JP2013151722A - Method for manufacturing semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a semiconductor device which increases film quality and productivity of an aluminum-containing titanium nitride film and lowers a thermal budget.SOLUTION: A method for manufacturing a semiconductor device includes the steps of: storing a substrate in a processing chamber 7 for processing a substrate 5; feeding a titanium-containing material and an aluminum-containing material to the processing chamber in an intermittently-pulsed manner; and feeding a nitrogen-containing material to the processing chamber continuously.

Description

  The present invention relates to a method for manufacturing a semiconductor device in which an aluminum-containing titanium nitride (TiAlN) film is formed on a substrate such as a silicon wafer or a glass substrate.

  During a manufacturing process of a semiconductor device (IC (Integrated Circuits)), there is a process of forming a conductive film such as a titanium nitride (TiN) film on a substrate. Conductive film formation is applied to capacitor upper and lower electrodes of DRAM elements, metal gate electrodes of MOS transistors, and in recent years, heater portions of next-generation memory elements such as PRAM. As a conductive film formation method, there is a CVD (Chemical Vapor Deposition) method or the like.

  In recent years, with further miniaturization of semiconductor devices and lower power consumption, it has become difficult to ensure the performance of semiconductor devices with conventional TiN films. New film types are being developed to ensure the performance of semiconductor devices. However, there are issues such as increased costs and effects on other processes due to the development of new film types. It is desired to improve performance by improving quality.

  For example, in the capacitor electrode of a DRAM element, an electrode material having high thermal mechanical strength is strongly desired due to a problem that the patterned electrode is deformed due to a thermal history after film formation, and a metal gate electrode of a MOS transistor. Therefore, an electrode material capable of obtaining a high effective work function in order to obtain a desired threshold voltage is strongly desired.

  In addition to the expectation of solving the above problems, an aluminum-containing titanium nitride (TiAlN) film has attracted attention as a heater material because of its high thermal conductivity.

  In view of such circumstances, the present invention provides a method for manufacturing a semiconductor device that improves the quality and productivity of an aluminum-containing titanium nitride film and reduces the thermal budget.

  The present invention includes a step of storing a substrate in a processing chamber for processing a substrate, a step of supplying a titanium-containing raw material and an aluminum-containing raw material to the processing chamber by intermittent pulses, and a nitrogen-containing raw material in the processing chamber continuously. And a step of supplying to the semiconductor device.

  According to the present invention, a step of accommodating a substrate in a processing chamber for processing a substrate, a step of supplying a titanium-containing raw material and an aluminum-containing raw material in intermittent pulses to the processing chamber, and a nitrogen-containing raw material in the processing chamber It has a continuous supply process, reducing the man-hours for gas supply and exhaust, improving productivity by increasing the film deposition rate, and achieving an excellent effect of reducing the thermal budget. To do.

It is an elevation sectional view of the processing furnace concerning the 1st example of the present invention. It is an AA arrow line view of FIG. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on 1st Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the 2nd Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the modification of the 2nd Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the 3rd Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the 4th Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the modification of the 4th Example of this invention. It is a sequence diagram which shows the supply order of the gas to the process chamber which concerns on the 5th Example of this invention.

  Embodiments of the present invention will be described below with reference to the drawings.

  First, referring to FIGS. 1 and 2, a processing furnace of a substrate processing apparatus according to a first embodiment of the present invention will be described.

  The processing furnace 1 according to the present embodiment is configured as, for example, a batch type vertical hot wall type processing furnace. As shown in FIG. 1, the processing furnace 1 includes a reaction tube 2 and a manifold 3 that supports the reaction tube 2 in the vertical direction. The reaction tube 2 is made of a heat-resistant nonmetallic material such as quartz (SiO2) or silicon carbide (SiC), and has a cylindrical shape with the upper end closed and the lower end open.

  The manifold 3 is made of a metal material such as SUS, for example, and has a cylindrical shape with an open upper end and a lower end. An annular flange is formed at each of the lower end of the reaction tube 2 and the upper and lower ends of the manifold 3. Further, a sealing member 4 such as an O-ring is interposed between the flange at the lower end of the reaction tube 2 and the flange at the upper end of the manifold 3. Is hermetically sealed.

  Inside the reaction tube 2 and the manifold 3, a processing chamber 7 is formed in which a boat 6 serving as a substrate holder for holding a plurality of wafers 5 serving as substrates is accommodated. The boat elevator 8 as an elevating mechanism is inserted into the processing chamber 7 from below.

  The boat 6 is mounted on a seal cap 11 via a boat support 9 as a holding body, and a plurality of (for example, about 50 to 150) wafers 5 are arranged at a predetermined pitch in a substantially horizontal state. It is configured to be held in multiple stages at intervals. The maximum outer diameter of the boat 6 loaded with wafers 5 is smaller than the inner diameters of the reaction tube 2 and the manifold 3.

  The seal cap 11 is a disk-shaped member made of a metal such as SUS, and is configured to come into contact with the lower end of the manifold 3 from the lower side in the vertical direction. When the boat elevator 8 is lifted, The inside of the processing chamber 7 is hermetically closed by a sealing member 12 interposed between the flange at the lower end of the manifold 3 and the seal cap 11. Further, the boat 6 can be transferred into and out of the processing chamber 7 by raising and lowering the seal cap 11 in the vertical direction by the boat elevator 8.

  A rotation mechanism 13 is provided below the seal cap 11, and a rotation shaft 14 of the rotation mechanism 13 passes through the seal cap 11 and is connected to the boat 6. The boat 6 on which the wafers 5 are held can be rotated while maintaining the properties. By rotating the boat 6, the processing uniformity of the wafer 5 can be improved.

  On the outer periphery of the reaction tube 2, a heater 15 as a cylindrical heating unit is provided concentrically with the reaction tube 2, and the wafer 5 loaded in the processing chamber 7 is heated to a predetermined temperature. It is configured to do. The heater 15 is vertically supported by a heater base 16 as a holding plate, and the heater base 16 is fixed to the manifold 3.

  Further, in the reaction tube 2, a temperature sensor 21 as a temperature detector formed in an L shape along the inner wall of the reaction tube 2 is provided in the same manner as the porous nozzles 17, 18, and 19 described later. Yes. By adjusting the power supply to the heater 15 based on the temperature information detected by the temperature sensor 21, the temperature in the processing chamber 7 has a desired temperature distribution.

  The manifold 3 is provided with the L-shaped perforated nozzles 17, 18, 19 having a vertical portion and a horizontal portion. The vertical portions of the perforated nozzles 17, 18, 19 are arranged in the vertical direction along the stacking direction of the wafers 5 so as to be along the inner wall of the processing chamber 7. The horizontal portions of the multi-hole nozzles 17, 18, 19 pass through the side walls of the manifold 3.

  A plurality of gas supply ports 22, 23, and 24 are provided at predetermined intervals in the vertical direction on the side surfaces of the vertical portions of the porous nozzles 17, 18, and 19, respectively. The gas supply ports 22, 23, and 24 are opened between the stacked wafers 5 so as to face the approximate center of the processing chamber 7, that is, the approximate center of the wafer 5 loaded into the processing chamber 7. The gases supplied from the gas supply ports 22, 23, and 24 are each injected toward the substantial center in the processing chamber 7. The gas supply ports 22, 23, 24 may have the same opening diameter from the lower part to the upper part, or may gradually increase from the lower part to the upper part.

  The porous nozzle 17 is provided at a position close to the porous nozzles 18 and 19 as shown in FIG. 2, but the porous nozzle 17 is opposed to the porous nozzles 18 and 19 in FIG. It is shown in the right side of the drawing.

  A nitrogen-containing gas (nitriding) such as ammonia (NH 3) gas, nitrogen (N 2) gas, nitrous oxide (N 2 O) gas, monomethyl hydrazine (CH 6 N 2) gas is provided at the upstream end (horizontal end) of the porous nozzle 17. As the agent, for example, a nitrogen-containing gas supply pipe 25 for supplying ammonia gas is connected. The nitrogen-containing gas supply pipe 25 is provided with an ammonia gas supply source (not shown), a first mass flow controller 26 that is a flow rate control mechanism, and a first valve 27 that is an on-off valve in order from the upstream side.

  A first inert gas supply pipe 28 that supplies an inert gas such as a carrier gas and a purge gas such as helium (He) gas, neon (Ne) gas, argon (Ar) gas, or the like downstream of the first valve 27. Is connected. The first inert gas supply pipe 28 is provided with an inert gas supply source (not shown), an inert gas mass flow controller (not shown), and a second valve 29 in order from the upstream side. By opening the first valve 27 and opening the second valve 29, the ammonia gas whose flow rate is controlled by the first mass flow controller 26 is supplied into the processing chamber 7 together with the inert gas. ing.

  Further, by closing the first valve 27 and opening the second valve 29, the flow rate of an inert gas as a purge gas is controlled by an inert gas mass flow controller (not shown) and supplied into the processing chamber 7. . By supplying an inert gas into the processing chamber 7, for example, after the supply of NH 3 gas is finished, ammonia gas remaining in the processing chamber 7 is removed, and other processing gas supplied to the processing chamber 7 is removed. The gas can be prevented from flowing into the nitrogen-containing gas supply pipe 25. A purge gas supply pipe for supplying purge gas and a carrier gas supply pipe for supplying carrier gas may be provided separately.

  The nitrogen-containing gas supply pipe 25, an ammonia gas supply source (not shown), the first mass flow controller 26, the first valve 27, the first inert gas supply pipe 28, an inert gas mass flow controller (see FIG. The second valve 29, the porous nozzle 17, and the gas supply port 22 constitute a nitrogen-containing gas supply system that supplies a nitrogen-containing gas into the processing chamber 7. Further, the first inert gas supply pipe 28, the inert gas mass flow controller (not shown), the nitrogen-containing gas supply pipe 25, the porous nozzle 17, and the gas supply port 22 are not filled in the processing chamber 7. An inert gas supply system for supplying the active gas is configured.

  Further, an aluminum-containing gas that supplies TMA gas as an aluminum-containing gas such as trimethylaluminum (TMA: (CH3) 3Al), aluminum trichloride (AlCl3), or the like at the upstream end (horizontal end) of the porous nozzle 18. A supply pipe 31 is connected. In this embodiment, the TMA gas obtained by supplying an inert gas such as helium (He) gas, neon (Ne) gas, argon (Ar) gas, etc. into the liquid TMA, together with the carrier gas, is used. A bubbling method for supplying into the processing chamber 7 is used.

  A first carrier gas supply pipe 33 for supplying a carrier gas via a TMA container 32 is provided on the upstream side of the aluminum-containing gas supply pipe 31. The first carrier gas supply pipe 33 is provided with a carrier gas supply source (not shown), a second mass flow controller 34, a third valve 35, and the TMA container 32 in order from the upstream side. The TMA liquid is stored in the TMA container 32, and the downstream end of the first carrier gas supply pipe 33 is immersed in the TMA liquid.

  An upstream end of the aluminum-containing gas supply pipe 31 is disposed above the TMA liquid level of the TMA container 32, and a fourth valve 36 is provided on the downstream side of the aluminum-containing gas supply pipe 31. The aluminum-containing gas supply pipe 31 is provided with a first pipe heater 37, and the first pipe heater 37 can keep the aluminum-containing gas supply pipe 31 at, for example, about 50 ° C. to 60 ° C. ing. By opening the third valve 35, the carrier gas whose flow rate is controlled by the second mass flow controller 34 is supplied into the TMA container 32, TMA gas is generated, and further the fourth valve 36 is opened. Thus, the TMA gas can be supplied into the processing chamber 7 together with the carrier gas.

  The TMA container 32 may be configured to be heatable by a heater (not shown). By adjusting the heating temperature with the heater, generation of TMA gas can be promoted or suppressed, and the supply flow rate of TMA gas into the processing chamber 7 can be controlled.

  The upstream end of the first gas exhaust pipe 38 is connected to the upstream side of the fourth valve 36 of the aluminum-containing gas supply pipe 31, and a fifth valve 39 is provided in the middle of the first gas exhaust pipe 38. Is provided. A downstream end of the first gas exhaust pipe 38 is connected to a downstream side of an APC (Auto Pressure Controller) valve 42 of an exhaust pipe 41 to be described later, and the fifth valve 39 is opened so that the processing chamber 7 is not interposed. In addition, TMA gas can be exhausted.

  A downstream end of a second inert gas supply pipe 43 that supplies an inert gas is connected to the aluminum-containing gas supply pipe 31 on the downstream side of the fourth valve 36. The second inert gas supply pipe 43 is provided with an inert gas supply source (not shown), an inert gas mass flow controller (not shown), and a sixth valve 44 in order from the upstream side. By opening the sixth valve 44, an inert gas as a purge gas whose flow rate is controlled by an inert gas mass flow controller can be supplied into the processing chamber 7. By supplying an inert gas into the processing chamber 7, for example, after the supply of TMA gas is completed, the TMA gas remaining in the processing chamber 7 is excluded, and other gases supplied into the processing chamber 7 are also removed. The gas can be prevented from flowing into the aluminum-containing gas supply pipe 31.

  The first carrier gas supply pipe 33, a carrier gas supply source (not shown), the second mass flow controller 34, the third valve 35, the TMA container 32, the aluminum-containing gas supply pipe 31, the fourth The valve 36, the porous nozzle 18, and the gas supply port 23 constitute an aluminum-containing gas supply system that supplies TMA gas into the processing chamber 7. The second inert gas supply pipe 43, an inert gas supply source (not shown), an inert gas mass flow controller (not shown), the sixth valve 44, the aluminum-containing gas supply pipe 31, the porous The nozzle 18 and the gas supply port 23 constitute an inert gas supply system that supplies an inert gas as a purge gas into the processing chamber 7.

  At the upstream end (horizontal end) of the porous nozzle 19, titanium tetrachloride (TiCl4), tetrakisdimethylaminotitanium (TDMAT: Ti [N (CH3) 2] 4), tetrakisdiethylaminotitanium (TDEAT: Ti [N ( A titanium-containing gas supply pipe 45 for supplying a titanium-containing gas such as CH2 CH3) 2] 4) such as titanium tetrachloride gas is connected. In this embodiment, as in the case of TMA gas, a bubbling method for supplying titanium tetrachloride gas obtained by supplying an inert gas into liquid titanium tetrachloride into the processing chamber 7 together with a carrier gas. Is used.

  On the upstream side of the titanium-containing gas supply pipe 45, a second carrier gas supply pipe 47 that supplies a carrier gas via a titanium tetrachloride container 46 is provided. The second carrier gas supply pipe 47 is provided with a carrier gas supply source (not shown), a third mass flow controller 48, a seventh valve 49, and the titanium tetrachloride container 46 in order from the upstream side. A titanium tetrachloride liquid is stored in the titanium tetrachloride container 46, and the downstream end of the second carrier gas supply pipe 47 is immersed in the titanium tetrachloride liquid.

  The upstream end of the titanium-containing gas supply pipe 45 is disposed above the titanium tetrachloride liquid surface of the titanium tetrachloride container 46, and an eighth valve 51 is provided downstream of the titanium-containing gas supply pipe 45. . The titanium-containing gas supply pipe 45 is provided with a second pipe heater 52, and the second pipe heater 52 can keep the titanium-containing gas supply pipe 45 at about 40 ° C., for example. By opening the seventh valve 49, the carrier gas whose flow rate is controlled by the third mass flow controller 48 is supplied into the titanium tetrachloride container 46, generating titanium tetrachloride gas, and further the eighth valve 51. Is opened so that the titanium tetrachloride gas can be supplied into the processing chamber 7 together with the carrier gas.

  The inside of the titanium tetrachloride container 46 may be configured to be heatable by a heater (not shown). By adjusting the heating temperature with the heater, the generation of titanium tetrachloride gas can be promoted or suppressed, and the supply flow rate of titanium tetrachloride gas into the processing chamber 7 can be controlled.

  The upstream end of the second gas exhaust pipe 53 is connected to the upstream side of the eighth valve 51 of the titanium-containing gas supply pipe 45, and a ninth valve 54 is connected to the middle portion of the second gas exhaust pipe 53. Is provided. The downstream end of the second gas exhaust pipe 53 is connected to the downstream side of the APC valve 42 of the exhaust pipe 41, and the ninth valve 54 is opened so that the titanium tetrachloride gas does not pass through the processing chamber 7. Can be exhausted.

  A downstream end of a third inert gas supply pipe 55 for supplying an inert gas is connected to the downstream side of the eighth valve of the titanium-containing gas supply pipe 45. The third inert gas supply pipe 55 is provided with an inert gas supply source (not shown), an inert gas mass flow controller (not shown), and a tenth valve 56 in order from the upstream side. By opening the tenth valve 56, an inert gas as a purge gas whose flow rate is controlled by an inert gas mass flow controller can be supplied into the processing chamber 7. By supplying an inert gas into the processing chamber 7, for example, after the supply of the titanium tetrachloride gas is finished, the titanium tetrachloride gas remaining in the processing chamber 7 is removed and supplied into the processing chamber 7. It is possible to prevent the other gas thus produced from flowing into the titanium-containing gas supply pipe 45.

  The second carrier gas supply pipe 47, a carrier gas supply source (not shown), the third mass flow controller 48, the seventh valve 49, the titanium tetrachloride container 46, the titanium-containing gas supply pipe 45, The eighth valve 51, the porous nozzle 19, and the gas supply port 24 constitute a titanium-containing gas supply system that supplies titanium tetrachloride gas into the processing chamber 7. The third inert gas supply pipe 55, an inert gas supply source (not shown), an inert gas mass flow controller (not shown), the tenth valve 56, the titanium-containing gas supply pipe 45, the porous The nozzle 19 and the gas supply port 24 constitute an inert gas supply system that supplies an inert gas as a purge gas into the processing chamber 7.

  The exhaust pipe 41 is connected to the side wall of the manifold 3. The exhaust pipe 41 includes, in order from the upstream side, a pressure sensor 57 as a pressure detector for detecting the pressure in the processing chamber 7, the APC valve 42 as a pressure regulator, and a vacuum pump 58 as a vacuum exhaust device. Is provided.

  The APC valve 42 is an on-off valve that can be evacuated and stopped by opening and closing the valve, and that the opening degree of the valve can be adjusted. By adjusting the opening degree of the APC valve 42 based on the pressure information detected by the pressure sensor 57 while operating the vacuum pump 58, the inside of the processing chamber 7 can be set to a desired pressure. It has become.

  The exhaust pipe 41, the pressure sensor 57, the APC valve 42, and the vacuum pump 58 constitute an exhaust system that exhausts the atmosphere in the processing chamber 7.

  The controller 59 as a control system includes the first to third mass flow controllers 26, 34, 48, the APC valve 42, the first to tenth valves 27, 29, 35, 36, 39, 44, 49. , 51, 54, 56, the temperature sensor 21, the heater 15, the pressure sensor 57, the vacuum pump 58, the rotating mechanism 13, the boat elevator 8, and the like. Flow control operation of the mass flow controllers 26, 34, 48, opening / closing operation of the first to tenth valves 27, 29, 35, 36, 39, 44, 49, 51, 54, 56, opening / closing operation of the APC valve 42 And pressure adjustment operation, temperature detection operation of the temperature sensor 21, temperature adjustment operation of the heater 15, pressure detection operation of the pressure sensor 57, Starting and stopping of the air pump 58, the rotational speed regulation of the rotating mechanism 13, the control of the vertical movement of the boat elevator 8 is made.

  Next, processing of the wafer 5 by the processing furnace 1 will be described.

  First, a plurality of wafers 5 are loaded into the boat 6 (wafer charging), and the boat 6 is lifted by the boat elevator 8 and loaded into the processing chamber 7 (boat loading). At this time, the inside of the processing chamber 7 is hermetically closed because the seal cap 11 seals the lower end of the manifold 3 via the sealing member 12. In this state, it is desirable that the second valve 29, the sixth valve 44, and the tenth valve 56 are opened and an inert gas such as helium gas is continuously supplied into the processing chamber 7.

  Subsequently, the second valve 29, the sixth valve 44, and the tenth valve 56 are closed, and the vacuum pump 58 is activated to exhaust the inside of the processing chamber 7. Further, the temperature in the processing chamber 7 is adjusted by feedback controlling the power supply to the heater 15 based on the temperature information from the temperature sensor 21 so that the wafer 5 has a temperature of 300 ° C. to 450 ° C., for example, 350 ° C. Next, the boat 6, that is, the wafer 5 is rotated by the rotation mechanism 13.

  In parallel with the above steps, the third valve 35 is opened with the fourth valve 36 closed, and the carrier gas is supplied into the TMA container 32 while the flow rate is controlled by the second mass flow controller 34. Thus, a liquid raw material containing aluminum, for example, TMA gas obtained by vaporizing TMA is generated in advance. At this time, by operating the vacuum pump 58 and opening the fifth valve 39 while closing the fourth valve 36, the processing chamber 7 is bypassed without supplying TMA gas into the processing chamber 7. And exhaust.

  At this time, the seventh valve 49 is opened with the eighth valve 51 closed, and the carrier gas is supplied to the titanium tetrachloride container 46 while the flow rate is controlled by the third mass flow controller 48. A liquid raw material containing, for example, titanium tetrachloride gas obtained by vaporizing titanium tetrachloride is generated in advance. At this time, by operating the vacuum pump 58 and opening the ninth valve 54 while closing the eighth valve 51, the titanium tetrachloride gas is not supplied into the processing chamber 7, and the processing chamber 7 Bypass and exhaust.

  In the supply method by bubbling, since it takes a predetermined time for the TMA gas and the titanium tetrachloride gas to be stably generated, the supply is started when the supply of the TMA gas and the titanium tetrachloride gas is started at an early stage of generation. Becomes unstable. Therefore, in this embodiment, TMA gas and titanium tetrachloride gas are generated in advance so that they can be stably supplied, and the fourth valve 36, the fifth valve 39, the eighth valve 51, and the ninth valve 54 are set. The flow paths of TMA gas and titanium tetrachloride gas are switched by switching the opening and closing of the. Thereby, supply start and stop of supply of TMA gas and titanium tetrachloride gas into the processing chamber 7 can be performed stably and rapidly.

  Next, a film forming process for generating a thin film on the wafer 5 in the processing chamber 7 is performed. FIG. 3 shows a sequence diagram in the film forming process in the first embodiment. In this embodiment, for example, 72 seconds is one cycle.

  First, the first valve 27 and the second valve 29 are opened, and together with an inert gas as a carrier gas, the first mass flow controller 26 controls the flow rate to a constant flow rate, for example, 0.5 SLM. A contained gas, for example, ammonia gas is continuously supplied into the processing chamber 7.

  Subsequently, a step of supplying an aluminum-containing gas such as TMA gas and a titanium-containing gas such as titanium tetrachloride gas into the processing chamber 7 simultaneously and intermittently (pulse-like) every cycle is performed a predetermined number of times. The The supply of ammonia gas is started before the cycle is started, and continues to be supplied into the processing chamber 7 until the predetermined cycle is completed.

  Specifically, the fifth valve 39 is closed and the fourth valve 36 is opened while the first valve 27 is opened and ammonia gas is supplied from the nitrogen-containing gas supply pipe 25. The TMA gas vaporized in the TMA container 32 is supplied into the processing chamber 7 from the gas supply port 23 together with the carrier gas. At this time, the fourth valve 36 is opened and closed once per cycle so that the supply of TMA gas into the processing chamber 7 is pulsed.

  In parallel with the supply of the TMA gas, the ninth valve 54 is closed and the eighth valve 51 is opened, so that the titanium tetrachloride gas vaporized in the titanium tetrachloride container 46 is combined with the carrier gas. The gas is supplied from the gas supply port 24 into the processing chamber 7. At this time, the eighth valve 51 is opened and closed once per cycle so that the supply of titanium tetrachloride gas into the processing chamber 7 is pulsed and simultaneous with the supply of the TMA gas.

  In the supply process of TMA gas and titanium tetrachloride gas, the simultaneous supply means a case where the time during which each gas is supplied overlaps even a little. That is, in addition to the case where one or both timings of supply start and stop of each gas coincide with each other, the case where both the start and stop timings of supply of each gas are shifted is included.

  At this time, the opening degree of the APC valve 42 is adjusted so that the inside of the processing chamber 7 becomes a predetermined pressure, for example, 20 Pa to 50 Pa.

  While ammonia gas is supplied into the processing chamber 7 through the gas supply port 22 at a constant flow rate, TMA gas and titanium tetrachloride gas are supplied through the gas supply ports 23 and 24 as described above. Are supplied into the processing chamber 7 at the same time and in pulses for a predetermined number of cycles, thereby forming a thin film of aluminum-containing titanium nitride (TiAlN) containing titanium, aluminum, and nitrogen on the wafer 5 by the CVD reaction.

  By supplying a pulse of TMA gas and titanium tetrachloride gas into the processing chamber 7 once, an aluminum-containing titanium nitride film of 0.5 nm (450 ° C.), for example, is formed on the wafer 5. That is, since the deposition rate of the aluminum-containing titanium nitride film is 0.5 nm / cycle (450 ° C.), the predetermined film is formed on the wafer 5 by performing the pulse supply of TMA gas and titanium tetrachloride gas for a predetermined cycle. A thick aluminum-containing titanium nitride film can be formed.

  Note that, during the film forming process of the wafer 5, the reaction of each gas may be promoted by performing plasma application, light irradiation, microwave irradiation, or the like on the wafer 5.

  The supply of TMA gas and titanium tetrachloride gas is performed for a predetermined cycle, and after an aluminum-containing titanium nitride film having a predetermined thickness is formed on the wafer 5, the inside of the processing chamber 7 is evacuated. The supply of each gas is stopped by closing the first valve 27, the fourth valve 36, and the eighth valve 51, the APC valve 42 is opened, and the pressure in the processing chamber 7 is, for example, 20 Pa or less. Each gas, reaction product, etc. remaining in the processing chamber 7 is removed through the exhaust pipe 41.

  At this time, the second valve 29, the sixth valve 44, and the tenth valve 56 are opened, and the first inert gas supply pipe 28, the second inert gas supply pipe 43, and the third inert gas. By supplying an inert gas into the processing chamber 7 via the supply pipe 55 and purging the processing chamber 7, the effect of removing residual gas and the like from the processing chamber 7 can be further enhanced.

  Thereafter, the power supply to the heater 15 is stopped, and the boat 6 and the wafer 5 are lowered to a predetermined temperature. While the temperature of the boat 6 and the wafer 5 is being lowered, the second valve 29, the sixth valve 44, and the tenth valve 56 are kept open, and the inert gas into the processing chamber 7 is maintained. Continue supplying. As a result, the inside of the processing chamber 7 is replaced with an inert gas, and the pressure in the processing chamber 7 is returned to normal pressure.

  After the boat 6 and the wafer 5 are lowered to a predetermined temperature and the pressure in the processing chamber 7 is restored to normal pressure, the seal cap 11 is lowered by the boat elevator 8 and the lower end of the manifold 3 is opened. At the same time, the boat 6 holding the processed wafers 5 is unloaded from the lower end of the manifold 3 to the outside of the reaction tube 2 (boat unloading).

  Thereafter, the processed wafer 5 is taken out from the boat 6 (wafer discharge). When the boat 6 is unloaded, the second valve 29, the sixth valve 44, and the tenth valve 56 are kept open, and the inert gas is continuously supplied into the processing chamber 7. Is desirable. Thus, the processing of the wafer 5 using the processing furnace 1 according to the present embodiment is completed.

  As described above, in this embodiment, while supplying ammonia gas into the processing chamber 7, TMA gas and titanium tetrachloride gas are supplied in pulses every predetermined time as one cycle, and this cycle is performed a predetermined number of times. As a result, an aluminum-containing titanium nitride film having a predetermined film thickness is formed on the wafer 5. Therefore, it is not necessary to separately supply ammonia gas, TMA gas, and titanium tetrachloride gas, and further, since the exhaust in the processing chamber 7 is not required at the time of switching each gas, man-hours for gas supply and gas exhaust can be reduced. In addition, the deposition rate of the aluminum-containing titanium nitride film can be improved, and the productivity of the wafer 5 can be improved and the thermal budget can be reduced.

  In this embodiment, ammonia gas is constantly flowing into the processing chamber 7 during the film forming process, so that nitriding of aluminum and nitriding of titanium can be performed reliably.

  In this embodiment, the ammonia gas flow is always formed by always supplying ammonia gas into the processing chamber 7, so that the diffusion of TMA gas and titanium tetrachloride gas in the processing chamber 7 is performed. And the flow of TMA gas and titanium tetrachloride gas can be stabilized.

  In this embodiment, since ammonia gas is always supplied into the processing chamber 7, pressure fluctuations in the processing chamber 7 can be suppressed, the processing characteristics of the wafer 5 can be stabilized, and The scattering of foreign matters such as particles in the processing chamber 7 can be suppressed.

  In this embodiment, since ammonia gas is always supplied into the processing chamber 7, the opening / closing operation of the valve in the nitrogen supply system can be reduced, the consumption of the valve can be suppressed, and the substrate processing apparatus can be controlled. It can be simplified.

  In addition, by appropriately adjusting the supply pressure and supply flow rate of titanium tetrachloride gas and TMA gas, the formed aluminum-containing titanium nitride film has a desired elemental composition ratio, the film quality is improved, and a desired film formation rate is obtained. can do.

  Further, in this embodiment, since a batch type vertical processing furnace is used, a thin film can be formed on the wafer 5 with high quality and high productivity.

  Next, a second embodiment of the present invention will be described with reference to FIGS. FIG. 4 is a sequence diagram of the film forming process in the second embodiment of the present invention. Since the configuration of the processing furnace in the second embodiment is the same as that of the processing furnace 1 of the first embodiment, the description of the processing furnace 1 is omitted with reference to FIGS. ing.

  In the film forming process of the second embodiment, first, the eighth valve 51 is opened, and titanium tetrachloride gas generated by bubbling in advance in the titanium tetrachloride container 46 is passed through the gas supply port 24 to the processing chamber 7. It is supplied intermittently (pulse-like). By supplying titanium tetrachloride gas into the processing chamber 7, the titanium tetrachloride gas contacts the wafer 5, and a first layer containing titanium of less than one atomic layer to several atomic layers is formed. .

  In addition to titanium tetrachloride gas, for example, tetrakisdimethylaminotitanium (TDMAT) gas or tetrakisdiethylaminotitanium (TDEAT) gas may be used as the titanium-containing gas. In this case, a TDMAT and TDEAT chemisorption layer and a titanium layer are formed on the wafer 5.

  Next, the eighth valve 51 is closed, the tenth valve 56 is opened, the inside of the processing chamber 7 is purged with an inert gas, and the APC valve 42 is opened to remove the inside of the processing chamber 7. Exhaust the titanium tetrachloride gas.

  After exhausting the titanium tetrachloride gas, the tenth valve 56 is closed, the fourth valve 36 is opened, and the TMA gas, which is an aluminum-containing gas previously generated by bubbling in the TMA container 32, is supplied to the gas supply port 23. Then, it is supplied in a pulsed manner into the processing chamber 7. By supplying TMA gas into the processing chamber 7, a second layer containing aluminum is formed in the first layer formed on the wafer 5, or titanium and aluminum are mixed. Layer is formed.

  As the aluminum-containing gas, for example, aluminum trichloride (AlCl3) may be used in addition to the TMA gas. In this case, an aluminum layer and a chemical adsorption layer of aluminum trichloride gas are formed on the first layer.

  After the second layer is formed, the processing chamber 7 is evacuated in the same manner as after the first layer is formed.

  When the exhaust of the processing chamber 7 is completed, the first valve 27 is opened and, for example, ammonia gas is supplied as a nitrogen-containing gas for modifying the first layer and the second layer formed on the wafer 5. A pulse is supplied into the processing chamber 7 through the port 22. By supplying ammonia gas into the processing chamber 7, the ammonia gas and the first layer and the second layer react with each other, and the first layer and the second layer are nitrided to form an aluminum-containing titanium nitride film. After that, the atmosphere in the processing chamber 7 is exhausted again.

  One cycle from the supply of titanium tetrachloride gas to the exhaust of ammonia gas as described above, that is, pulse supply of titanium tetrachloride gas, exhaust of titanium tetrachloride gas, and pulse supply of TMA gas after exhaust of titanium tetrachloride gas. The TMA gas is exhausted, the ammonia gas is pulse-supplied after the TMA gas is exhausted, and the ammonia gas is exhausted to one cycle. By performing this cycle a predetermined number of times, an aluminum-containing titanium nitride film having a predetermined thickness is obtained. Can be formed. Therefore, the titanium tetrachloride gas supply, the TMA gas supply, and the ammonia gas supply are supplied into the processing chamber 7 without overlapping each other.

  In the second embodiment, a titanium-containing layer is formed as the first layer by supplying pulses into the processing chamber 7 in the order of titanium tetrachloride gas, TMA gas, and ammonia gas. Although the aluminum-containing layer is formed as the second layer, as in the modification shown in FIG. 5, by supplying pulses into the processing chamber 7 in the order of TMA gas, titanium tetrachloride gas, and ammonia gas, Needless to say, an aluminum-containing layer may be formed as the first layer, and a titanium-containing layer may be formed as the second layer.

  In the second embodiment, either the titanium-containing layer or the aluminum-containing layer is formed as the first layer, and either the titanium-containing layer or the aluminum-containing layer is formed as the second layer. Since the layer and the second layer are nitrided at the same time, there is no need to separately nitride the first layer and the second layer, man-hours can be reduced, and productivity can be improved.

  In addition, by appropriately adjusting the supply flow rate, supply frequency, and supply pressure of the titanium tetrachloride gas and the TMA gas, the formed aluminum-containing titanium nitride film has a desired elemental composition ratio, the film quality is improved, and the desired composition is achieved. It can be a membrane rate.

  Next, a third embodiment of the present invention will be described with reference to FIGS. FIG. 6 is a sequence diagram of the film forming process in the third embodiment of the present invention. Since the configuration of the processing furnace in the third embodiment is the same as that of the processing furnace 1 of the first embodiment, the description of the processing furnace 1 is omitted with reference to FIGS. ing.

  In the third embodiment, first, a titanium-containing gas previously generated by bubbling in the titanium tetrachloride container 46, for example, titanium tetrachloride gas, and an aluminum-containing gas previously generated by bubbling in the TMA container 32, for example, TMA gas. Are supplied into the processing chamber 7 simultaneously and intermittently (in a pulse manner) through the gas supply ports 23 and 24. Thereafter, a nitrogen-containing gas such as ammonia gas is supplied into the processing chamber 7 through the gas supply port 22 to form an aluminum-containing titanium nitride film on the wafer 5.

  Specifically, first, the eighth valve 51 and the fourth valve 36 are opened simultaneously and in pulses, and titanium tetrachloride gas and TMA gas are supplied into the processing chamber 7 simultaneously and in pulses.

  Titanium tetrachloride gas and TMA gas are supplied into the processing chamber 7 through the gas supply ports 23 and 24, so that the gas is adsorbed on the wafer 5, or titanium and aluminum are laminated. A layer in which titanium and aluminum of less than atomic layers to several atomic layers are mixed is formed.

  Next, by closing the eighth valve 51 and the fourth valve 36 and opening the tenth valve 56 and the sixth valve 44, the inside of the processing chamber 7 is purged with an inert gas, and the APC valve By opening 42, the titanium tetrachloride gas and the TMA gas are exhausted from the processing chamber 7.

  When the exhaust of the titanium tetrachloride gas and the TMA gas is completed, the opening degree of the APC valve 42 is adjusted so that the inside of the processing chamber 7 becomes a predetermined pressure, then the first valve 27 is opened, and the gas supply port 22 is opened. Ammonia gas is supplied in a pulsed manner into the processing chamber 7. By supplying ammonia gas into the processing chamber 7, a layer in which ammonia gas, titanium and aluminum are mixed reacts with the surface, and the layer is nitrided to form an aluminum-containing titanium nitride film, and then the exhaust pipe The atmosphere in the processing chamber 7 is exhausted again via 41.

  One cycle from the supply of titanium tetrachloride gas and TMA gas to the exhaust of ammonia gas, that is, pulse supply of titanium tetrachloride gas and TMA gas simultaneously, exhaust of titanium tetrachloride gas and TMA gas, and ammonia gas after exhaust 1 is a cycle until the ammonia gas is exhausted, and an aluminum-containing titanium nitride film having a predetermined thickness can be formed by repeating this cycle a predetermined number of times. Since the inside of the processing chamber 7 is exhausted after the supply of the titanium tetrachloride gas and the TMA gas, the supply of the titanium tetrachloride gas and the TMA gas and the supply of the ammonia gas are supplied into the processing chamber 7 without overlapping. .

  In the third embodiment, titanium tetrachloride gas and TMA gas are supplied into the processing chamber 7 simultaneously and in a pulsed manner, and a layer in which titanium and aluminum are mixed is nitrided at once with ammonia gas. Therefore, it is not necessary to separately nitride the titanium-containing layer and the aluminum-containing layer, and the man-hour for gas supply can be reduced, and the productivity can be improved.

  In addition, by appropriately adjusting the supply flow rate, supply frequency, and supply pressure of titanium tetrachloride gas and TMA gas when forming a layer in which titanium and aluminum are mixed, an aluminum-containing titanium nitride film to be formed is formed in a desired manner. The element composition ratio can be used to improve the film quality and to achieve a desired film formation rate.

  Next, a fourth embodiment of the present invention will be described with reference to FIGS. FIG. 7 is a sequence diagram of the film forming process in the fourth embodiment of the present invention. Since the configuration of the processing furnace in the fourth embodiment is the same as that of the processing furnace 1 of the first embodiment, the description of the processing furnace 1 is omitted with reference to FIGS. ing.

  In the fourth embodiment, first, an aluminum-containing gas previously generated by bubbling in the TMA container 32, for example, TMA gas, is pulsed into the processing chamber 7 through the gas supply port 23, and the first layer is formed on the wafer. Form. Thereafter, a titanium-containing gas previously generated by bubbling in the titanium tetrachloride container 46, for example, titanium tetrachloride gas, and a nitrogen-containing gas, for example, ammonia gas, are introduced into the processing chamber 7 through the gas supply ports 22 and 24. Simultaneously and in pulses, an aluminum-containing titanium nitride film is formed on the wafer 5.

  Specifically, first, the fourth valve 36 is opened, and TMA gas is supplied into the processing chamber 7 in a pulsed manner through the gas supply port 23. By supplying TMA gas into the processing chamber 7, a first layer made of a TMA chemical adsorption layer or an aluminum layer is formed on the wafer 5.

  Next, the fourth valve 36 is closed and the sixth valve 44 is opened, thereby purging the inside of the processing chamber 7 with an inert gas, and the APC valve 42 is opened via the exhaust pipe 41. Then, the TMA gas is exhausted from the processing chamber 7.

  When the exhaust of TMA gas is completed, the opening degree of the APC valve 42 is adjusted so that the inside of the processing chamber 7 becomes a predetermined pressure, and then the eighth valve 51 and the first valve 27 are opened, and the inside of the processing chamber 7 In addition, titanium tetrachloride gas and ammonia gas are simultaneously and pulsedly supplied through the gas supply ports 22 and 24. By supplying titanium tetrachloride gas and ammonia gas into the processing chamber 7, the first layer containing aluminum is nitrided by ammonia gas and is generated on the first layer by a CVD reaction. A second layer made of titanium nitride is formed. Thereby, an aluminum-containing titanium nitride film is formed on the wafer 5, and then the atmosphere in the processing chamber 7 is exhausted again.

  One cycle from the supply of the TMA gas to the exhaust of the titanium tetrachloride gas and the ammonia gas, that is, the TMA gas is supplied, the TMA gas is exhausted, and after the TMA gas is exhausted, the titanium tetrachloride gas and the ammonia gas are simultaneously pulsed. The cycle until the titanium tetrachloride gas and the ammonia gas are exhausted is one cycle. By performing this cycle a predetermined number of times, an aluminum-containing titanium nitride film having a predetermined thickness can be formed. Therefore, the TMA gas supply and the titanium tetrachloride gas and ammonia gas supply are supplied into the processing chamber 7 without overlapping.

  In the fourth embodiment, first, TMA gas is pulse-supplied, and then titanium tetrachloride gas and ammonia gas are simultaneously pulsed into the processing chamber 7 so that the first layer contains aluminum. The titanium nitride layer is formed as the second layer. As in the modification shown in FIG. 8, the titanium tetrachloride gas is first supplied in pulses, and then the TMA gas and the ammonia gas are simultaneously supplied with the TMA gas and the ammonia gas. It goes without saying that a titanium-containing layer may be formed as the first layer and an aluminum nitride layer may be formed as the second layer by supplying pulses into the processing chamber 7.

  In the fourth embodiment, after forming either the titanium-containing layer or the aluminum-containing layer as the first layer, the titanium tetrachloride gas, the TMA gas, and the ammonia gas are simultaneously and pulsed. Since the aluminum-containing titanium nitride film is formed on the wafer 5 by supplying it into the processing chamber 7, there is no need to separately nitride the titanium-containing layer and the aluminum-containing layer, and the man-hour for gas supply Can be reduced, and productivity can be improved.

  In addition, the supply flow rate, supply frequency and supply pressure of titanium tetrachloride gas and TMA gas when forming the first layer, or supply flow rate and supply of titanium tetrachloride gas and TMA gas that are pulsed simultaneously with ammonia gas. By appropriately adjusting the number of times and the supply pressure, the formed aluminum-containing titanium nitride film can have a desired element composition ratio, improve the film quality, and achieve a desired film formation rate.

  Next, a fifth embodiment of the present invention will be described with reference to FIGS. FIG. 9 is a sequence diagram of a film forming process in the fifth embodiment of the present invention. Since the configuration of the processing furnace in the fifth embodiment is the same as that of the processing furnace 1 of the first embodiment, the description of the processing furnace 1 is omitted with reference to FIGS. ing.

  In the fifth embodiment, a titanium-containing gas previously generated by bubbling in the titanium tetrachloride container 46, for example, titanium tetrachloride gas, and an aluminum-containing gas previously generated by bubbling in the TMA container 32, for example, TMA gas, A nitrogen-containing gas such as ammonia gas is continuously supplied into the processing chamber 7 through the gas supply ports 22, 23, and 24 simultaneously for a predetermined time so that an aluminum-containing titanium nitride film is formed on the wafer 5. It has become.

  Specifically, the eighth valve 51, the fourth valve 36, and the first valve 27 are opened, and titanium tetrachloride gas, TMA gas, and ammonia are introduced into the processing chamber 7 through the gas supply ports 22, 23, and 24. By simultaneously supplying the gas, an aluminum-containing titanium nitride film is formed on the wafer 5 by the CVD reaction.

  In the fifth embodiment, since ammonia gas is continuously supplied into the processing chamber 7 through the gas supply port 22, the CVD reaction with the titanium tetrachloride gas and the TMA gas can be performed more reliably.

  Further, since titanium tetrachloride gas, TMA gas, and ammonia gas are continuously supplied into the processing chamber 7, the number of valve opening / closing operations can be reduced, and the control of the substrate processing apparatus can be simplified.

  In addition, by appropriately adjusting the supply time, supply flow rate and supply pressure of titanium tetrachloride gas and TMA gas, the formed aluminum-containing titanium nitride film has a desired elemental composition ratio, the film quality is improved, and the desired composition is achieved. It can be a membrane rate.

  In the fifth embodiment, titanium tetrachloride gas, TMA gas, and ammonia gas are supplied simultaneously and continuously, but the aluminum-containing titanium nitride film formed on the wafer 5 has a desired element composition ratio. Needless to say, the supply time of each gas may be varied.

(Appendix)
The present invention includes the following embodiments.

  (Supplementary note 1) A substrate processing apparatus for supplying a titanium-containing raw material, an aluminum-containing raw material, and a nitrogen-containing raw material into a processing chamber for processing a substrate and reacting them on the substrate to form an aluminum-containing titanium nitride film on the substrate. A substrate processing apparatus characterized by supplying at least one of a titanium-containing raw material, an aluminum-containing raw material, and a nitrogen-containing raw material in a pulsed manner.

  (Supplementary note 2) The substrate processing apparatus according to supplementary note 1, wherein a titanium-containing raw material and an aluminum-containing raw material are simultaneously and pulsed into the processing chamber, and a nitrogen-containing raw material is independently pulsed.

  (Supplementary note 3) The substrate processing apparatus according to supplementary note 1, wherein a titanium-containing raw material and a nitrogen-containing raw material are simultaneously and pulsedly supplied into the processing chamber, and an aluminum-containing raw material is independently pulsedly supplied.

  (Supplementary note 4) The substrate processing apparatus according to supplementary note 1, wherein the aluminum-containing raw material and the nitrogen-containing raw material are simultaneously and pulsedly supplied into the processing chamber, and the titanium-containing raw material is independently pulsedly supplied.

  (Supplementary note 5) A substrate processing apparatus for reacting a titanium-containing raw material, an aluminum-containing raw material, and a nitrogen-containing raw material on a substrate housed in a processing chamber for processing the substrate to form an aluminum-containing titanium nitride film on the substrate. A substrate processing apparatus, wherein a titanium-containing raw material, an aluminum-containing raw material, and a nitrogen-containing raw material are supplied simultaneously and continuously into the processing chamber.

  (Additional remark 6) The substrate processing apparatus of Additional remark 5 which makes supply time of the titanium containing raw material, the aluminum containing raw material, and the nitrogen containing raw material into the said processing chamber differ, respectively.

  (Supplementary note 7) The substrate processing apparatus according to supplementary notes 1 to 6, wherein the titanium-containing raw material is titanium tetrachloride.

  (Supplementary note 8) The substrate processing apparatus according to supplementary notes 1 to 6, wherein the aluminum-containing raw material is trimethylaluminum.

  (Supplementary note 9) The substrate processing apparatus according to supplementary notes 1 to 6, wherein the nitrogen-containing raw material is ammonia.

  (Additional remark 10) When supplying a titanium containing raw material, an aluminum containing raw material, and a nitrogen containing raw material in the said process chamber, any one of additional plasma 1 to additional light 6 which performs plasma application, light irradiation, and microwave irradiation with respect to a board | substrate is performed. Substrate processing equipment.

  (Supplementary note 11) The substrate processing apparatus according to supplementary notes 1 to 10, which is a batch-type apparatus in which a plurality of substrates are held in multiple stages in the vertical direction by a substrate holder and can process a plurality of substrates simultaneously in the processing chamber.

  (Additional remark 12) The substrate processing apparatus of additional remark 11 by which a titanium containing raw material, an aluminum containing raw material, and a nitrogen containing raw material are supplied between each board | substrate from the side of a board | substrate, and are exhausted.

  (Supplementary note 13) The substrate processing apparatus according to supplementary notes 1 to 10, which is a single wafer processing apparatus capable of processing substrates one by one in the processing chamber.

  (Additional remark 14) It has the process of accommodating a board | substrate in the process chamber which processes a board | substrate, and the process of supplying at least any one of a titanium containing raw material, an aluminum containing raw material, and a nitrogen containing raw material to the said processing chamber in a pulsed manner A method for manufacturing a semiconductor device.

  (Supplementary note 15) The method of manufacturing a semiconductor device according to supplementary note 14, wherein a titanium-containing raw material and an aluminum-containing raw material are simultaneously and pulsedly supplied into the processing chamber, and a nitrogen-containing raw material is independently pulsed into the processing chamber.

  (Additional remark 16) The manufacturing method of the semiconductor device of Additional remark 14 which supplies a titanium containing raw material and a nitrogen containing raw material to the said processing chamber simultaneously and in a pulse, and supplies an aluminum containing raw material in the said processing chamber independently in a pulse.

  (Supplementary note 17) The method of manufacturing a semiconductor device according to supplementary note 14, wherein an aluminum-containing raw material and a nitrogen-containing raw material are simultaneously and pulsedly supplied into the processing chamber, and a titanium-containing raw material is independently pulsed into the processing chamber.

  (Additional remark 18) It has the process of accommodating a board | substrate in the processing chamber which processes a board | substrate, and the process of supplying a titanium containing raw material, an aluminum containing raw material, and a nitrogen containing raw material simultaneously and continuously in the said processing chamber, It is characterized by the above-mentioned. A method for manufacturing a semiconductor device.

DESCRIPTION OF SYMBOLS 1 Processing furnace 2 Reaction tube 5 Wafer 7 Processing chamber 17-19 Porous nozzle 22-24 Gas supply port 25 Nitrogen containing gas supply pipe 26 1st mass flow controller 27 1st valve 31 Aluminum containing gas supply pipe 32 TMA container 36 4th valve 41 Exhaust pipe 42 APC valve 45 Titanium-containing gas supply pipe 46 Titanium tetrachloride container 51 Eighth valve 58 Vacuum pump 59 Controller

Claims (1)

  A step of accommodating the substrate in a processing chamber for processing the substrate, a step of supplying the titanium-containing raw material and the aluminum-containing raw material in intermittent pulses to the processing chamber, and a step of continuously supplying the nitrogen-containing raw material to the processing chamber A method for manufacturing a semiconductor device, comprising:

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