッ化窒素ガスを用いる請求項2に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記基板の温度を300℃以上500℃以下の範囲内の温度とする請求項2に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記基板が存在する空間の圧力を50Torr以上300Torr以下の範囲内の圧力とする請求項2に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記膜の表面を、炭素およびフッ素を含み前記所定元素および酸素非含有の層へ改質させる請求項1に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記フッ素系ガスとして、フッ素ガス、フッ化ヨウ素ガス、フッ化塩素ガスおよびフッ化水素ガスからなる群より選択される少なくとも1つを用いる請求項6に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記基板の温度を室温以上100℃以下の範囲内の温度とする請求項6に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程では、前記基板が存在する空間の圧力を0.1Torr以上10Torr以下の範囲内の圧力とする請求項6に記載の半導体装置の製造方法。
- 前記基板の表面には凹部が設けられており、前記膜は少なくとも前記凹部内に形成されている請求項1に記載の半導体装置の製造方法。
- 前記基板に対して複数種類の処理ガスを非同時に供給することで前記基板上に前記膜を形成する工程をさらに有する請求項1に記載の半導体装置の製造方法。
- 前記基板上に前記膜を形成する工程と、少なくとも前記膜の表面を改質させる工程と、をin-situで行う請求項11に記載の半導体装置の製造方法。
- 前記基板上に前記膜を形成する工程と、少なくとも前記膜の表面を改質させる工程と、をex-situで行う請求項11に記載の半導体装置の製造方法。
- 少なくとも前記膜の表面を改質させる工程は、ノンプラズマの雰囲気下で行われる請求項1に記載の半導体装置の製造方法。
- 基板を収容する処理室と、
前記処理室内の基板に対し炭素非含有のフッ素系ガスを供給する供給系と、
前記処理室内の基板の温度を調整する温度調整部と、
前記処理室内に、表面に所定元素、酸素および炭素を含む膜が形成された基板を準備した後、前記膜のエッチングが生じない条件下で前記基板に対して前記フッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる処理を行わせるように、前記供給系および前記温度調整部を制御するよう構成される制御部と、
を有する基板処理装置。 - 表面に所定元素、酸素および炭素を含む膜が形成された基板を準備する手順と、
前記膜のエッチングが生じない条件下で前記基板に対して炭素非含有のフッ素系ガスを供給することで、少なくとも前記膜の表面を改質させる手順と、
をコンピュータに実行させるプログラムを記録したコンピュータ読み取り可能な記録媒体。
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