Substrate processing device, gas nozzle, and method for manufacturing semiconductor device

Abstract

The present invention provides a substrate processing device, a gas nozzle, and a method for manufacturing a semiconductor device, wherein when a raw material gas is supplied from a raw material gas nozzle to a reaction tube containing a substrate, the inside of the raw material gas nozzle is suppressed or prevented from being heated to a substrate processing temperature. A technique is provided, comprising: a reaction tube, which is composed of a first component and contains a substrate; and a raw material gas nozzle, which is arranged in the reaction tube, at least a part of which is composed of a second component and supplies raw material gas to the reaction tube, wherein the reflectivity of the second component is higher than that of the first component, and the second component has a rougher surface than the first component due to bubbles contained therein.

Description

Technical Field

[0001] The present disclosure relates to a substrate processing apparatus, a gas nozzle, and a method for manufacturing a semiconductor device. Background Art

[0002] When processing a substrate and forming a film, a raw material gas is sometimes supplied from a raw material gas nozzle into a reaction tube that accommodates the substrate (for example, refer to Japanese Patent Application Laid-Open No. 2017-147262 (Patent Document 1)). When the raw material gas is supplied from the raw material gas nozzle into the reaction tube that accommodates the substrate, the raw material gas nozzle is sometimes heated to the substrate processing temperature and foreign matter is generated in the raw material gas nozzle, which becomes a major cause that hinders the stable operation of the substrate processing device. Summary of the invention

[0003] Problem that the invention aims to solve

[0004] The main object of the present disclosure is to provide a technology capable of suppressing or preventing the inside of a raw material gas nozzle from being heated to a substrate processing temperature.

[0005] Solution

[0006] According to one embodiment of the present disclosure, a technology is provided, comprising: a reaction tube, which is composed of a first component and accommodates a substrate; and a raw material gas nozzle, which is arranged in the reaction tube and at least a part of which is composed of a second component and supplies raw material gas into the reaction tube, the reflectivity of the second component is higher than that of the first component, and the second component has a surface rougher than the first component due to bubbles contained therein.

[0007] Effects of the Invention

[0008] According to the present disclosure, it is possible to suppress or prevent the inside of the raw material gas nozzle from being heated to the substrate processing temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 This is a schematic longitudinal cross-sectional view for explaining a substrate processing apparatus for forming a film on a substrate in a preferred embodiment of the present disclosure.

[0010] Figure 2 yes Figure 1 AA line schematic cross-sectional view.

[0011] Figure 3 It is a diagram for explaining a raw material gas nozzle and a temperature inside the raw material gas nozzle used in a substrate processing apparatus according to a preferred embodiment of the present disclosure.

[0012] Figure 4 This is a schematic longitudinal cross-sectional view for explaining the flow of gas in a raw material gas nozzle used in a substrate processing apparatus according to a preferred embodiment of the present disclosure.

[0013] Figure 5 This is a schematic longitudinal cross-sectional view for explaining a raw material gas nozzle used in a substrate processing apparatus according to a preferred embodiment of the present disclosure.

[0014] Figure 6 This is a schematic diagram for explaining a controller of a substrate processing apparatus according to a preferred embodiment of the present disclosure.

[0015] Figure 7 It is a flowchart for explaining a preferred film forming process flow of a preferred embodiment of the present disclosure.

[0016] Figure 8 It is a diagram for explaining the flow of gases in the raw material gas nozzle and the reaction gas nozzle in the preferred embodiment of the present disclosure.

[0017] Fig. 9 It is a diagram for explaining a raw material gas nozzle used in a substrate processing apparatus for comparison and the temperature inside the raw material gas nozzle. DETAILED DESCRIPTION

[0018] Next, preferred embodiments of the present disclosure will be described.

[0019] In recent years, with the high density of semiconductor devices, there are also various requirements for the thin films that form semiconductor devices. For example, even if you want to form a 1.6nm thick film with a silicon oxide film (SiO film), it is difficult due to electrical constraints. However, if it is a hafnium oxide film (HfO film) with a high dielectric constant, the capacitance equivalent to that of SiO can be obtained at a thickness of 4.5nm.

[0020] Thus, due to the emergence of high dielectric constant films, aluminum oxide films (AlO films), HfO films, and zirconium oxide films (ZrO films) are used as insulating films represented by DRAM capacitors, and as their manufacturing methods, a film forming method in which liquid raw materials of organic compounds such as TMA (trimethylaluminum, (CH3)3Al), TEMAH (tetrakis(ethylmethylamino)hafnium, Hf[N(CH3)CH2CH3]4), TEMAZ (tetrakis(ethylmethylamino)zirconium, Zr[N(CH3)CH2CH3]4) as the first material are vaporized using a vaporizer and ozone as the second material is alternately supplied to a processing chamber to form a film has become the mainstream.

[0021] When using organic compounds such as TMA, TEMAH, and TEMAZ for film formation, since organic matter easily enters the film at the same time, it is preferred to increase the substrate temperature as much as possible to form the film in order to prevent organic matter from entering the film at the same time. However, organic compounds generally have low heat resistance. For example, in the case of TMA, if the temperature of the processing chamber is increased to 450-500°C or above, problems such as deterioration of film thickness uniformity or generation of foreign matter are likely to occur.

[0022] The authors of the present application have found that the problem occurs because the temperature of the raw material gas in the raw material gas nozzle for supplying the raw material gas such as the organic compound is the same as the temperature of the substrate in the processing chamber.

[0023] Furthermore, after careful research, the authors of the present application constructed at least a portion of the raw gas nozzle with a component having a higher reflectivity than the component of the reaction tube constituting the processing chamber, and utilized the bubbles contained inside the component with high reflectivity to make the surface of the raw gas nozzle rougher than the surface of the component of the reaction tube. As a result, the temperature of the raw gas in the raw gas nozzle supplying the raw gas such as organic compounds can be made lower than the temperature in the processing chamber. As a result, it was found that the deterioration of the film thickness uniformity and the generation of foreign matter can be suppressed or prevented.

[0024] Preferred embodiments of the present disclosure are based on such insights and will hereinafter be described in detail with reference to the accompanying drawings.

[0025] (First Embodiment)

[0026] Reference Figure 1 The substrate processing apparatus 10 of the preferred embodiment includes a processing furnace 202. The processing furnace 202 has a heater 207 as a heating system (temperature adjustment unit). The heater 207 is cylindrical and is vertically installed by being supported on a heater base (not shown) as a holding plate. The heater 207 uses infrared rays to heat the inside of a processing chamber 201 described later to a predetermined temperature.

[0027] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold (inlet flange) 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS) and is formed into a cylindrical shape with an upper end and a lower end open. The upper end of the manifold 209 is configured to engage with the lower end of the reaction tube 203 and support the reaction tube 203. An O-ring 220 as a sealing member is provided between the manifold 209 and the reaction tube 203. By supporting the manifold 209 on a heater base (not shown), the reaction tube 203 is in a vertically mounted state. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing container. The processing chamber 201 is configured to accommodate a plurality of wafers 200 as substrates in a horizontal position in a state of being loaded in multiple layers in a vertical direction using a boat 217 described later. In addition, a heater 207 is provided to heat at least from one end side to the other end side of the wafer arrangement area where the wafers 200 are arranged.

[0028] In the processing chamber 201, nozzles 410 and 420 are provided in a manner penetrating the side wall of the manifold 209. Gas supply pipes 310 and 320 serving as gas supply lines are connected to the nozzles 410 and 420, respectively. In this way, two nozzles 410 and 420 and two gas supply pipes 310 and 320 are connected to the processing container (manifold 209), so that a variety of gases can be supplied to the processing chamber 201.

[0029] The gas supply pipes 310 and 320 are provided with mass flow controllers (MFC) 312 and 322 as flow controllers (flow control units) and valves 314 and 324 as on-off valves, respectively, in order from the upstream side. Gas supply pipes 510 and 520 as gas supply lines for supplying inert gas are connected to the downstream sides of the valves 314 and 324 of the gas supply pipes 310 and 320, respectively. The gas supply pipes 510 and 520 are provided with MFCs 512 and 522 as flow controllers (flow control units) and valves 514 and 524 as on-off valves, respectively, in order from the upstream side.

[0030] Nozzles 410 and 420 are connected to the top ends of the gas supply pipes 310 and 320, respectively. Figure 2As shown, the nozzles 410 and 420 are respectively arranged in the annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, extending from the lower part to the upper part of the inner wall of the reaction tube 203, and standing and extending upward in the loading direction of the wafer 200. That is, the nozzles 410 and 420 are respectively arranged along the wafer arrangement area in the area on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounding the wafer arrangement area. That is, the nozzles 410 and 420 are respectively arranged perpendicularly to the surface (flat surface) of the wafer 200 on the side of the end (peripheral portion) of each wafer 200 carried into the processing chamber 201. The nozzles 410 and 420 are respectively configured as L-shaped long nozzles, and their respective horizontal portions are arranged to penetrate the side wall of the manifold 209, and their respective vertical portions are arranged to stand up from at least one end side of the wafer arrangement area to the other end side, and extend from the one end side to the other end side.

[0031] A plurality of supply holes 410a (first gas supply hole, first raw material gas supply hole) and 420a (second gas supply hole) for supplying gas are provided at the height corresponding to the wafer 200 (the height corresponding to the substrate loading area) on the side of the nozzles 410 and 420. The supply holes 410a and 420a are opened toward the center of the reaction tube 203 and can supply gas toward the wafer 200. The supply holes 410a and 420a are provided at a position of the reaction tube 203 that is opposite to the substrate support 217 where the wafer 200 is present, in other words, from the lower end to the upper part of the heater 207.

[0032] The plurality of supply holes 420a provided on the nozzle 420 are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided with the same opening spacing. However, the supply hole 420a is not limited to the above-mentioned manner. For example, the opening area may be gradually increased from the lower part (upstream side) to the upper part (downstream side) of the nozzle 420. Thus, the flow rate of the gas supplied from the supply hole 420a can be made more uniform.

[0033] Thus, in this embodiment, the gas is supplied through the nozzles 410 and 420 arranged in the cylindrical space which is an annular longitudinal space defined by the inner wall of the side wall of the reaction tube 203 and the ends (peripheral portions) of the plurality of wafers 200 arranged in the reaction tube 203 in a plan view. Then, the gas is ejected into the reaction tube 203 near the wafer 200 from the supply holes 410a and 420a opened in the nozzles 410 and 420, respectively. Furthermore, the main flow of the gas in the reaction tube 203 is parallel to the surface of the wafer 200, that is, in the horizontal direction.

[0034] A raw material gas is supplied from a gas supply pipe 310 to the processing chamber 201 via MFC 312, a valve 314, and a nozzle 410. As the raw material gas, for example, in the case of forming an AlO film, it is preferred to use a TMA gas containing aluminum (Al) as a metal element, in the case of forming an HfO film, it is preferred to use a TEMAH gas containing hafnium (Hf) as a metal element, and in the case of forming a ZrO film, it is preferred to use a TEMAZ gas containing zirconium (Zr) as a metal element, etc. as an organic compound containing a metal gas. In addition, an inorganic compound may also be used depending on the type of film to be formed. In the case where the raw material gas flows out from the nozzle 410, the nozzle 410 may also be referred to as a raw material gas nozzle.

[0035] Raw material gas refers to a raw material in a gaseous state, for example, a gas raw material in a gaseous state at normal temperature and pressure, a gas obtained by vaporizing a liquid raw material in a liquid state at normal temperature and pressure, etc. When the word "raw material" is used in this specification, it sometimes means "raw material in a liquid state", sometimes means "raw material in a gaseous state (raw material gas)", or sometimes means both. Since organic compounds such as TMA, TEMAH, and TEMAZ are liquid raw materials, the substances obtained by vaporizing and gasifying using a vaporizer or the like are used as raw material gases.

[0036] The following reaction gas is supplied from the gas supply pipe 320 to the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420. That is, as a reaction gas with a molecular structure different from that of the raw material gas, for example, when forming an oxide film such as an AlO film, an HfO film, and a ZrO film, it is an oxygen-containing gas (oxidizing gas, oxidizing agent) as a reaction gas (reactant) containing oxygen (O) and reacting with Al, Hf, and Zr respectively. As the O-containing gas, for example, ozone (O3) gas can be preferably used. The ozone gas is supplied by an ozone generator or the like.

[0037] An inert gas such as N 2 gas is supplied into the processing chamber 201 from the gas supply pipes 510 and 520 via the MFCs 512 and 522 , the valves 514 and 524 , the gas supply pipes 310 and 320 , and the nozzles 410 and 420 , respectively.

[0038] When the raw material gas is supplied from the gas supply pipe 310, the raw material gas supply system is mainly composed of the gas supply pipe 310, the MFC 312, the valve 314, and the nozzle 410. The raw material gas supply system may also be referred to as the raw material supply system. When the metal-containing gas is supplied from the gas supply pipe 310, the raw material gas supply system may also be referred to as the metal-containing gas supply system.

[0039] When a reaction gas (reactant) is supplied from the gas supply pipe 320, a reaction gas supply system (reactant supply system) is mainly composed of the gas supply pipe 320, the MFC 322, the valve 324, and the nozzle 420. When an oxygen-containing gas (oxidizing gas, oxidant) is supplied as the reaction gas, when the reaction gas flows out from the nozzle 420, the nozzle 420 may also be referred to as a reaction gas nozzle.

[0040] The inert gas supply system is mainly composed of gas supply pipes 510 , 520 , MFCs 512 , 522 , and valves 514 , 325 .

[0041] The raw material gas supply system and the reaction gas supply system are collectively referred to as a gas supply system. The inert gas supply system may also be considered to be included in the gas supply system.

[0042] Next, the nozzle 410 through which the raw material gas flows is described in more detail. The reaction tube 203 constituting the processing chamber 201 is made of transparent quartz (first member) having a low reflectivity to infrared rays. If the nozzle 410 is also made of the same member as the member constituting the reaction tube 203, i.e., transparent quartz having a low reflectivity to infrared rays, then Fig. 9 As shown, the nozzle 410 is heated by absorbing infrared rays from the heater 207, and the gas flowing inside the nozzle 410 is heated by heat transfer (H1) from the tube wall inside the nozzle 410 and absorption (H2) of infrared rays from the heater 207. At this time, the temperature of the gas flowing inside the nozzle 410 becomes substantially the same temperature as the set temperature in the furnace (the temperature in the reaction tube 203), and becomes substantially the same temperature as the temperature of the wafer 200.

[0043] If the temperature of the wafer 200 is increased by increasing the set temperature in the furnace, it is difficult for organic matter to enter the film formed on the wafer 200. However, the temperature of the gas flowing inside the nozzle 410 also becomes high. The raw material gas such as organic compounds such as TMA, TEMAH, and TEMAZ flowing inside the nozzle 410 has low heat resistance, so it causes thermal decomposition inside the nozzle 410. The pressure inside the nozzle 410 is higher than the pressure inside the processing chamber 201 where the wafer 200 is installed. Accordingly, foreign matter is generated in the nozzle 410, and the problem of foreign matter mixing into the film occurs. In addition, with the increase in the film forming speed caused by the thermal decomposition of the raw material gas, the uniformity of the film thickness is also deteriorated. On the other hand, if the set temperature in the furnace is lowered, the temperature of the gas flowing inside the nozzle 410 becomes low, and it is difficult to cause the problem of foreign matter in the nozzle 410. However, the temperature of the wafer 200 also becomes low, and organic matter easily enters the film formed on the wafer 200.

[0044] In contrast, in this embodiment, the reaction tube 203 constituting the processing chamber 201 is made of transparent quartz having a low reflectivity to infrared rays, but the nozzle 410 is made of opaque quartz (second member) having a higher reflectivity to infrared rays than the member constituting the reaction tube 203. Figure 3 As shown, the nozzle 410 is heated by absorbing infrared rays from the heater 207, and the gas flowing inside the nozzle 410 is heated by heat transfer (H1) from the tube wall inside the nozzle 410 and absorption of infrared rays from the heater 207 (H2). However, since the nozzle 410 is made of opaque quartz with high reflectivity to infrared rays, the absorption of infrared rays from the heater 207 (H2) becomes smaller, and the temperature of the gas flowing inside the nozzle 410 is lower than the set temperature in the furnace (the temperature inside the reaction tube 203).

[0045] In addition, since the opaque quartz with high reflectivity to infrared rays used in the nozzle 410 contains bubbles inside, the surface inside the nozzle 410 becomes finely convex and concave due to the bubbles. As a result, the surface of the opaque quartz constituting the nozzle 410 can be rougher than the surface of the transparent quartz (first member) constituting the reaction tube 203. In the case where the nozzle 410 uses transparent quartz with low reflectivity to infrared rays, since the surface inside the nozzle 410 is very smooth, the flow of the gas in the nozzle 410 is as follows. Figure 4 As shown in (a), the flow rate becomes laminar, and the flow velocity decreases as it approaches the inner wall surface of the nozzle 410. In contrast, when the inner surface of the nozzle 410 is made of opaque quartz with fine convex and concave shapes, the flow of the gas in the nozzle 410 is as follows: Figure 4 As shown in (b), the flow becomes turbulent, and the overall average flow velocity is slightly smaller than that of the laminar flow. However, the flow velocity on the wall side inside the nozzle 410 becomes larger, and the heat transfer from the tube wall inside the nozzle 410 becomes smaller, making it difficult for the gas flowing inside the nozzle 410 to be heated.

[0046] In this way, compared with the set temperature in the furnace and the temperature of the chip 200, since the temperature of the gas flowing inside the nozzle 410 becomes lower, the temperature of the chip 200 is increased, making it difficult for organic matter to enter the film formed on the chip 200, and it is also difficult for foreign matter to be generated in the nozzle 410.

[0047] In addition, the nozzle 410 may be made of quartz having different reflectivity to infrared rays according to the heat load. Figure 5 As shown in (a), in this embodiment, the L-shaped nozzle 410 is composed of opaque quartz 411 with high reflectivity from the bottom to the top, but the nozzle 410 can also be composed of quartz with different reflectivity according to the heat load. Figure 5As shown in (b), the lower side (upstream side) of the nozzle 410 may be composed of transparent quartz 412 with low reflectivity, and the upper (downstream side) heater area uniformly heated by the heater 207 may be composed of opaque quartz 411 with high reflectivity, as shown in FIG. Figure 5 As shown in (c), the middle of the wafer area where the wafer 200 is provided on the lower side (upstream side) of the nozzle 410 may be composed of transparent quartz 412 with low reflectivity, and the area above (downstream side) thereof may be composed of opaque quartz 411 with high reflectivity. That is, the entire nozzle 410 may be composed of an opaque quartz member (second member) with high reflectivity, and a part of the nozzle 410 may be composed of an opaque quartz member (second member) with high reflectivity. If transparent quartz 412 with low reflectivity is used on the lower side (upstream side) of the nozzle 410, the preheating of the gas can be effectively performed, and the thermal decomposition of the gas can be suppressed in the area where the opaque quartz 411 with high reflectivity is used. As a result, both the suppression of the thermal decomposition of the gas and the preheating of the gas can be achieved.

[0048] In addition, a tank (not shown) for storing raw gas is provided in the middle of the gas supply pipe 510 upstream of the nozzle 410, and a valve (not shown) is provided on the gas supply pipe 510 connected to the tank, so that the raw gas compressed in the tank flows into the nozzle 410, cooling the supplied gas itself, thereby further reducing the temperature of the gas flowing inside the nozzle 410.

[0049] In addition, the nozzle 420 may be made of transparent quartz having a low reflectivity to infrared rays, similar to the reaction tube 203 constituting the processing chamber 201, or may be made of a different member.

[0050] For example, the nozzle 420 may be composed of a member (third member) having a lower reflectivity to infrared rays than the first member and the second member. As a result, the gas flowing through the nozzle 420 can easily absorb thermal energy and promote gas heating, can be more quickly and uniformly heated to the same temperature as the wafer 200, can easily activate the gas, and can also suppress reliquefaction. The heating temperature of the gas in the nozzle 420 is preferably a temperature lower than the thermal decomposition temperature of each gas. For example, in the case of using transparent quartz of synthetic quartz as the first member, fused quartz having a lower reflectivity than synthetic quartz can be used as the third member. In addition, the third member may be a member having a lower reflectivity than the first member and a smooth surface, or may be a member having a lower reflectivity than the second member and a smooth surface.

[0051] In addition, the nozzle 420 may be composed of a member (fourth member) having a higher infrared absorption rate than the first member and the second member. Thus, the gas flowing through the nozzle 420 easily absorbs heat energy and can promote gas heating, can be heated more quickly and uniformly to the same temperature as the wafer 200, can easily activate the gas, and can also suppress reliquefaction. The heating temperature of the gas in the nozzle 420 is preferably a temperature lower than the thermal decomposition temperature of each gas. For example, black quartz can be used as the fourth member.

[0052] The infrared transmittance of transparent quartz with low infrared reflectivity is preferably 80-90%, the reflectivity is preferably 5-15%, and the absorptivity is preferably 5-10%. The infrared transmittance of opaque quartz with high infrared reflectivity is preferably less than 10%, the reflectivity is preferably 75-90%, and the absorptivity is preferably 5-15%. The infrared transmittance of black quartz with high infrared absorptivity is preferably less than 2%, the reflectivity is preferably 5-15%, and the absorptivity is preferably 80-90%. Each value is selected in each component so that transmittance + reflectivity + absorptivity = 100%.

[0053] The higher the reflectivity of the opaque quartz, the better. If the reflectivity is lower than 75%, the inside of the nozzle 410 is also heated to the substrate processing temperature, and foreign matter may be generated in the nozzle 410.

[0054] An exhaust pipe 231 is provided on the manifold 209 as an exhaust flow path for exhausting the ambient gas in the processing chamber 201. The exhaust pipe 231 is connected to a vacuum pump 246 as a vacuum exhaust device via a pressure sensor 245 and an APC (Auto Pressure Controller) valve 243. The pressure sensor 245 serves as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, and the APC valve 243 serves as an exhaust valve (pressure adjustment unit). The APC valve 243 is a valve constructed as follows: by opening and closing the valve in a state where the vacuum pump 246 is operated, the vacuum exhaust in the processing chamber 201 and the vacuum exhaust stop can be performed, and further, by adjusting the valve opening according to the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is operated, the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. It is also conceivable to include the vacuum pump 246 in the exhaust system.

[0055] A sealing cover 219 as a furnace cover body capable of airtightly closing the lower end opening of the manifold 209 is provided below the manifold 209. The sealing cover 219 is configured to abut against the lower end of the manifold 209 from the lower side in the vertical direction. The sealing cover 219 is formed of a metal such as SUS and is formed in a disc shape. An O-ring 220 as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the boat 217 described later is provided on the side of the sealing cover 219 opposite to the processing chamber 201. The rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the boat lifter 115 as a lifting mechanism vertically provided outside the reaction tube 203. The boat elevator 115 is configured to carry the boat 217 in and out of the processing chamber 201 by raising and lowering the sealing cover 219. The boat elevator 115 is configured as a conveying device (conveying mechanism) for conveying the boat 217, i.e., the wafer 200, in and out of the processing chamber 201. In addition, a baffle (not shown) as a furnace cover is provided below the manifold 209, and the baffle can airtightly close the lower end opening of the manifold 209 while the sealing cover 219 is lowered by the boat elevator 115. The baffle (not shown) is made of metal such as SUS, for example, and is formed into a disc shape. An O-ring (not shown) as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the baffle (not shown). The opening and closing action (lifting action, rotation action, etc.) of the baffle (not shown) is controlled by the baffle opening and closing mechanism (not shown).

[0056] The boat 217 as a substrate support tool (substrate loading unit) is configured to support multiple wafers 200, for example 25 to 200, in a horizontal posture and in a state where the centers are aligned with each other in a vertical direction and arranged in multiple layers, that is, arranged at intervals. The boat 217 is composed of a heat-resistant material such as quartz, SiC, etc. In the lower part of the boat 217, a heat insulation plate (not shown) composed of a heat-resistant material such as quartz, SiC, etc. is supported in multiple layers. With this structure, it is difficult for the heat from the heater 207 to be transferred to the sealing cover 219 side. However, for example, instead of setting a heat insulation plate at the lower part of the boat 217, a heat insulation tube 218 composed of a cylindrical member composed of a heat-resistant material such as quartz, SiC, etc. may be set.

[0057] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby making the temperature in the processing chamber 201 a desired temperature distribution. The temperature sensor 263 is configured in an L shape similarly to the nozzles 410 and 420, and is provided along the inner wall of the reaction tube 203.

[0058] like Figure 3 As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus. The controller 121 is connected to an input / output device 122 such as a touch panel.

[0059] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), etc. A control program for controlling the actions of the substrate processing device, a process plan recording the order and conditions of the substrate processing described later, etc., are readable and stored in the storage device 121c. The process plan is combined to enable the controller 121 to execute each step in the film forming process described later and to obtain a predetermined result, and the process plan functions as a program. Hereinafter, the process plan, control program, etc. are collectively referred to as a program. In addition, the process plan is also referred to as a plan. When the word "program" is used in this specification, sometimes only the process plan body is included, sometimes only the control program body is included, or sometimes both are included. RAM121b is configured as a memory area (working area) that temporarily holds programs, data, etc. read out by CPU121a.

[0060] The I / O port 121d is connected to the above-mentioned MFC512, 522, 312, 322, valves 514, 524, 314, 324, pressure sensor 245, APC valve 243, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, boat elevator 115, baffle opening and closing mechanism (not shown), etc.

[0061] The CPU 121a reads out and executes the control program from the storage device 121c, and reads out the recipe from the storage device 121c according to the input of the operation command from the input / output device 122. The CPU 121a controls the flow rate adjustment operation of various gases performed by the MFCs 512, 522, 312, and 322, the opening and closing operation of the valves 514, 524, 314, and 324, the opening and closing operation of the APC valve 243 and the pressure adjustment operation of the APC valve 243 by the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 by the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the baffle (not shown) by the baffle opening and closing mechanism (not shown), etc. according to the contents of the read recipe.

[0062] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a magnetic tape, a floppy disk or a hard disk, an optical disk such as a CD or a DVD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory or a memory card) 123 into a computer. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are collectively referred to as recording media. When the term recording medium is used in this specification, sometimes only the storage device 121c monomer is included, sometimes only the external storage device 123 monomer is included, or sometimes both are included. In addition, providing the program to the computer can also be carried out without using the external storage device 123, but using communication means such as the Internet or a dedicated line.

[0063] Using the above-mentioned substrate processing apparatus 10, as one of the steps in the manufacturing process of a semiconductor device (element), refer to Figure 7 , Figure 8 An example of a sequence for forming a film on a substrate will be described. In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121 .

[0064] In this embodiment, an aluminum oxide film (AlO film) as a film containing Al and O is formed on the chip 200 by performing the following process a predetermined number of times (n times), the process being: heating the processing chamber 201 that accommodates a plurality of chips 200 as substrates in a loaded state to a predetermined temperature, and simultaneously supplying TMA gas as a raw material gas to the processing chamber 201 from a plurality of supply holes 410a and a pressure reducing hole 410b opened on the nozzle 410; and supplying O3 gas as a reaction gas from a plurality of supply holes 420a opened on the nozzle 420.

[0065] When the word "wafer" is used in this specification, it sometimes means the wafer itself, and sometimes means a laminate of a wafer and a predetermined layer or film formed on its surface. When the word "surface of a wafer" is used in this specification, it sometimes means the surface of the wafer itself, and sometimes means the surface of a predetermined layer, etc. formed on the wafer. When it is recorded in this specification as "forming a predetermined layer on a wafer", it sometimes means directly forming a predetermined layer on the surface of the wafer itself, and sometimes means forming a predetermined layer on a layer, etc. formed on a wafer. In this specification, the use of the word "substrate" is synonymous with the use of the word "wafer".

[0066] (Wafer loading, boat loading) (Steps S101, S102)

[0067] A plurality of wafers 200 are loaded (wafer loading) into the boat 217 (step S101). The shutter opening and closing mechanism (not shown) is used to move the shutter to open the lower end opening of the manifold 209 (shutter opening). Figure 1 As shown, the boat 217 storing a plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading) (step S102). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0068] (Pressure and temperature adjustment) (Step S103)

[0069] The vacuum pump 246 is used to perform vacuum exhaust so that the space in the processing chamber 201, i.e., the space where the wafer 200 is located, reaches the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 (pressure adjustment) is feedback-controlled based on the measured pressure information. The vacuum pump 246 is kept in an operating state at least until the processing of the wafer 200 is completed. In addition, the processing chamber 201 is heated by the heater 207 to reach the desired temperature. At this time, in order to achieve the desired temperature distribution in the processing chamber 201, the amount of power supplied to the heater 207 is feedback-controlled (temperature adjustment) based on the temperature information detected by the temperature sensor 263. The heating of the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed. Next, the rotation of the boat 217 and the wafer 200 is started by the rotation mechanism 267. The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continued at least until the processing of the wafer 200 is completed.

[0070] (Film Forming Step) (Step S110)

[0071] Thereafter, the raw material gas supply step (step S111 ), the residual gas removal step (step S112 ), the reaction gas supply step (step S113 ), and the residual gas removal step (step S114 ) are performed a predetermined number of times in this order.

[0072] [Raw material gas supply step] (step S111)

[0073] Open valve 314 to allow TMA gas (raw material gas) to flow to gas supply pipe 310. TMA gas is flow-regulated by MFC312 and supplied to wafer 200 from supply hole 410a opening in nozzle 410. That is, wafer 200 is exposed to TMA gas. TMA gas supplied from supply hole 410a is discharged from exhaust pipe 231. At the same time, open valve 514 to allow N2 gas to flow into gas supply pipe 510 as carrier gas. N2 gas is flow-regulated by MFC512 and supplied to processing chamber 201 from supply hole 410a of nozzle 410 together with TMA gas, and discharged from exhaust pipe 231.

[0074] In order to prevent TMA gas from entering the nozzle 420 (prevent backflow), the valve 524 is opened to allow N2 gas to flow into the gas supply pipe 520. N2 gas is supplied (purged) into the processing chamber 201 through the gas supply pipe 520 and the nozzle 420, and exhausted from the exhaust pipe 231.

[0075] At this time, the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 1 to 1000Pa, preferably 1 to 100Pa, and more preferably a pressure in the range of 10 to 50Pa. In addition, in this specification, as a numerical range, for example, when recorded as 1 to 1000Pa, it means above 1Pa and below 1000Pa. That is to say, the numerical range includes 1Pa and 1000Pa. Not only pressure, but also all numerical values ​​recorded in this specification such as flow rate, time, and temperature are the same. The supply flow rate of TMA gas controlled by MFC312 is, for example, 10 to 2000sccm, preferably 50 to 1000sccm, and more preferably a flow rate in the range of 100 to 500sccm. The supply flow rate of N2 gas controlled by MFC512 is, for example, 1 to 30slm, preferably 1 to 20slm, and more preferably a flow rate in the range of 1 to 10slm. The time for supplying the TMA gas to the wafer 200 is, for example, in the range of 1 to 60 seconds, preferably 1 to 20 seconds, and more preferably 2 to 15 seconds.

[0076] The heater 207 heats the wafer 200 so that the temperature is, for example, 400 to 600°C, preferably 400 to 550°C, and more preferably 450 to 550°C. By making the temperature below 600°C, the excessive thermal decomposition of the TMA gas can be suppressed, and at the same time, the film formation rate can be appropriately obtained, and the situation where impurities enter the film and the resistivity increases can be suppressed. In addition, the thermal decomposition of the TMA gas starts at about 450°C under conditions close to the treatment, so it is more effective to use the present disclosure in the treatment chamber 201 heated to a temperature below 550°C. On the other hand, by making the temperature above 400°C, the reactivity is high and the film can be effectively formed.

[0077] By supplying TMA gas into the processing chamber 201 under the above conditions, an Al-containing layer is formed on the outermost surface of the wafer 200. The Al-containing layer may contain C and H in addition to the Al layer. The Al-containing layer is formed by physically adsorbing TMA on the outermost surface of the wafer 200, or chemically adsorbing a substance obtained by decomposing a part of TMA, or depositing Al by thermally decomposing TMA. That is, the Al-containing layer may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of TMA or a substance obtained by decomposing a part of TMA, or may be a deposition layer (Al layer) of Al.

[0078] [Residual Gas Removal Step] (Step S112)

[0079] After the Al-containing layer is formed, the valve 314 is closed to stop the supply of TMA gas. At this time, the APC valve 243 remains open, and the vacuum pump 246 is used to evacuate the processing chamber 201, and the unreacted TMA gas or the TMA gas that helps to form the Al-containing layer remaining in the processing chamber 201 is discharged from the processing chamber 201. Valves 514 and 524 are kept open to supply N2 gas to the processing chamber 201. The N2 gas acts as a purge gas, which can improve the effect of discharging the unreacted TMA gas or the TMA gas that helps to form the Al-containing layer remaining in the processing chamber 201 from the processing chamber 201. In addition, the N2 gas from valves 514 and 524 can flow continuously during the residual gas removal step, or it can be supplied intermittently (pulsed).

[0080] [Reaction Gas Supply Step] (Step S113)

[0081] After the residual gas in the processing chamber 201 is removed, the valve 324 is opened to allow O3 gas (reactive gas) as a reactive gas to flow into the gas supply pipe 320. The O3 gas is flow-regulated by the MFC 322, supplied from the supply hole 420a of the nozzle 420 to the wafer 200 in the processing chamber 201, and exhausted from the exhaust pipe 231. That is, the wafer 200 is exposed to the O3 gas. At this time, the valve 524 is opened to allow N2 gas to flow into the gas supply pipe 520. The N2 gas is flow-regulated by the MFC 522, supplied to the processing chamber 201 together with the O3 gas, and exhausted from the exhaust pipe 231. At this time, in order to prevent the O3 gas from intruding into the nozzle 410 (preventing backflow), the valve 514 is opened to allow N2 gas to flow into the gas supply pipe 510. The N2 gas is supplied (purged) to the processing chamber 201 via the gas supply pipe 510 and the nozzle 410, and exhausted from the exhaust pipe 231.

[0082] At this time, the APC valve 243 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 1 to 1000 Pa, preferably 1 to 100 Pa, and more preferably 10 to 40 Pa. The supply flow rate of the O3 gas controlled by the MFC 322 is, for example, 5 to 40 slm, preferably 5 to 30 slm, and more preferably 10 to 20 slm. The time for supplying the O3 gas to the wafer 200 is, for example, 1 to 60 seconds, preferably 1 to 30 seconds, and more preferably 5 to 25 seconds. The other processing conditions are the same as those in the above-mentioned raw material gas supply step.

[0083] At this time, the gas flowing into the processing chamber 201 is only O3 gas and inert gas (N2 gas). The O3 gas reacts with at least a portion of the Al-containing layer formed on the wafer 200 in the raw material gas supply step. The Al-containing layer is oxidized to form an aluminum oxide layer (AlO layer) containing Al and O as a metal oxide layer. That is, the Al-containing layer is modified into an AlO layer.

[0084] [Residual gas removal step] (step S114)

[0085] After the AlO layer is formed, the valve 324 is closed to stop the supply of O3 gas. At this time, the APC valve 243 remains open, and the valves 514 and 524 are kept open to supply N2 gas (purge) into the processing chamber 201. The unreacted O3 gas or the reaction byproducts that contribute to the formation of the AlO layer and remain in the processing chamber 201 are discharged from the processing chamber 201 through the same processing sequence as the residual gas removal step after the raw material gas supply step.

[0086] [Perform the scheduled number of times] (step S115)

[0087] By performing the above-mentioned raw gas supply step, residual gas removal step, reaction gas supply step, and residual gas supply step in sequence for more than one time (predetermined number of times), an AlO film is formed on the wafer 200. The number of cycles is appropriately selected according to the film thickness required for the AlO film finally formed, and the cycle is preferably repeated multiple times. The thickness (film thickness) of the AlO film is, for example, 0.1 to 150 nm, preferably 0.1 to 10 nm. By setting it to less than 150 nm, the surface roughness can be reduced, and by setting it to more than 0.1 nm, the occurrence of film peeling caused by the stress difference with the base film can be suppressed.

[0088] (Post-purge, atmospheric pressure recovery) (Steps S121, S122)

[0089] If the film forming step is completed, valves 514 and 524 are opened to supply N2 gas from gas supply pipes 310 and 320 to the processing chamber 201, respectively, and exhaust it from exhaust pipe 231. N2 gas acts as a purge gas to remove gas and byproducts remaining in the processing chamber 201 (post-purge) (step S121). After that, the atmosphere in the processing chamber 201 is replaced with N2 gas (N2 gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery) (step S122).

[0090] (Boat unloading, wafer unloading) (steps S123, S124)

[0091] After that, the sealing cover 219 is lowered by the boat elevator 115, the lower end of the manifold 209 is opened, and the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading) (step S123). After the boat is unloaded, the baffle (not shown) is moved, and the lower end opening of the manifold 209 is sealed by the baffle (not shown) via an O-ring (not shown) (closing the baffle). After the processed wafers 200 are carried out to the outside of the reaction tube 203, they are taken out from the boat 217 (wafer unloading) (step S124).

[0092] In addition, during the non-operating time other than the above-mentioned film forming process (step S110 (steps S111 to S114)), the inert gas (N2 gas) is flowed into the nozzle 410 by opening the valve 514 (see Figure 8 (b)) is used to promote heat dissipation from the inner wall of the nozzle 410, which is also effective in reducing the temperature of TMA (raw material gas) flowing into the nozzle 410 in the subsequent film forming process.

[0093] (Modification of the first embodiment)

[0094] Next, a modification of the preferred first embodiment of the present disclosure will be described. The difference from the first embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3 is used in the first embodiment, but in this modification, NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent). The rest is substantially the same as the first embodiment. In this modification, TMA and NH3 are alternately supplied into the processing chamber 201 to form an aluminum nitride film (AlN film) on the wafer 200.

[0095] (Second Embodiment)

[0096] Next, a preferred second embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the second embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 into the processing chamber 201, TMA is used in the first embodiment, but in this embodiment, TEMAH is used as an example of an organic compound containing hafnium element. As the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3, which is the same as the first embodiment, is used. TEMAH and O3 are alternately supplied into the processing chamber 201 to form an HfO film on the wafer 200. The timing of forming the HfO film is also the same as that of the first embodiment.

[0097] (Variation of the Second Embodiment)

[0098] Next, a modification of the preferred second embodiment of the present disclosure will be described. The difference from the second embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3 is used in the first embodiment, but NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent) in this modification. The rest is substantially the same as the third embodiment. In this modification, TEMAH and NH3 are alternately supplied into the processing chamber 201 to form a hafnium nitride film (HfN film) on the wafer 200.

[0099] (Third Embodiment)

[0100] Next, a preferred third embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the third embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 into the processing chamber 201, TMA is used in the first embodiment, but in this embodiment, TEMAZ is used as an example of an organic compound containing a zirconium element. As the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3, which is the same as the first embodiment, is used. TEMAZ and O3 are alternately supplied into the processing chamber 201 to form a ZrO film on the wafer 200. The timing of forming the ZrO film is also the same as the first embodiment.

[0101] (Variation of the Third Embodiment)

[0102] Next, a modification of the preferred third embodiment of the present disclosure will be described. The difference from the third embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3 is used in the first embodiment, but NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent) in this modification. The rest is substantially the same as the third embodiment. In this modification, TEMAZ and NH3 are alternately supplied into the processing chamber 201 to form a zirconium nitride film (ZrN film) on the wafer 200.

[0103] (Fourth Embodiment)

[0104] Next, a preferred fourth embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the fourth embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 into the processing chamber 201, TMA is used in the first embodiment, but in this embodiment, TDMAT (tetrakis(dimethylamino)titanium, Ti[N(CH3)2]4) is used as an example of an organic compound containing a titanium element. As the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3, which is the same as the first embodiment, is used. TDMAT and O3 are alternately supplied into the processing chamber 201 to form a titanium oxide film (TiO film) on the wafer 200. The timing of forming the TiO film is also the same as the first embodiment.

[0105] (Variation of the Fourth Embodiment)

[0106] Next, a modification of the preferred fourth embodiment of the present disclosure will be described. The difference from the fourth embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3 is used in the fourth embodiment, but NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent) in this modification. The rest is substantially the same as the fourth embodiment. In this modification, TDMAT and NH3 are alternately supplied into the processing chamber 201 to form a titanium nitride film (TiN film) on the wafer 200.

[0107] (Fifth Embodiment)

[0108] Next, a preferred fifth embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the fifth embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 into the processing chamber 201, TMA is used in the first embodiment, but in this embodiment, as an example of an organic compound containing silicon element, 3DMAS (tris(dimethylamino)silane, SiH(N(CH3)2)3) is used. As the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3, which is the same as the first embodiment, is used. 3DMAS and O3 are alternately supplied into the processing chamber 201 to form a SiO film on the wafer 200. The timing of forming the SiO film is also the same as the first embodiment.

[0109] (Variation of the Fifth Embodiment)

[0110] Next, a modification of the preferred fifth embodiment of the present disclosure will be described. The difference from the fifth embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O3 is used in the fifth embodiment, but NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent) in this modification. The rest is substantially the same as the fifth embodiment. In this modification, 3DMAS and NH3 are alternately supplied into the processing chamber 201 to form a silicon nitride film (SiN film) on the wafer 200.

[0111] (Sixth Embodiment)

[0112] Next, the preferred sixth embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the sixth embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 to the processing chamber 201, TMA is used in the first embodiment, but in this embodiment, HCDS (hexachlorodisilane, Si2Cl6) is used as an example of a compound containing silicon element. As the gas supplied from the gas supply pipe 320 via the nozzle 420 to the processing chamber 201, O3 is used in the first embodiment, but in this embodiment, oxygen (O2) and hydrogen (H2) are used as oxidizing gases (oxidants). HCDS, O2 and H2 are alternately supplied to the processing chamber 201 to form a SiO film on the wafer 200. The timing of forming the SiO film is also the same as that of the first embodiment.

[0113] (Variation of Sixth Embodiment)

[0114] Next, a modification of the preferred sixth embodiment of the present disclosure will be described. The difference from the sixth embodiment is that, as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, O2 and H2 are used in the sixth embodiment, but NH3 is used as the nitrogen-containing gas (nitriding gas, nitriding agent) in this modification. The rest is substantially the same as the sixth embodiment. In this modification, HCDS and NH3 are alternately supplied into the processing chamber 201 to form a silicon nitride film (SiN film) on the wafer 200.

[0115] (Seventh Embodiment)

[0116] Next, the preferred seventh embodiment of the present disclosure will be described. The substrate processing device 10 preferably used in the seventh embodiment has the same structure as the substrate processing device 10 preferably used in the above-mentioned first embodiment. As the gas supplied from the gas supply pipe 310 via the nozzle 410 to the processing chamber 201, TMA is used in the first embodiment, but tungsten hexafluoride (WF6) gas is used in the present embodiment. As the gas supplied from the gas supply pipe 320 via the nozzle 420 to the processing chamber 201, O3 is used in the first embodiment, but diborane (B2H6) gas is used in the present embodiment. B2H6 is used as a reducing agent. WF6 and B2H6 are alternately supplied to the processing chamber 201 to form a tungsten film (W film) on the wafer 200. The timing of forming the W film is also the same as that of the first embodiment.

[0117] (Variation 1 of the Seventh Embodiment)

[0118] Next, a modification example 1 of the preferred seventh embodiment of the present disclosure will be described. The difference from the seventh embodiment is that, in the seventh embodiment, B2H6 gas is used as the gas supplied from the gas supply pipe 320 via the nozzle 420 into the processing chamber 201, but in this modification example 1, O3 gas is used in addition to B2H6 gas. The rest is essentially the same as the seventh embodiment. However, O3 gas can also flow by newly setting other gas supply pipes and nozzles. In this modification example 1, WF6, B2H6, and O3 gases are repeatedly supplied to the processing chamber 201 in a manner that they are not mixed with each other, and a tungsten oxide film (WO film) is formed on the wafer 200.

[0119] (Variation 2 of the Seventh Embodiment)

[0120] Next, a modification example 2 of the preferred seventh embodiment of the present disclosure will be described. The difference from the modification example 1 of the seventh embodiment is that, as the gas supplied from the gas supply pipe 320 to the processing chamber 201 via the nozzle 420, B2H6 gas and O3 gas are used in the modification example 1 of the seventh embodiment, but B2H6 gas and NH3 gas are used in this modification example 2. The rest is substantially the same as the modification example 1 of the seventh embodiment. In this modification example 2, WF6, B2H6, and NH3 gases are repeatedly supplied to the processing chamber 201 in a manner that they are not mixed with each other, and a tungsten nitride film (WN film) is formed on the wafer 200.

[0121] In the second to seventh embodiments, the reaction tube 203 constituting the processing chamber 201 is made of transparent quartz having a low reflectivity to infrared rays, but the nozzle 410 is made of opaque quartz having a higher reflectivity to infrared rays than the member constituting the reaction tube 203. In addition, since the opaque quartz having a high reflectivity to infrared rays used in the nozzle 410 contains bubbles inside, the surface inside the nozzle 410 becomes finely convex and concave due to the bubbles, and the flow of gas inside the nozzle 410 becomes turbulent. As a result, the temperature of the gas flowing inside the nozzle 410 becomes lower than the set temperature in the furnace and the temperature of the wafer 200, so that the temperature of the wafer 200 is increased, impurities (organic matter in organic compounds) are less likely to enter the film formed on the wafer 200, and the problem of foreign matter being generated inside the nozzle 410 is less likely to occur.

[0122] Thus, the substrate processing apparatus 10 used in the first to seventh embodiments can be applied to the formation of oxide films, nitride films, and metal films regardless of the type of film to be formed, and is particularly effective for processes of forming films at a temperature higher than the autodecomposition temperature.

[0123] In addition, regardless of the type of gas supplied to the nozzle 410 for the raw material gas formed by the second member having a higher reflectivity to infrared rays than the member constituting the reaction tube 203, the substrate processing apparatus 10 used in the first embodiment to the seventh embodiment can be applied, and is particularly effective for the raw material gas used in the process of forming a film at a temperature higher than the autodecomposition temperature. For example, in addition to the gas types used in the first embodiment to the seventh embodiment, DCS (dichlorosilane, SiH2Cl2), BTBAS (bis (tert-butylamino) silane, SiH2[NH(C4H9)]2), monosilane (SiH4), titanium chloride (TiCl4), etc. can also be applied. Among them, organic raw materials are particularly effective due to their low thermal decomposition temperature.

[0124] In addition, the substrate processing apparatus 10 used in the first to seventh embodiments can be applied regardless of the type of gas supplied to the nozzle 420 for the reaction gas, and the nozzle 420 for the reaction gas is composed of a third member having a lower reflectivity to infrared rays than the first and second members, or a fourth member having a higher absorptivity to infrared rays than the first and second members, and is particularly effective for a reaction gas used in a process of forming a film at a temperature lower than the autodecomposition temperature, that is, a reaction gas that is difficult to deactivate. For example, it can also be applied to O2, O2 and H2, nitrous oxide (N2O), water vapor (H2O), NH3, etc.

[0125] In addition, in the substrate processing apparatus 10 used in the first to seventh embodiments, when a process of forming a film at a temperature lower than the autodecomposition temperature is performed, the nozzle 410 for the raw material gas may be formed by a third member having a lower reflectivity to infrared rays than the first and second members, or a fourth member having a higher absorptivity to infrared rays than the first and second members. In this case, the raw material gas used can be applied regardless of the type of gas as long as it is a raw material gas used in a process of forming a film at a temperature lower than the autodecomposition temperature. For example, in addition to the gas types used in the first to seventh embodiments, DCS, BTBASSiH4, TiCl4, etc. may also be applied.

[0126] The first to seventh embodiments described above can also be appropriately combined and applied to the case of forming a composite film of the films formed in each embodiment. For example, the first embodiment and the fifth embodiment can be combined to form a titanium aluminum oxide film (TiAlO film) using a plurality of organic compounds. In addition, for example, the sixth embodiment and its modified example can be combined to form a silicon oxynitride film (SiON film) using an oxygen-containing gas and a nitrogen-containing gas as a plurality of reaction gases.

[0127] In addition, the source gas nozzle in this specification is preferably used in a path where the pressure is equal to or higher than the pressure on the wafer 200 during gas supply, and is not limited to a batch type or a single wafer type.

[0128] Various typical embodiments of the present disclosure have been described above, but the present disclosure is not limited to these embodiments. Therefore, the scope of the present disclosure is limited only by the technical solutions.

[0129] The disclosed contents of Japanese Patent Application No. 2018-063255 are incorporated in their entirety into this specification as a reference.

[0130] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

[0131] Description of Reference Numerals

[0132] 10. substrate processing device;

[0133] 200 wafers;

[0134] 203 reaction tube;

[0135] 410 Nozzle;

[0136] 420 Nozzle.

Claims

1. A substrate processing device, characterized in that: The substrate processing device comprises: A reaction tube, which is composed of a first member and accommodates a substrate; a substrate loading unit capable of loading a plurality of the substrates in a horizontal position and in multiple layers in a vertical direction; and a raw material gas nozzle disposed in the reaction tube and supplying a raw material gas into the reaction tube, wherein at least a portion of the raw material gas nozzle is composed of a second member, the second member has a higher reflectivity than the first member, and the second member has a surface rougher than the first member due to bubbles contained therein, The raw material gas nozzle extends from at least one end side of the area where the substrate is mounted to the other end side, the downstream area has the second component, and the upstream area has the first component. The first component and the second component are provided with a plurality of supply holes at the upper and lower parts of the reaction tube for supplying the raw material gas into the reaction tube.

2. The substrate processing device according to claim 1, characterized in that: The reflectivity of the second member is 75% or more.

3. The substrate processing device according to claim 1, characterized in that: The second member has a higher reflectivity to infrared rays than the first member.

4. The substrate processing device according to claim 3, characterized in that: The substrate processing apparatus further includes a heater for heating the inside of the reaction tube using the infrared rays.

5. The substrate processing device according to claim 4, characterized in that: The heater is provided to heat at least from one end side to the other end side of the region where the substrate is mounted.

6. The substrate processing apparatus according to claim 1, wherein: The substrate processing device comprises: a raw material gas supply system including the raw material gas nozzle and supplying the raw material gas; and a control unit configured to control the raw material gas supply system, The raw gas supply system includes a tank for storing the raw gas, a valve is provided on a gas supply pipe connected to the tank, and the control unit is configured to control the valve so that the raw gas compressed in the tank flows into the raw gas nozzle.

7. The substrate processing apparatus according to claim 1, wherein: The substrate processing device comprises: a raw material gas supply system including the raw material gas nozzle and supplying the raw material gas; and a control unit configured to control the raw material gas supply system, The raw material gas supply system includes an inert gas supply system for supplying an inert gas, The control unit is configured to control the inert gas supply system so as to supply the inert gas to the raw material gas nozzle in a process other than a process in which the raw material gas is supplied from the raw material gas nozzle.

8. The substrate processing apparatus according to claim 1, wherein: The substrate processing device comprises: a raw material gas supply system, which is provided with the raw material gas nozzle and supplies the raw material gas; A reaction gas supply system including a reaction gas nozzle for supplying a reaction gas having a molecular structure different from that of the raw material gas into the reaction tube; and a control unit configured to control the raw gas supply system and the reaction gas supply system, The control unit is configured to supply the raw material gas from the raw material gas nozzle into the reaction tube that accommodates the substrate, and to supply the reaction gas from the reaction gas nozzle into the reaction tube, and is capable of controlling the raw material gas supply system and the reaction gas supply system to form a film on the substrate.

9. The substrate processing device according to claim 8, characterized in that: The reaction gas nozzle is formed of a third member having a lower reflectivity than the first member and a smoother surface than the first member.

10. The substrate processing apparatus according to claim 8, wherein: The reaction gas nozzle is formed of a third member having a lower reflectivity than the second member and a smoother surface than the first member.

11. The substrate processing apparatus according to claim 8, wherein: The reaction gas nozzle is constituted by the first member.

12. A gas nozzle, which is arranged in a reaction tube and supplies a raw material gas into the reaction tube, wherein the reaction tube is horizontally loaded with a plurality of substrates in multiple layers in a vertical direction, wherein at least a portion of the gas nozzle is composed of a second member, the second member has a higher reflectivity than a first member constituting the reaction tube, and has a surface rougher than the first member due to bubbles contained therein, wherein the gas nozzle is characterized in that: The gas nozzle extends from at least one end side of the area where the substrate is mounted to the other end side, the downstream area has the second component, and the upstream area has the first component. The first component and the second component are provided with a plurality of supply holes at the upper and lower parts of the reaction tube for supplying the raw material gas into the reaction tube.

13. A method for manufacturing a semiconductor device, characterized in that: The method for manufacturing a semiconductor device comprises: A process of accommodating a substrate in a reaction tube of a substrate processing device, wherein the substrate processing device comprises: the reaction tube composed of a first member and accommodating the substrate; a substrate loading unit capable of loading a plurality of substrates in a horizontal posture in a vertical direction in multiple layers; a raw material gas nozzle, which is arranged in the reaction tube and supplies raw material gas into the reaction tube, at least a part of which is composed of a second member, the reflectivity of the second member is higher than that of the first member, and the second member has a surface rougher than that of the first member due to bubbles contained therein, the raw material gas nozzle is extended from at least one end side to the other end side of the region where the substrate is loaded, and the region from the middle of the region where the substrate is loaded to the upstream side is composed of the first member, and a plurality of supply holes for supplying the raw material gas into the reaction tube are provided in the first member and the second member constituting the raw material gas nozzle at the upper part and the lower part of the reaction tube, and and supplying the raw material gas to the substrate from the raw material gas nozzle.

14. A computer-readable recording medium, characterized in that: The computer-readable recording medium records a program for causing a substrate processing apparatus to execute the following steps through a computer: The step of accommodating a substrate in a reaction tube of a substrate processing device, wherein the substrate processing device comprises: The reaction tube is composed of a first component and accommodates the substrate; a substrate mounting unit capable of mounting a plurality of substrates in a horizontal posture in a vertical direction in multiple layers; a raw material gas nozzle, which is arranged in the reaction tube and supplies raw material gas into the reaction tube, at least a part of which is composed of a second component, the reflectivity of the second component is higher than that of the first component, and the second component has a surface rougher than that of the first component due to bubbles contained therein, the raw material gas nozzle is extended from at least one end side of the region where the substrate is mounted to the other end side, and the region from the middle of the region where the substrate is mounted to the upstream side is composed of the first component, and a plurality of supply holes for supplying the raw material gas into the reaction tube are provided in the first component and the second component constituting the raw material gas nozzle at the upper part and the lower part of the reaction tube, and and supplying the raw material gas to the substrate from the raw material gas nozzle.

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