WO2020178973A1 - 半導体装置の製造方法、基板処理装置、およびプログラム - Google Patents
半導体装置の製造方法、基板処理装置、およびプログラム Download PDFInfo
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- WO2020178973A1 WO2020178973A1 PCT/JP2019/008550 JP2019008550W WO2020178973A1 WO 2020178973 A1 WO2020178973 A1 WO 2020178973A1 JP 2019008550 W JP2019008550 W JP 2019008550W WO 2020178973 A1 WO2020178973 A1 WO 2020178973A1
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- H01L21/022—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
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- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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Definitions
- the present disclosure relates to a semiconductor device manufacturing method, a substrate processing apparatus, and a program.
- a step of forming a low dielectric constant film on the substrate may be performed by supplying a processing gas containing an oxidation gas to the heated substrate (for example, a patent). References 1 to 4).
- An object of the present disclosure is to provide a technique capable of suppressing oxidation of a film formed on a substrate while using a film having a low dielectric constant as a base film containing a metal element. ..
- FIG. 3 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that is preferably used in one aspect of the present disclosure, and is a diagram illustrating a vertical cross-sectional view of a processing furnace portion. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus preferably used in one aspect of this disclosure, and is the figure which shows the processing furnace part in the cross-sectional view taken along line AA of FIG.
- FIG. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus that is preferably used in one aspect of the present disclosure, and is a block diagram of a control system of the controller. It is a figure which shows the substrate processing sequence in one aspect of this indication.
- FIG. 3 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that is preferably used in one aspect of the present disclosure, and is a diagram illustrating a vertical cross-sectional view of a processing furnace portion. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus preferably used in
- FIG. 4 is a diagram showing a gas supply sequence in a first film formation according to one aspect of the present disclosure.
- FIG. 8 is a diagram showing a gas supply sequence in the second film formation according to one aspect of the present disclosure.
- (A) is a cross-sectional enlarged view of the surface of the wafer to be processed W film on the surface is exposed, (b) from the surface of the W film is carried out ramp up + H 2 preflow after removal of the native oxide layer
- FIG. 3C is an enlarged cross-sectional view on the surface of the wafer
- FIG. 3C is an enlarged cross-sectional view on the surface of the wafer after the first film formation is carried out to form a SiN film on the W film
- FIG. 7 is an enlarged cross-sectional view of the surface of the wafer after the film is formed to form the SiOCN film on the SiN film and the SiN film formed in the first film formation is modified into the SiON film. It is a figure which shows the evaluation result regarding the oxidation suppression effect of W film by performing 1st film formation before 2nd film formation.
- the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjusting unit).
- the heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate.
- the heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.
- a reaction tube 203 is arranged concentrically with the heater 207.
- the reaction tube 203 is made of, for example, a heat resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and has a cylindrical shape with an upper end closed and a lower end opened.
- a manifold 209 is arranged concentrically with the reaction tube 203.
- the manifold 209 is made of, for example, a metal material such as stainless steel (SUS), and has a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is engaged with the lower end 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 is vertically installed like the heater 207.
- a processing container (reaction container) is mainly configured by the reaction tube 203 and the manifold 209.
- a processing chamber 201 is formed in the hollow cylindrical portion of the processing container.
- the processing chamber 201 is configured to be able to accommodate the wafer 200 as a substrate.
- the wafer 200 is processed in the processing chamber 201.
- nozzles 249a and 249b as a first supply unit and a second supply unit are provided so as to penetrate the side wall of the manifold 209, respectively.
- the nozzles 249a and 249b are also referred to as a first nozzle and a second nozzle, respectively.
- the nozzles 249a and 249b are each made of a non-metal material which is a heat resistant material such as quartz or SiC.
- the nozzles 249a and 249b are each configured as a common nozzle used for supplying a plurality of types of gas.
- First and second gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively.
- Each of the gas supply pipes 232a and 232b is configured as a common pipe used for supplying a plurality of types of gas.
- the gas supply pipes 232a and 232b are provided with mass flow controllers (MFC) 241a and 241b, which are flow rate controllers (flow rate control units), and valves 243a and 243b, which are open/close valves, in order from the upstream side of the gas flow. ..
- Gas supply pipes 232e and 232g are connected to the gas supply pipe 232a on the downstream side of the valve 243a.
- the gas supply pipes 232e and 232g are provided with MFCs 241e and 241g and valves 243e and 243g in this order from the upstream side of the gas flow.
- Gas supply pipes 232c, 232d, 232f, and 232h are connected to the downstream side of the gas supply pipe 232b with respect to the valve 243b, respectively.
- the gas supply pipes 232c, 232d, 232f, 232h are provided with MFCs 241c, 241d, 241f, 241h and valves 243c, 243d, 243f, 243h in order from the upstream side of the gas flow.
- the gas supply pipes 232a to 232h are made of a metal material such as SUS.
- the nozzles 249 a and 249 b are arranged in the annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part of the inner wall of the reaction tube 203 and above the wafer 200. They are provided so as to rise upward in the arrangement direction. That is, the nozzles 249a and 249b are respectively provided along the wafer arrangement region in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged. Gas supply holes 250a and 250b for supplying gas are provided on the side surfaces of the nozzles 249a and 249b, respectively.
- Each of the gas supply holes 250a and 250b opens toward the center of the wafer 200 in a plan view, and gas can be supplied toward the wafer 200.
- a plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.
- a halosilane-based gas containing Si as a main element (predetermined element) that constitutes the film and a halogen element is supplied as a source gas into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a.
- the raw material gas is a raw material in a gaseous state, for example, a gas obtained by vaporizing a raw material in a liquid state under normal temperature and pressure, a raw material in a gaseous state under normal temperature and pressure, and the like.
- Halosilane is a silane having a halogeno group (halogen group).
- the halogeno group includes a chloro group, a fluoro group, a bromo group, an iodo group and the like. That is, the halogeno group contains halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I).
- a raw material gas containing Si and Cl that is, a chlorosilane-based gas can be used.
- HCDS hexachlorodisilane
- the HCDS gas acts as a Si source.
- nitrogen (N) and hydrogen (H) -containing gas as reaction gas is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.
- N- and H-containing gas for example, an ammonia (NH 3 ) gas that is a hydrogen nitride-based gas can be used.
- NH 3 gas acts as a nitriding gas, that is, an N source.
- a carbon (C)-containing gas is supplied as a reaction gas into the processing chamber 201 through the MFC 241c, the valve 243c, the gas supply pipe 232b, and the nozzle 249b.
- the C-containing gas for example, propylene (C 3 H 6 ) gas, which is a hydrocarbon-based gas, can be used.
- the C 3 H 6 gas acts as a C source.
- an oxygen (O)-containing gas is supplied as a reaction gas into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232b, and the nozzle 249b.
- oxygen (O 2 ) gas can be used as the O-containing gas.
- O 2 gas acts as an oxidizing gas, that is, an O source.
- hydrogen (H 2 ) gas which is an H-containing gas
- the reducing gas such as MFC241e, 241f, valve 243e, 243f, gas supply pipes 232a, 232b, nozzles 249a, 249b, respectively. It is supplied into the processing chamber 201 via.
- nitrogen (N 2 ) gas is treated as an inert gas via MFC 241g, 241h, valves 243g, 243h, gas supply pipes 232a, 232b, nozzles 249a, 249b, respectively. It is supplied into the room 201.
- the N 2 gas acts as a purge gas, a carrier gas, a diluent gas and the like.
- a raw material gas supply system (Si source supply system) is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a.
- a reaction gas supply system (N source supply system, C source supply system, O source supply system) is mainly configured by the gas supply pipes 232b to 232d, the MFCs 241b to 241d, and the valves 243b to 243d.
- the reducing gas supply system is mainly composed of gas supply pipes 232e and 232f, MFC241e and 241f, and valves 243e and 243f.
- the inert gas supply system is mainly composed of gas supply pipes 232 g, 232 h, MFC 241 g, 241 h, and valves 243 g, 243 h.
- the raw material gas and the reaction gas used in the first film formation which will be described later, are collectively referred to as the first processing gas.
- the source gas supply system and the reaction gas supply system used in the first film formation are collectively referred to as a first process gas supply system.
- the raw material gas and the reaction gas used in the second film formation described later are collectively referred to as a second processing gas.
- the source gas supply system and the reaction gas supply system used in the second film formation are collectively referred to as a second process gas supply system.
- any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243h and MFCs 241a to 241h are integrated.
- the integrated supply system 248 is connected to each of the gas supply pipes 232a to 232h, and supplies various gases into the gas supply pipes 232a to 232h, that is, opens and closes the valves 243a to 243h and controls the MFCs 241a to 241h.
- the flow rate adjusting operation and the like are configured to be controlled by the controller 121 described later.
- the integrated type supply system 248 is configured as an integrated type or a divided type integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232h in units of integrated units. It is configured so that maintenance, replacement, expansion, etc. can be performed in units of integrated units.
- An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203.
- the exhaust port 231a may be provided along the upper portion of the side wall of the reaction tube 203, that is, along the wafer arrangement region.
- An exhaust pipe 231 is connected to the exhaust port 231a.
- 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 regulator) are provided in the exhaust pipe 231.
- a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201
- an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator) are provided.
- a vacuum pump 246 as a vacuum exhaust device is connected.
- the APC valve 244 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operated, and further, in a state where the vacuum pump 246 is operated, By adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted.
- 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 installed as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209.
- the seal cap 219 is made of, for example, a metal material such as SUS and has a disc shape.
- an O-ring 220b is provided as a seal member that contacts the lower end of the manifold 209.
- a rotation mechanism 267 for rotating the boat 217 described later is installed below the seal cap 219.
- the rotating shaft 255 of the rotating mechanism 267 penetrates 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 vertically moved by a boat elevator 115 as an elevating mechanism installed outside the reaction tube 203.
- the boat elevator 115 is configured as a transport system (convey mechanism) for carrying in and out (transporting) the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.
- a shutter 219s as a furnace port lid that can hermetically close the lower end opening of the manifold 209 in a state where the seal cap 219 is lowered and the boat 217 is carried out from the processing chamber 201.
- the shutter 219s is made of a metal material such as SUS and has a disk shape.
- an O-ring 220c is provided as a seal member that contacts the lower end of the manifold 209.
- 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 the substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers in a horizontal posture and in a vertically aligned manner with the centers thereof aligned in a vertical direction, that is, It is configured to be arranged at intervals.
- the boat 217 is made of, for example, a heat resistant material such as quartz or SiC.
- a plurality of heat insulating plates 218 made of a heat resistant material such as quartz or SiC are supported in multiple stages.
- a temperature sensor 263 as a temperature detector is installed in the reaction tube 203. By adjusting the degree of energization of 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 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 including 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 so that data can be exchanged with the CPU 121a via the internal bus 121e.
- An input/output device 122 configured as, for example, a touch panel or the like is connected to the controller 121.
- the storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), or the like.
- a control program for controlling the operation of the substrate processing device, a process recipe in which the procedures and conditions for substrate processing described later are described, and the like are readablely stored.
- the process recipes are combined so that the controller 121 can execute each procedure in the substrate processing described later and obtain a predetermined result, and functions as a program.
- control programs, process recipes, and the like are collectively referred to simply as programs.
- the process recipe is also simply referred to as a recipe.
- the word program is used in this specification, it may include only the recipe alone, may include only the control program alone, or may include both of them.
- the RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily stored.
- the I/O port 121d includes the MFCs 241a to 241h, the valves 243a to 243h, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the temperature sensor 263, the heater 207, the rotating mechanism 267, the boat elevator 115, the shutter opening/closing mechanism 115s, and the like. It is connected to the.
- the CPU 121a is configured to read and execute a control program from the storage device 121c, and read a recipe from the storage device 121c in response to input of an operation command from the input/output device 122.
- the CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241h, opens/closes the valves 243a to 243h, opens/closes the APC valve 244, and adjusts the pressure by the APC valve 244 based on the pressure sensor 245 so as to follow the contents of the read recipe.
- the controller 121 can be configured by installing the above program stored in the external storage device 123 into a computer.
- the external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory.
- the storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. 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 by using communication means such as the Internet or a dedicated line without using the external storage device 123.
- Substrate processing step As one step in the manufacturing process of the semiconductor device using the above-mentioned substrate processing apparatus, a conductive metal element-containing film exposed on the wafer 200 as a substrate (hereinafter, also simply referred to as a metal-containing film).
- a substrate treatment sequence example in which a natural oxide film formed on the surface of the metal-containing film is removed and then a low dielectric constant film is formed on the metal-containing film while suppressing oxidation of the metal-containing film is mainly shown in FIGS. This will be described using 7.
- the operation of each part of the substrate processing apparatus is controlled by the controller 121.
- H 2 gas as a reducing gas to the wafer 200 while increasing the temperature of the wafer 200 to a second temperature higher than the first temperature in the processing chamber 201 (ramp-up+H 2 preflow)
- the processing chamber 201 by supplying the HCDS gas and the NH 3 gas as the first processing gas containing no oxidizing gas to the wafer 200 at the second temperature, Si, N, and Forming a silicon nitride film (SiN film) as a first film containing at least one of C and not containing O (first film formation);
- SiN film silicon nitrid
- the cycle of supplying the HCDS gas and the NH 3 gas to the wafer 200 is performed a predetermined number of times.
- the cycle of supplying the HCDS gas, the O 2 gas, the C 3 H 6 gas, and the NH 3 gas to the wafer 200 is performed a predetermined number of times.
- the gas supply sequence shown in FIG. 6 involves n cycles of intermittently and non-simultaneously supplying HCDS gas, O 2 gas, C 3 H 6 gas, and NH 3 gas to the wafer 200 in the second film formation. (N is an integer of 1 or more) An example of the sequence to be performed is shown.
- gas supply sequence for the first film formation shown in FIG. 5 and the gas supply sequence for the second film formation shown in FIG. 6 may be shown as follows for convenience. The same notation will be used in the description of other aspects below.
- wafer When the word “wafer” is used in this specification, it may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on the surface thereof.
- surface of a wafer When the term “surface of a wafer” is used in this specification, it may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer.
- the description of “forming a predetermined layer on a wafer” means directly forming a predetermined layer on the surface of the wafer itself, a layer formed on the wafer, etc. It may mean that a predetermined layer is formed on.
- substrate is also synonymous with the term “wafer”.
- the shutter opening/closing mechanism 115s moves the shutter 219s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.
- a Si substrate composed of single crystal Si or a substrate having a single crystal Si film formed on the surface can be used as the wafer 200.
- a W film which is a conductive metal element-containing film is provided on at least a part of the surface of the wafer 200, and at least a part thereof is exposed.
- a natural oxide layer may be formed on the exposed surface of the W film.
- the thickness of the W layer which is the part of the W film where the natural oxide layer is not formed (not oxidized), and the composition of WO x , which is the part where the natural oxide layer is formed (oxidized),
- the ratio (%) of the thickness of the layer (hereinafter, also simply referred to as a WO layer) to the layer is about 70:30.
- the temperature in the processing chamber 201 be a predetermined first temperature, that is, a predetermined temperature in the range of room temperature (25° C.) or higher and 200° C. or lower, preferably room temperature or higher and 150° C. or lower.
- a predetermined first temperature that is, a predetermined temperature in the range of room temperature (25° C.) or higher and 200° C. or lower, preferably room temperature or higher and 150° C. or lower.
- the temperature in the processing chamber 201 By setting the temperature in the processing chamber 201 to be 200° C. or lower, it is less likely to be affected by moisture that has entered the processing chamber 201, moisture remaining in the processing chamber 201, or the like, and the W film is oxidized. It is possible to avoid. By setting the temperature in the processing chamber 201 to 150° C. or lower, it becomes possible to reliably avoid the oxidation of the W film when boat loading is performed.
- the temperature inside the processing chamber 201 When the temperature inside the processing chamber 201 is set below room temperature, a cooling device for cooling the inside of the processing chamber 201 is required, and the temperature rising time after that becomes long. As a result, the device cost may increase and the productivity may decrease.
- a cooling device for cooling the inside of the processing chamber 201 becomes unnecessary, and the subsequent heating time can be shortened. As a result, it is possible to reduce the cost of the device and improve the productivity.
- the valves 243g and 243h are opened, N 2 gas is supplied into the processing chamber 201 through the nozzles 249a and 249b, and the inside of the processing chamber 201 is purged with N 2 gas. This makes it possible to prevent water and the like from entering the processing chamber 201 and promote discharge of residual water and the like from the processing chamber 201.
- the supply flow rate of N 2 gas (for each gas supply pipe) is, for example, within a range of 0.5 to 20 slm.
- a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to N 2 gas. This point is the same in each step described later.
- the inside of the processing chamber 201 is evacuated (decompressed exhaust) by the vacuum pump 246 (pressure adjustment) so as to have a desired pressure. Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 and heated to a desired second temperature higher than the first temperature (ramp up). Further, the rotation of the wafer 200 by the rotation mechanism 267 is started (rotation). Exhaust in the processing chamber 201, heating and rotation of the wafer 200 are all continuously performed at least until the processing of the wafer 200 is completed.
- H 2 preflow is performed. That is, the valves 243e and 243f are opened and the H 2 gas is flown into the gas supply pipes 232e and 232f.
- the flow rate of the H 2 gas is adjusted by the MFCs 241e and 241f, is supplied into the processing chamber 201 through the nozzles 249a and 249b, and is exhausted from the exhaust port 231a.
- H 2 gas is supplied to the wafer 200 (H 2 preflow).
- the valve 243 g, open the 243 h, nozzles 249a may be supplied to the N 2 gas into the via 249b processing chamber 201.
- the processing conditions in this step are: H 2 gas supply flow rate (per gas supply pipe): 1 to 10 slm N 2 gas supply flow rate (per gas supply pipe): 1 to 10 slm Each gas supply time: 1 to 120 minutes, preferably 1 to 60 minutes Temperature rise start temperature (first temperature): Room temperature to 200 ° C., preferably room temperature to 150 ° C. Temperature raising target temperature (second temperature): 500 to 800°C, preferably 600 to 700°C Rate of temperature rise: 1 to 30°C/min, preferably 1 to 20°C/min Processing pressure: 20 to 10000 Pa, preferably 1000 to 5000 Pa Is exemplified.
- the target temperature increase temperature is also the processing temperature in the first film formation described below.
- the wafer 200 By supplying H 2 gas to the wafer 200 while raising the temperature of the wafer 200 under the above conditions, that is, by raising the temperature of the wafer 200 in the H 2 gas atmosphere, the wafer 200 is exposed on the surface of the wafer 200. It is possible to reduce a part of the W film and remove the WO layer formed on the surface of the W film as shown in FIG. 7 (b).
- the O component contained in the WO layer constitutes a gaseous substance containing at least O in the course of the reaction that occurs when the WO layer is removed, and is discharged from the processing chamber 201. Further, in this step, it is possible to prevent oxidation of the surface of the W film after removing the WO layer by raising the temperature of the wafer 200 in an H 2 gas atmosphere.
- the second temperature is lower than 500° C., the effect of removing the WO layer by the above-described reduction reaction and the effect of preventing the oxidation of the surface of the W film after removing the WO layer may be insufficient.
- the second temperature is set to 500° C. or higher, these effects can be sufficiently obtained.
- the second temperature is set to 600° C. or higher, these effects can be reliably obtained.
- the second temperature exceeds 800° C.
- an excessive gas phase reaction may occur in the processing chamber 201 during the first film formation described later, and the film thickness uniformity of the film formed on the wafer 200 deteriorates.
- the quality may be deteriorated.
- deuterium (D 2 ) gas can be used in addition to H 2 gas.
- the valves 243e and 243f are closed and the supply of H 2 gas into the processing chamber 201 is stopped. Then, the inside of the processing chamber 201 is evacuated to remove gas and the like remaining in the processing chamber 201 from the inside of the processing chamber 201 (purge). At this time, the valves 243g and 243h are opened and N 2 gas is supplied into the processing chamber 201. The N 2 gas acts as a purge gas. Even after the removal of the WO layer from the surface of the W film is completed, the supply of H 2 gas into the processing chamber 201 should be continued (maintained) for a predetermined period until the first film formation is started.
- the supply of the H 2 gas into the process chamber 201 may be continued for a predetermined period until the first film formation is started.
- the antioxidant effect on the surface of the W film after the WO layer is removed can be continued for a predetermined period until the first film formation is started.
- Step C1 In this step, HCDS gas is supplied to the wafer 200 in the processing chamber 201 (HCDS gas supply). Specifically, the valve 243a is opened to flow the HCDS gas into the gas supply pipe 232a. The flow rate of the HCDS gas is adjusted by the MFC 241a, is supplied into the processing chamber 201 via the nozzle 249a, and is exhausted from the exhaust port 231a. At this time, HCDS gas is supplied to the wafer 200. At this time, the valve 243 g, open the 243 h, nozzles 249a, may be supplied to the N 2 gas into the via 249b processing chamber 201.
- the processing conditions in this step are: HCDS gas supply flow rate: 0.01 to 2 slm, preferably 0.1 to 1 slm N 2 gas supply flow rate (for each gas supply pipe): 0 to 10 slm
- Each gas supply time 1 to 120 seconds, preferably 1 to 60 seconds
- Processing pressure 1 to 2666 Pa, preferably 67 to 1333 Pa Is exemplified.
- a Si-containing layer containing Cl is formed on the outermost surface of the wafer 200.
- the Si-containing layer containing Cl is formed by physically adsorbing HCDS on the outermost surface of the wafer 200, chemically adsorbing a substance in which a part of HCDS is decomposed (hereinafter referred to as Si x Cl y ), or thermally decomposing HCDS. It is formed by deposition or the like.
- the Si-containing layer containing Cl may be an HCDS or Si x Cl y adsorption layer (physical adsorption layer or chemical adsorption layer), or may be a Cl-containing Si deposition layer. In the present specification, the Si-containing layer containing Cl is also simply referred to as a Si-containing layer.
- the valve 243a is closed and the supply of HCDS gas into the processing chamber 201 is stopped. Then, the inside of the processing chamber 201 is evacuated to remove gas and the like remaining in the processing chamber 201 from the inside of the processing chamber 201 (purge). At this time, the valves 243g and 243h are opened and N 2 gas is supplied into the processing chamber 201. The N 2 gas acts as a purge gas.
- the raw material gas includes monochlorosilane (SiH 3 Cl, abbreviated as MCS) gas, dichlorosilane (SiH 2 Cl 2 , abbreviated as DCS) gas, trichlorosilane (SiHCl 3 , abbreviation: TCS) gas, and tetra.
- MCS monochlorosilane
- DCS dichlorosilane
- TCS trichlorosilane
- Chlorosilane-based gases such as chlorosilane (SiCl 4 , abbreviated as STC) gas and octachlorotrisilane (Si 3 Cl 8 , abbreviated as OCTS) gas can be used. This point is the same in step D1 described later.
- Step C2 After step C1 is completed, NH 3 gas is supplied to the wafer 200 in the processing chamber 201, that is, the Si-containing layer formed on the wafer 200 (NH 3 gas supply). Specifically, the valve 243b is opened, and NH 3 gas is flown into the gas supply pipe 232b. The flow rate of the NH 3 gas is adjusted by the MFC 241b, is supplied into the processing chamber 201 via the nozzle 249b, and is exhausted from the exhaust port 231a. At this time, NH 3 gas is supplied to the wafer 200. At this time, the valve 243 g, open the 243 h, nozzles 249a, may be supplied to the N 2 gas into the via 249b processing chamber 201.
- the processing conditions in this step are: NH 3 gas supply flow rate: 0.1 to 10 slm NH 3 gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa Is exemplified.
- the other processing conditions are the same as the processing conditions in step C1.
- SiN layer silicon nitride layer
- impurities such as Cl contained in the Si-containing layer in the course of the reforming reaction of the Si-containing layer by the NH 3 gas constitutes a gaseous material containing at least Cl, the process chamber 201 It is discharged from inside.
- the SiN layer has less impurities such as Cl than the Si-containing layer formed in step C1.
- the valve 243b is closed and the supply of NH 3 gas into the processing chamber 201 is stopped. Then, the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing procedure as the purging in step C1 (purge).
- reaction gas gas containing N and H
- hydrogen nitride gas such as diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, and N 3 H 8 gas is used. Can be used. This also applies to step D4 described later.
- the wafer 200 is formed by performing the above-mentioned steps 1 and 2 non-simultaneously, that is, by performing a predetermined number of cycles (m times, m is an integer of 1 or more and 3 or less) without synchronization. It is possible to form an SiN film having a predetermined composition and a predetermined film thickness on the W film from which the WO layer has been removed by heating the wafer 200 in the H 2 gas atmosphere.
- the thickness of the SiN film is, for example, 0.16 nm or more and 1 nm or less, preferably 0.16 nm or more and 0.48 nm or less, and more preferably 0.16 nm or more and 0.32 nm or less.
- the oxidation blocking effect described later becomes insufficient, and a part of the W film may be oxidized in the second film formation described later.
- the oxidation blocking effect can be sufficiently obtained, and the oxidation of the W film can be avoided in the second film formation described later.
- the thickness of the SiN film exceeds 1 nm, the total dielectric constant of the laminated film described below may increase.
- the thickness of the SiN film By setting the thickness of the SiN film to 1 nm or less, it becomes possible to suppress an increase in the total dielectric constant of the laminated film described later.
- the thickness of the SiN film By setting the thickness of the SiN film to 0.48 nm or less, this effect can be surely obtained, and by setting the thickness of the SiN film to 0.32 nm or less, this effect can be more surely obtained. Will be obtained.
- the thickness of the SiN layer formed when the above-described cycle is performed once is made smaller than the desired film thickness, and the SiN film formed by stacking the SiN layers has the desired film thickness. Until then, it is preferable to repeat the above-mentioned cycle a plurality of times. By setting the number of times of performing the above-mentioned cycle to a predetermined number of times of 1 time or more and 3 times or less, the thickness of the SiN film can be set within the above-mentioned range.
- Step D1 In this step, HCDS gas is supplied to the wafer 200 in the processing chamber 201 by the same processing procedure as the processing procedure in step C1 described above (HCDS gas supply).
- the processing conditions in this step are: HCDS gas supply flow rate: 0.01 to 2 slm, preferably 0.1 to 1 slm N 2 gas supply flow rate (for each gas supply pipe): 0 to 10 slm
- Each gas supply time 1 to 120 seconds, preferably 1 to 60 seconds
- Processing pressure 1 to 2666 Pa, preferably 67 to 1333 Pa Is exemplified.
- the third temperature is higher than the first temperature. Further, it is preferable that the third temperature is the same as the above-mentioned second temperature.
- a Si-containing layer is formed on the wafer 200, that is, on the SiN film formed on the wafer 200.
- Step D2 C 3 H 6 gas is supplied to the wafer 200 in the processing chamber 201, that is, the Si-containing layer formed on the SiN film on the wafer 200 (C 3 H 6 gas supply). .. Specifically, the valve 243c is opened and the C 3 H 6 gas is flown into the gas supply pipe 232c. The flow rate of the C 3 H 6 gas is adjusted by the MFC 241c, is supplied into the processing chamber 201 via the gas supply pipe 232b and the nozzle 249b, and is exhausted from the exhaust port 231a. At this time, the C 3 H 6 gas is supplied to the wafer 200. At this time, the valve 243 g, open the 243 h, nozzles 249a, may be supplied to the N 2 gas into the via 249b processing chamber 201.
- the processing conditions in this step are C 3 H 6 gas supply flow rate: 0.1 to 10 slm C 3 H 6 Gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa Is exemplified.
- the other processing conditions are the same as the processing conditions in step D1.
- the C-containing layer is formed on the Si-containing layer.
- a layer containing Si and C is formed by laminating a C containing layer on the Si containing layer.
- the valve 243c is closed to stop the supply of C 3 H 6 gas into the processing chamber 201. Then, the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing procedure as the purging in step C1 (purge).
- reaction gas (C-containing gas) a hydrocarbon-based gas such as acetylene (C 2 H 2 ) gas or ethylene (C 2 H 4 ) gas can be used in addition to C 3 H 6 gas.
- acetylene (C 2 H 2 ) gas or ethylene (C 2 H 4 ) gas can be used in addition to C 3 H 6 gas.
- Step D3 O 2 gas is supplied to the wafer 200 in the processing chamber 201, that is, the layer containing Si and C formed on the SiN film on the wafer 200 (O 2 gas supply).
- the valve 243d is opened and O 2 gas is flown into the gas supply pipe 232d.
- the flow rate of the O 2 gas is adjusted by the MFC 241d, is supplied into the processing chamber 201 via the gas supply pipe 232b and the nozzle 249b, and is exhausted from the exhaust port 231a.
- O 2 gas is supplied to the wafer 200.
- the valve 243 g, open the 243 h, nozzles 249a may be supplied to the N 2 gas into the via 249b processing chamber 201.
- the processing conditions in this step are: O 2 gas supply flow rate: 0.1 to 10 slm O 2 gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa Is exemplified.
- the other processing conditions are the same as the processing conditions in step D1.
- the SiOC layer By supplying O 2 gas to the wafer 200 under the above-described conditions, at least a part of the layer containing Si and C formed on the SiN film on the wafer 200 is oxidized (modified).
- a carbonized silicon acid layer SiOC layer
- a gaseous material containing at least Cl It is configured and discharged from the processing chamber 201.
- the SiOC layer has less impurities such as Cl than the Si-containing layer formed in step D1 and the layer containing Si and C formed in step D2.
- the valve 243d is closed and the supply of O 2 gas into the processing chamber 201 is stopped. Then, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201 (purge) by the same processing procedure as in the purging in step C1.
- the reaction gas (O-containing gas), the other of the O 2 gas, for example, ozone (O 3) gas, water vapor (H 2 O gas), nitrogen monoxide (NO) gas, nitrous oxide (N 2 O) gas Etc. can be used.
- Step D4 After step D3 is completed, NH 3 gas is supplied to the wafer 200 in the processing chamber 201 (NH 3 gas supply) by the same processing procedure as the above-described processing procedure in step C2.
- the processing conditions in this step are: NH 3 gas supply flow rate: 0.1 to 10 slm NH 3 gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa Is exemplified.
- the other processing conditions are the same as the processing conditions in step D1.
- SiOCN layer silicon acid carbonitriding layer
- impurities such as Cl contained in the SiOC layer form a gaseous substance containing at least Cl in the process of reforming the SiOC layer with NH 3 gas, and are removed from the inside of the processing chamber 201. Emitted.
- the SiOCN layer has less impurities such as Cl than the SiOC layer formed in step D3.
- the supply of NH 3 gas into the processing chamber 201 is stopped, and the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing procedure as the purging in step C1. Yes (Purge).
- the wafer 200 that is, the first film formation is performed.
- a SiOCN film having a predetermined composition and a predetermined film thickness can be formed on the SiN film formed on the wafer 200.
- a part of the O component supplied to the wafer 200 and a part of the O component contained in the SiOCN layer formed on the wafer 200 are used in the process of forming the SiOCN film. It is also possible to supply it to the SiN film which is the base of the two film formations. As a result, the O component can be diffused and added into the SiN film which is the base of the second film formation, and this SiN film is modified (oxidized) into a SiON film having a dielectric constant lower than that of the SiN film. It becomes possible. As a result, as shown in FIG.
- This laminated film is a so-called low dielectric constant film (Low-k film).
- the O component that tends to diffuse below the SiN film, that is, toward the W film side that is the base for forming the laminated film, is generated by the SiN film, that is, the SiN film itself. Is trapped by being oxidized, and its diffusion to the W film side is blocked.
- the diffusion blocking effect of the O component obtained by the SiN film on the W film, that is, the oxidation suppressing effect of the W film is also referred to as an oxidation blocking effect.
- the thickness of the SiOCN film formed by the second film formation is preferably thicker than the thickness of the SiN film formed by the first film formation. That is, the thickness of the SiN film formed by the first film formation is preferably thinner than the thickness of the SiOCN film formed by the second film formation.
- the thickness of the SiOCN film having a lower dielectric constant than that of the SiON film thicker than that of the SiON film, that is, the thickness of the SiON film having a higher dielectric constant than that of the SiOCN film is made thinner than that of the SiOCN film. By doing so, it is possible to reduce the average dielectric constant of the laminated film formed by laminating these.
- the thickness of the SiOCN layer formed when the above-mentioned cycle is performed once is made thinner than the desired film thickness, and the film thickness of the SiOCN film formed by stacking the SiOCN layers becomes the desired film thickness. Until then, it is preferable to repeat the above-mentioned cycle a plurality of times.
- N 2 gas as a purge gas is processed from each of the nozzles 249a and 249b.
- the gas is supplied into the chamber 201 and exhausted from the exhaust port 231a.
- the inside of the treatment chamber 201 is purged, and the gas and reaction by-products remaining in the treatment chamber 201 are removed from the inside of the treatment chamber 201 (after-purge).
- the atmosphere in the treatment chamber 201 is replaced with the inert gas (replacement of the inert gas), and the pressure in the treatment chamber 201 is restored to normal pressure (return to atmospheric pressure).
- the boat elevator 115 lowers the seal cap 219 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out (boat unloading) from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217. After the boat is unloaded, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). The processed wafer 200 is carried out of the reaction tube 203 and then taken out from the boat 217 (wafer discharge).
- the SiOCN film having a low dielectric constant can be formed on the wafer 200 by using the second treatment gas containing an oxidation gas.
- the SiN film formed by the first film formation can be oxidized to form a SiON film.
- the laminated film formed by laminating the first film and the second film can be a low dielectric constant film.
- the oxide film (laminated film of the first film and the second film) formed on the W film is a low dielectric constant film, but it is the base of the film. It becomes possible to suppress the oxidation of the W film.
- the laminated film formed by the method of this embodiment can be suitably applied to, for example, a side wall spacer, a hard mask, an etch stopper or the like in a logic device such as MPU or a memory device such as DRAM or 3D NAND.
- the W film which is a simple metal film is exemplified as the conductive metal-containing film exposed on the surface of the substrate, but the present disclosure is not limited to such an aspect.
- the conductive metal-containing film exposed on the surface of the substrate may be a metal nitride film such as a titanium nitride film (TiN film) or a tungsten nitride film (WN film), or an aluminum film (Al film). ), Cobalt film (Co film), nickel film (Ni film), platinum film (Pt film), copper film (Cu film), or the like.
- a conductive metal-containing film such as a TiN film or a W film is also simply referred to as a metal film.
- 1,1,2,2-tetrachloro-1,2-dimethyldisilane (CH 3 ) 2 Si 2 Cl 4 , an alkylhalosilane-based gas such as an abbreviation: TCDMDS gas, an alkylsilane such as hexamethyldisilane ((CH 3 ) 3 -Si—Si—(CH 3 ) 3 , an abbreviation: HMDS) gas
- TCDMDS an alkylsilane such as hexamethyldisilane
- HMDS an abbreviation: HMDS
- a base gas or an alkylenesilane-based gas such as 1,4-disilabutane (Si 2 C 2 H 10 , abbreviation: DSB) gas may be used.
- the raw material gas as a gas to promote its degradation, eg, H 2 gas and trichloroborane (BCl 3) may be added to the gas.
- an amine-based gas such as triethylamine ((C 2 H 5 ) 3 N, abbreviation: TEA) gas may be used in addition to the various reaction gases described above.
- TEA triethylamine
- SiN film, silicon carbide film (SiC film), silicon carbonitride film (SiCN film) may be formed.
- the alkylhalosilane-based gas, the alkylsilane-based gas, and the alkylenesilane-based gas are gases that act as a Si source and a C source, respectively, and the amine-based gas is a gas that acts as an N source and a C source, respectively. ..
- the SiC film or the SiCN film formed in the first film formation is oxidized by performing the second film formation, respectively.
- the SiOC film or the SiOCN film can be modified.
- the SiOC film or the SiOCN film since the SiOC film or the SiOCN film has a lower dielectric constant than the SiON film, it becomes possible to further lower the dielectric constant of the laminated film in which the first film and the second film are laminated.
- the second processing gas in addition to the above-mentioned various halosilane-based gases such as HCDS gas, alkylhalosilane-based gas such as TCDMDS gas, alkylsilane-based gas such as HMDS gas, An alkylene silane-based gas such as DSB gas may be used.
- the second processing gas reaction gas
- amine-based gas such as TEA gas may be used in addition to the various reaction gases described above.
- a SiOCN film may be formed as the second film on the wafer 200, that is, on the first film by the gas supply sequence described below.
- the type of the second processing gas may be appropriately selected, and a silicon oxide film (SiO film), a silicon oxynitride film (SiON film), or a silicon oxycarbide film (SiOC film) may be formed as the second film. Good. Also in these cases, the same effect as the above-mentioned aspect can be obtained.
- the recipes used for each process are individually prepared according to the processing content and stored in the storage device 121c via a telecommunication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe from a plurality of recipes stored in the storage device 121c according to the processing content. As a result, it becomes possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility with one substrate processing apparatus. In addition, the burden on the operator can be reduced, and each processing can be started quickly while avoiding an operation error.
- the above recipe is not limited to the case of newly creating, for example, it may be prepared by changing an existing recipe already installed in the board processing apparatus.
- the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium in which the recipe is recorded.
- the input/output device 122 included in the existing substrate processing apparatus may be operated to directly change the existing recipe already installed in the substrate processing apparatus.
- an example of forming a film using a batch type substrate processing apparatus that processes a plurality of substrates at once has been described.
- the present disclosure is not limited to the above-described embodiment, and can be suitably applied to, for example, when a film is formed by using a single-wafer type substrate processing apparatus that processes one or several substrates at a time.
- the example of forming the film by using the substrate processing apparatus having the hot wall type processing furnace has been described.
- the present disclosure is not limited to the above embodiment, and can be suitably applied to the case where a film is formed using a substrate processing apparatus having a cold wall type processing furnace.
- each processing can be performed under the same processing procedure and processing conditions as those in the above-described embodiment, and the same effects as those in the above-described embodiment can be obtained.
- the processing procedure and the processing condition at this time can be the same as the processing procedure and the processing condition of the above-described aspect, for example.
- the SiOCN film was formed on the wafer in which the W film was exposed on the surface by the gas supply sequence shown in FIG. 6 using the above-mentioned substrate processing apparatus.
- the composition of the wafers of Samples 1 to 5 in the thickness direction in the initial state was measured by XPS.
- the ratio (%) of the thickness of the layer to the thickness of the WO layer which is the oxidized portion was 70:30.
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Abstract
Description
(a)表面に導電性の金属元素含有膜が露出した基板を、第1温度下で処理室内へ搬入する工程と、
(b)前記処理室内において、前記基板を前記第1温度よりも高い第2温度まで昇温させつつ、前記基板に対して還元ガスを供給する工程と、
(c)前記処理室内において、前記第2温度下で、前記基板に対して酸化ガス非含有の第1処理ガスを供給することで、前記金属元素含有膜上に、シリコンと、窒素および炭素のうち少なくともいずれかと、を含み酸素非含有の第1膜を形成する工程と、
(d)前記処理室内において、前記第1温度よりも高い第3温度下で、前記基板に対して酸化ガスを含む第2処理ガスを供給することで、前記第1膜上に、シリコン、酸素、炭素、および窒素を含む第2膜を前記第1膜よりも厚く形成する工程と、
を有する技術が提供される。
以下、本開示の一態様について、主に、図1~図7を用いて説明する。
図1に示すように、処理炉202は加熱機構(温度調整部)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、ガスを熱で活性化(励起)させる活性化機構(励起部)としても機能する。
上述の基板処理装置を用い、半導体装置の製造工程の一工程として、基板としてのウエハ200上に露出した導電性の金属元素含有膜(以下、単に金属含有膜ともいう)の表面に形成された自然酸化膜を除去し、その後、金属含有膜上に、金属含有膜の酸化を抑制しつつ低誘電率膜を形成する基板処理シーケンス例について、主に、図4~図7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。
表面に導電性の金属元素含有膜としてのタングステン(W)膜が露出したウエハ200を、第1温度下で処理室201内へ搬入するステップ(ウエハチャージ、ボートロード)と、
処理室201内において、ウエハ200を第1温度よりも高い第2温度まで昇温させつつ、ウエハ200に対して還元ガスとしてH2ガスを供給するステップ(ランプアップ+H2プリフロー)と、
処理室201内において、第2温度下で、ウエハ200に対して酸化ガス非含有の第1処理ガスとして、HCDSガスおよびNH3ガスを供給することで、W膜上に、Siと、NおよびCのうち少なくともいずれかと、を含みO非含有の第1膜として、シリコン窒化膜(SiN膜)を形成するステップ(第1成膜)と、
処理室201内において、第1温度よりも高い第3温度下で、ウエハ200に対して酸化ガスを含む第2処理ガスとして、HCDSガス、O2ガス、C3H6ガス、およびNH3ガスを供給することで、SiN膜上に、Si、O、C、およびNを含む第2膜として、シリコン酸炭窒化膜(SiOCN膜)をSiN膜よりも厚く形成するステップ(第2成膜)と、
を行う。
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。
ボートロードが終了した後、処理室201内が所望の圧力となるように、真空ポンプ246によって真空排気(減圧排気)される(圧力調整)。また、処理室201内のウエハ200が、第1温度よりも高い所望の第2温度となるように、ヒータ207によって加熱されて昇温される(ランプアップ)。また、回転機構267によるウエハ200の回転を開始する(回転)。処理室201内の排気、ウエハ200の加熱および回転は、いずれも、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。
H2ガス供給流量(ガス供給管毎):1~10slm
N2ガス供給流量(ガス供給管毎):1~10slm
各ガス供給時間:1~120分、好ましくは1~60分
昇温開始温度(第1温度):室温~200℃、好ましくは室温~150℃
昇温目標温度(第2温度):500~800℃、好ましくは600~700℃
昇温レート:1~30℃/min、好ましくは1~20℃/min
処理圧力:20~10000Pa、好ましくは1000~5000Pa
が例示される。なお、昇温目標温度は、後述する第1成膜における処理温度でもある。
その後、次のステップC1,C2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HCDSガスを供給する(HCDSガス供給)。具体的には、バルブ243aを開き、ガス供給管232a内へHCDSガスを流す。HCDSガスは、MFC241aにより流量調整され、ノズル249aを介して処理室201内へ供給され、排気口231aより排気される。このとき、ウエハ200に対してHCDSガスが供給される。このとき、バルブ243g,243hを開き、ノズル249a,249bを介して処理室201内へN2ガスを供給するようにしてもよい。
HCDSガス供給流量:0.01~2slm、好ましくは0.1~1slm
N2ガス供給流量(ガス供給管毎):0~10slm
各ガス供給時間:1~120秒、好ましくは1~60秒
処理温度(第2温度):500~800℃、好ましくは600~700℃
処理圧力:1~2666Pa、好ましくは67~1333Pa
が例示される。
ステップC1が終了した後、処理室201内のウエハ200、すなわち、ウエハ200上に形成されたSi含有層に対してNH3ガスを供給する(NH3ガス供給)。具体的には、バルブ243bを開き、ガス供給管232b内へNH3ガスを流す。NH3ガスは、MFC241bにより流量調整され、ノズル249bを介して処理室201内へ供給され、排気口231aより排気される。このとき、ウエハ200に対してNH3ガスが供給される。このとき、バルブ243g,243hを開き、ノズル249a,249bを介して処理室201内へN2ガスを供給するようにしてもよい。
NH3ガス供給流量:0.1~10slm
NH3ガス供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップC1における処理条件と同様な処理条件とする。
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行うサイクルを所定回数(m回、mは1以上3以下の整数)行うことにより、図7(c)に示すように、ウエハ200上、すなわち、H2ガス雰囲気下でのウエハ200の昇温によりWO層が除去されたW膜上に、所定組成および所定膜厚のSiN膜を形成することが可能となる。
その後、次のステップD1~D4を順次実行する。
このステップでは、上述のステップC1における処理手順と同様の処理手順により、処理室201内のウエハ200に対してHCDSガスを供給する(HCDSガス供給)。
HCDSガス供給流量:0.01~2slm、好ましくは0.1~1slm
N2ガス供給流量(ガス供給管毎):0~10slm
各ガス供給時間:1~120秒、好ましくは1~60秒
処理温度(第3温度):250~800℃、好ましくは400~700℃
処理圧力:1~2666Pa、好ましくは67~1333Pa
が例示される。なお、第3温度を、上述の第1温度よりも高い温度とするのが好ましい。また、第3温度を、上述の第2温度と同一の温度とするのが好ましい。
ステップD1が終了した後、処理室201内のウエハ200、すなわち、ウエハ200上のSiN膜上に形成されたSi含有層に対してC3H6ガスを供給する(C3H6ガス供給)。具体的には、バルブ243cを開き、ガス供給管232c内へC3H6ガスを流す。C3H6ガスは、MFC241cにより流量調整され、ガス供給管232b、ノズル249bを介して処理室201内へ供給され、排気口231aより排気される。このとき、ウエハ200に対してC3H6ガスが供給される。このとき、バルブ243g,243hを開き、ノズル249a,249bを介して処理室201内へN2ガスを供給するようにしてもよい。
C3H6ガス供給流量:0.1~10slm
C3H6ガス供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップD1における処理条件と同様な処理条件とする。
ステップD2が終了した後、処理室201内のウエハ200、すなわち、ウエハ200上のSiN膜上に形成されたSiおよびCを含む層に対してO2ガスを供給する(O2ガス供給)。具体的には、バルブ243dを開き、ガス供給管232d内へO2ガスを流す。O2ガスは、MFC241dにより流量調整され、ガス供給管232b、ノズル249bを介して処理室201内へ供給され、排気口231aより排気される。このとき、ウエハ200に対してO2ガスが供給される。このとき、バルブ243g,243hを開き、ノズル249a,249bを介して処理室201内へN2ガスを供給するようにしてもよい。
O2ガス供給流量:0.1~10slm
O2ガス供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップD1における処理条件と同様な処理条件とする。
ステップD3が終了した後、上述のステップC2における処理手順と同様の処理手順により、処理室201内のウエハ200に対してNH3ガスを供給する(NH3ガス供給)。
NH3ガス供給流量:0.1~10slm
NH3ガス供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップD1における処理条件と同様な処理条件とする。
上述したステップD1~D4を非同時に、すなわち、同期させることなく行うサイクルを所定回数(n回、nは1以上の整数)行うことにより、ウエハ200上、すなわち、第1成膜を行うことでウエハ200上に形成されたSiN膜上に、所定組成および所定膜厚のSiOCN膜を形成することが可能となる。
第2膜としてのSiOCN膜の形成、および、第1膜として形成されたSiN膜のSiON膜への改質がそれぞれ終了した後、ノズル249a,249bのそれぞれから、パージガスとしてのN2ガスを処理室201内へ供給し、排気口231aから排気する。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)。
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。そして、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(ウエハディスチャージ)。
本態様によれば、以下に示す一つ又は複数の効果が得られる。
以上、本開示の態様を具体的に説明した。しかしながら、本開示は上述の態様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。
(HCDS→C3H6→NH3)×m ⇒ SiCN
(HCDS→TEA)×m ⇒ SiCN
(TCDMDS→NH3)×m ⇒ SiCN
(DSB+H2)×m ⇒ SiC
(DSB+BCl3)×m ⇒ SiC
(HCDS→TEA→O2)×n ⇒ SiOCN
(TCDMDS→NH3→O2)×n ⇒ SiOCN
201 処理室
Claims (20)
- (a)表面に導電性の金属元素含有膜が露出した基板を、第1温度下で処理室内へ搬入する工程と、
(b)前記処理室内において、前記基板を前記第1温度よりも高い第2温度まで昇温させつつ、前記基板に対して還元ガスを供給する工程と、
(c)前記処理室内において、前記第2温度下で、前記基板に対して酸化ガス非含有の第1処理ガスを供給することで、前記金属元素含有膜上に、シリコンと、窒素および炭素のうち少なくともいずれかと、を含み酸素非含有の第1膜を形成する工程と、
(d)前記処理室内において、前記第1温度よりも高い第3温度下で、前記基板に対して酸化ガスを含む第2処理ガスを供給することで、前記第1膜上に、シリコン、酸素、炭素、および窒素を含む第2膜を前記第1膜よりも厚く形成する工程と、
を有する半導体装置の製造方法。 - 前記第1温度を室温以上200℃以下とする請求項1に記載の半導体装置の製造方法。
- 前記第1温度を室温以上150℃以下とする請求項1に記載の半導体装置の製造方法。
- 前記還元ガスとして、水素ガスおよび重水素ガスのうち少なくともいずれかを用いる請求項1に記載の半導体装置の製造方法。
- (b)では、前記還元ガス雰囲気下での前記昇温により前記金属元素含有膜の表面に形成された自然酸化膜を除去する請求項1に記載の半導体装置の製造方法。
- (b)では、自然酸化膜を除去した後の前記金属元素含有膜の表面の酸化を防止する請求項5に記載の半導体装置の製造方法。
- 前記第2温度を500℃以上800℃以下とする請求項6に記載の半導体装置の製造方法。
- 前記第2温度を600℃以上700℃以下とする請求項6に記載の半導体装置の製造方法。
- 前記第1膜は、シリコン窒化膜、シリコン炭化膜、およびシリコン炭窒化膜のうち少なくともいずれかを含む請求項1に記載の半導体装置の製造方法。
- 前記第1膜の厚さを0.16nm以上1nm以下とする請求項1に記載の半導体装置の製造方法。
- 前記第1膜の厚さを0.16nm以上0.48nm以下とする請求項1に記載の半導体装置の製造方法。
- 前記第1膜の厚さを0.16nm以上0.32nm以下とする請求項1に記載の半導体装置の製造方法。
- 前記第1処理ガスは、シリコン源となるガスまたはシリコン源および炭素源となるガスと、窒素源および炭素源のうち少なくともいずれかとなるガスと、を含み、(c)では、それぞれのガスを供給するサイクルを1回以上3回以下行う請求項1に記載の半導体装置の製造方法。
- 前記第1処理ガスは、シリコン源となるガスまたはシリコン源および炭素源となるガスと、窒素源および炭素源のうち少なくともいずれかとなるガスと、を含み、(c)では、それぞれのガスを前記基板に対して間欠的に供給し、
前記第2処理ガスは、シリコン源となるガスまたはシリコン源および炭素源となるガスと、窒素源および炭素源のうち少なくともいずれかとなるガスと、酸素源となるガスと、を含み、(d)では、それぞれのガスを前記基板に対して間欠的かつ非同時に供給する請求項1に記載の半導体装置の製造方法。 - (d)では、(c)において形成した前記第1膜を、(d)を行う前の前記第1膜よりも誘電率が低い膜に改質させる請求項1に記載の半導体装置の製造方法。
- (c)では、前記第1膜としてシリコン炭窒化膜を形成し、
(d)では、前記第2膜としてシリコン酸炭窒化膜を形成すると共に、前記第1膜をシリコン炭窒化膜からシリコン酸炭窒化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。 - 前記第1処理ガスは、シリコン源となるガスと、炭素源となるガスと、窒素源となるガスと、を含み、(c)では、それぞれのガスを前記基板に対して間欠的に供給し、
前記第2処理ガスは、前記シリコン源となるガスと、前記炭素源となるガスと、前記窒素源となるガスと、酸素源となるガスと、を含み、(d)では、それぞれのガスを前記基板に対して間欠的かつ非同時に供給する請求項16に記載の半導体装置の製造方法。 - 前記第2温度と前記第3温度とを同一温度とする請求項1に記載の半導体装置の製造方法。
- 基板が処理される処理室と、
前記処理室内の基板を加熱するヒータと、
前記処理室内の前記基板に対して還元ガスを供給する還元ガス供給系と、
前記処理室内の前記基板に対して酸化ガス非含有の第1処理ガスを供給する第1処理ガス供給系と、
前記処理室内の前記基板に対して酸化ガスを含む第2処理ガスを供給する第2処理ガス供給系と、
前記基板を前記処理室内へ搬送する搬送系と、
(a)表面に導電性の金属元素含有膜が露出した基板を、第1温度下で前記処理室内へ搬入する処理と、(b)前記処理室内において、前記基板を前記第1温度よりも高い第2温度まで昇温させつつ、前記基板に対して前記還元ガスを供給する処理と、(c)前記処理室内において、前記第2温度下で、前記基板に対して前記第1処理ガスを供給することで、前記金属元素含有膜上に、シリコンと、窒素および炭素のうち少なくともいずれかと、を含み酸素非含有の第1膜を形成する処理と、(d)前記処理室内において、前記第1温度よりも高い第3温度下で、前記基板に対して前記第2処理ガスを供給することで、前記第1膜上に、シリコン、酸素、炭素、および窒素を含む第2膜を前記第1膜よりも厚く形成する処理と、を行わせるように、前記ヒータ、前記還元ガス供給系、前記第1処理ガス供給系、前記第2処理ガス供給系、および前記搬送系を制御することが可能なよう構成される制御部と、
を有する基板処理装置。 - (a)表面に導電性の金属元素含有膜が露出した基板を、第1温度下で基板処理装置の処理室内へ搬入する手順と、
(b)前記処理室内において、前記基板を前記第1温度よりも高い第2温度まで昇温させつつ、前記基板に対して還元ガスを供給する手順と、
(c)前記処理室内において、前記第2温度下で、前記基板に対して酸化ガス非含有の第1処理ガスを供給することで、前記金属元素含有膜上に、シリコンと、窒素および炭素のうち少なくともいずれかと、を含み酸素非含有の第1膜を形成する手順と、
(d)前記処理室内において、前記第1温度よりも高い第3温度下で、前記基板に対して酸化ガスを含む第2処理ガスを供給することで、前記第1膜上に、シリコン、酸素、炭素、および窒素を含む第2膜を前記第1膜よりも厚く形成する手順と、
をコンピュータによって前記基板処理装置に実行させるプログラム。
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JP2004153066A (ja) * | 2002-10-31 | 2004-05-27 | Fujitsu Ltd | 半導体装置の製造方法 |
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US11515143B2 (en) | 2019-06-20 | 2022-11-29 | Kokusai Electric Corporation | Method of manufacturing semiconductor device, substrate processing apparatus, recording medium, and method of processing substrate |
US11967499B2 (en) | 2019-06-20 | 2024-04-23 | Kokusai Electric Corporation | Method of processing substrate, method of manufacturing semiconductor device, substrate processing apparatus, and recording medium |
WO2022085498A1 (ja) * | 2020-10-20 | 2022-04-28 | 東京エレクトロン株式会社 | 成膜方法及び成膜装置 |
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US11823886B2 (en) | 2023-11-21 |
SG11202109666TA (en) | 2021-10-28 |
JPWO2020178973A1 (ja) | 2020-09-10 |
US20210398794A1 (en) | 2021-12-23 |
KR20210124375A (ko) | 2021-10-14 |
CN113243042B (zh) | 2024-04-09 |
US20240014032A1 (en) | 2024-01-11 |
KR102652234B1 (ko) | 2024-04-01 |
CN113243042A (zh) | 2021-08-10 |
JP7149407B2 (ja) | 2022-10-06 |
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