Semiconductor device manufacturing method, substrate processing method, substrate processing device and recording medium

Abstract

The present invention relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus and a recording medium. The in-plane film thickness distribution of a film formed on a substrate having a pattern formed on the surface is controlled. An oxide film containing a specified element is formed on the substrate by performing the following (a) and (b) non-simultaneously for a specified number of times: (a) for a substrate having a pattern formed on the surface, a process of supplying a raw material gas containing a specified element from the periphery of the substrate into the surface of the substrate, thereby forming a first layer containing the specified element on the surface; (b) for a substrate, a process of supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate, thereby oxidizing the first layer and forming an oxide layer containing the specified element on the surface, wherein in (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a specified distribution.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus and a recording medium. Background Art

[0002] In some cases, a substrate support on which substrates having patterns formed on their surfaces are dispersed and loaded is accommodated in a processing chamber, and a predetermined film is formed on the surface of the substrate (see, for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent document 1: International Publication No. 2017 / 168675 pamphlet. Summary of the invention

[0006] Problems to be solved by the invention

[0007] When a predetermined film is formed on the surface of a substrate having a pattern formed on the surface, the pattern is formed on the surface to increase the surface area, thereby sometimes causing the uniformity of the film thickness within the surface of the substrate to deteriorate.

[0008] An object of the present invention is to control the in-plane film thickness distribution of a film formed on a substrate having a pattern formed on its surface.

[0009] Means for solving problems

[0010] According to one embodiment of the present invention, the following technology is provided, wherein an oxide film containing a specified element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a specified number of times: (a) for a substrate having a pattern formed on the surface, a process of forming a first layer containing the specified element on the surface by supplying a raw material gas containing the specified element from the periphery of the substrate to the surface of the substrate; (b) for the substrate, a process of forming an oxide layer containing the specified element on the surface by oxidizing the first layer by supplying an oxidizing gas from the periphery of the substrate to the surface of the substrate, wherein in (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a specified distribution.

[0011] Effects of the Invention

[0012] According to the present invention, it is possible to control the in-plane film thickness distribution of a film formed on a substrate having a pattern formed on its surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic longitudinal sectional view of a substrate processing apparatus used for forming a film on a substrate in order to explain a preferred embodiment of the present invention.

[0014] Figure 2 for Figure 1 AA schematic cross-sectional view.

[0015] Figure 3 It is a schematic diagram for explaining a controller of a substrate processing apparatus according to a preferred embodiment of the present invention.

[0016] Figure 4 It is a flowchart for explaining a preferred film forming process flow according to a preferred embodiment of the present invention.

[0017] Figure 5 It is a figure for demonstrating the evaluation method used in an Example.

[0018] Figure 6 (A) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the bare surface when the interval between the substrates is a first distance and the supply time of the oxidizing gas; Figure 6 (B) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the pattern surface when the distance between the substrates is the first distance and the supply time of the oxidizing gas.

[0019] Figure 7 (A) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the bare surface when the interval between the substrates is the second distance and the supply time of the oxidizing gas; Figure 7 (B) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the pattern surface when the distance between the substrates is the second distance and the supply time of the oxidizing gas.

[0020] Figure 8 It is a diagram showing the relationship between the film thickness of the oxide film formed at the center of each of the bare surface and the pattern surface, the supply time of the oxidizing gas, and the distance between the substrates.

[0021] Fig. 9 It is a graph showing the relationship between the film thickness projection from the center of the substrate to 150 mm, the film thickness projection from the center of the substrate to 100 mm, and the supply time of the oxidizing gas.

[0022] Description of Reference Numerals

[0023] 121 controller (control unit)

[0024] 200 Wafer (substrate)

[0025] 202 Treatment furnace DETAILED DESCRIPTION

[0026] <One embodiment of the present invention>

[0027] Hereinafter, an embodiment of the present invention will be described. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. on the drawings may not be consistent with the actual situation. In addition, the dimensional relationship of each element, the ratio of each element, etc. may not be consistent between multiple drawings.

[0028] (1) Configuration of substrate processing apparatus

[0029] The substrate processing apparatus 10 of the preferred embodiment of the present invention is provided with 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 by 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 at a predetermined temperature.

[0030] 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. A manifold (inlet flange) 209 is arranged concentrically with the reaction tube 203 below 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 open upper end and a lower end. The upper end of the manifold 209 is configured to engage with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220 as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is supported on a heater base (not shown) by the manifold 209, so that the reaction tube 203 is installed vertically. The reaction tube 203 and the manifold 209 constitute a processing container (reaction container). 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 and in a multi-layered state in the vertical direction through a wafer boat 217 as a substrate holder. It should be noted that the heater 207 is provided to heat from at least one end side to the other end side of the wafer arrangement area where the wafers 200 are arranged.

[0031] In the processing chamber 201, nozzles 410 and 420 are provided so as to penetrate 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.

[0032] 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 opening and closing 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 gas supply pipes 310 and 320 downstream of the valves 314 and 324, 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 opening and closing valves, respectively, in order from the upstream side.

[0033] The front ends of the gas supply pipes 310 and 320 are connected to nozzles 410 and 420, respectively. Figure 2 As shown in FIG. 1 , the nozzles 410 and 420 are respectively arranged in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, so as to stand and extend upward from the lower part to the upper part of the inner wall of the reaction tube 203 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 horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged. That is, the nozzles 410 and 420 are respectively arranged on the side of the end (peripheral part) of each wafer 200 carried into the processing chamber 201 and perpendicular to the surface (flat surface) of the wafer 200. 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 upward from at least one end side to the other end side of the wafer arrangement area, and extend from the one end side to the other end side.

[0034] A plurality of supply holes 410a (first gas supply hole, raw material gas supply hole) and 420a (second gas supply hole, oxidation gas supply hole) as gas supply ports for supplying gas are provided at the height corresponding to the wafer 200 (the height corresponding to the substrate loading area) on the side surface 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 from the outer periphery of the wafer 200 to the surface of the wafer 200. A plurality of supply holes 410a and 420a are provided at a position opposite to the wafer boat 217 in the reaction tube 203 where the wafer 200 exists, in other words, from the lower end to the upper part of the heater 207.

[0035] As for the supply holes 410a and 420a, a plurality of them are provided in the range from the bottom to the top of the reaction tube 203, each having the same opening area and further provided at the same opening spacing. However, the supply holes 410a and 420a are not limited to the above-mentioned form. For example, the opening area may be gradually increased from the bottom (upstream side) of the nozzles 410 and 420 toward the top (downstream side). Thus, the flow rate of the gas supplied from the supply holes 410a and 420a can be made more uniform.

[0036] Thus, in this embodiment, the gas is transported through the nozzles 410 and 420 arranged in the longitudinal space which is annular in plan view, that is, in the cylindrical 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. 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. Then, 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. That is, the plurality of supply holes 410a and 420a are arranged on the outer periphery of the wafer 200, and the gas is supplied from the outer periphery (end portion) of the wafer 200 to the in-plane (e.g., center) of the wafer 200 (side flow configuration).

[0037] A source gas containing a predetermined element is supplied from the gas supply pipe 310 into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410. When the source gas flows out from the nozzle 410, the nozzle 410 may also be referred to as a source gas nozzle.

[0038] 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 gasifying a liquid raw material in a liquid state at normal temperature and pressure, etc. When the term "raw material" is used in this specification, it sometimes means "a liquid raw material", sometimes means "a raw material in a gaseous state (raw material gas)", or sometimes means both of the above. Organic compounds such as TMA, TEMAH, and TEMAZ are liquid raw materials, so substances that are gasified by a vaporizer or the like to form a gas are used as raw material gases.

[0039] An oxygen-containing gas serving as an oxidizing gas (oxidant) is supplied from a gas supply pipe 320 into the processing chamber 201 via the MFC 322 , the valve 324 , and the nozzle 420 .

[0040] The inert 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.

[0041] 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 can also be referred to as a raw material supply system.

[0042] When the oxidizing gas is supplied from the gas supply pipe 320 , the oxidizing gas supply system is mainly composed of the gas supply pipe 320 , the MFC 322 , the valve 324 , and the nozzle 420 .

[0043] The inert gas supply system is mainly composed of the gas supply pipes 510 and 520 , the MFCs 512 and 522 , and the valves 514 and 524 .

[0044] The raw material gas supply system and the oxidizing gas supply system may be 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.

[0045] An exhaust pipe 231 is provided on the manifold 209 as an exhaust flow path for exhausting the atmosphere 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 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, and an APC (Auto Pressure Controller) valve 243 as an exhaust valve (pressure regulating unit). The APC valve 243 is a valve configured as follows: by opening and closing the valve while the vacuum pump 246 is in operation, vacuum exhaust and vacuum exhaust stop in the processing chamber 201 can be performed, and further, by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, 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.

[0046] Below the manifold 209, a sealing cover 219 as a furnace port cover that can hermetically seal the lower end opening of the manifold 209 is provided. 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 made of metal such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220 as a sealing member that abuts against the lower end of the manifold 209 is provided. On the side of the sealing cover 219 opposite to the processing chamber 201, a rotating mechanism 267 for rotating the wafer boat 217 is provided. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism vertically provided outside the reaction tube 203. The boat elevator 115 is configured to move the boat 217 into and out of the processing chamber 201 by raising and lowering the sealing cover 219. The boat elevator 115 is configured as a transport device (transport mechanism) that transports the boat 217, i.e., the wafer 200, into and out of the processing chamber 201. In addition, a gate (not shown) as a furnace cover is provided below the manifold 209, and the lower end opening of the manifold 209 can be airtightly closed while the sealing cover 219 is lowered by the boat elevator 115. The gate (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 gate (not shown). The opening and closing action (lifting action, rotation action, etc.) of the gate (not shown) is controlled by a gate opening and closing mechanism (not shown).

[0047] The wafer boat 217 as a substrate support (substrate loading means) is configured to support multiple (for example, 25 to 200) wafers 200 in a horizontal posture and arranged in a vertical direction in a state where the centers are aligned with each other, that is, arranged in multiple layers at predetermined intervals (inter-wafer spacing). The wafer boat 217 is composed of, for example, a heat-resistant material such as quartz or SiC. In the lower part of the wafer boat 217, a heat insulation plate (not shown) composed of, for example, a heat-resistant material such as quartz or SiC is supported in multiple layers. With this configuration, the heat from the heater 207 is not easily transferred to the sealing cover 219 side. However, for example, instead of providing a heat insulation plate at the lower part of the wafer boat 217, a heat insulation tube 218 that is a cylindrical member composed of a heat-resistant material such as quartz or SiC may be provided.

[0048] 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, so that the temperature in the processing chamber 201 reaches 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.

[0049] like Figure 3 As shown in FIG. 1 , the controller 121 as a control unit (control means) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus. The controller 121 is connected to an input / output device 122 configured in the form of a touch panel, etc.

[0050] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. A control program for controlling the operation of the substrate processing device, a process recipe recording the steps and conditions of the substrate processing described later, etc. are readable and stored in the storage device 121c. The process recipe is obtained by combining the steps in the film forming process described later in such a way that the controller 121 executes and can obtain a specified result, and functions as a program. Hereinafter, the process recipe, control program, etc. are also collectively referred to as a program. In addition, the process recipe is also referred to as a process. When the term program is used in this specification, there is a case where only the process recipe is included, only the control program is included, or both of the above are included. RAM121b is configured as a storage area (working area) for temporarily holding programs, data, etc. read by CPU121a.

[0051] 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, wafer elevator 115, gate opening and closing mechanism (not shown), etc.

[0052] The CPU 121a is configured to read a control program from the storage device 121c and execute it, and to read a process from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read process, the flow rate adjustment operation of various gases 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 by the pressure sensor 245 and the APC valve 243, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 by the temperature sensor 263, the rotation of the wafer boat 217 by the rotation mechanism 267 and the rotation speed adjustment operation, the lifting operation of the wafer boat 217 by the wafer boat elevator 115, the opening and closing operation of the shutter (not shown) by the shutter opening and closing mechanism (not shown), and the like.

[0053] 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, a hard disk, an optical disk such as a CD, a DVD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory, an SSD, etc.) 123 into a computer. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, the above-mentioned components are also collectively referred to as recording media. When the term recording medium is used in this specification, there is a case where only the storage device 121c is included alone, a case where only the external storage device 123 is included alone, or a case where both of the above are included. It should be noted that providing a program to a computer can also be carried out without using the external storage device 123 and using communication means such as the Internet and dedicated lines.

[0054] (2) Substrate processing step

[0055] As one of the steps in the manufacturing process of a semiconductor device (apparatus), a film is formed on a wafer 200 having a pattern formed on its surface using the substrate processing apparatus 10 as described above. Figure 4 In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121 .

[0056] In this embodiment, the wafer 200 is a large surface area substrate having a pattern formed on the surface and having an upper surface area that is, for example, 3 / 2 times or more, preferably 10 times or more, and more preferably 50 times or more of the upper surface area of ​​a bare wafer having no pattern formed on the surface. That is, when the wafer 200 is circular, the upper surface area having the pattern formed thereon is, for example, 3πr with respect to the radius r of the wafer 200. 2 above.

[0057] In addition, in this embodiment, an oxide film (hereinafter, sometimes simply referred to as an oxide film) containing a predetermined element is formed on the wafer 200 by performing the following steps non-simultaneously for a predetermined number of times (n times):

[0058] A step of heating a processing chamber 201 in which a plurality of wafers 200 are loaded to a predetermined temperature and supplying a gas containing a predetermined element as a raw material gas to the processing chamber 201 from a plurality of supply holes 410a opened in a nozzle 410; and

[0059] A step of supplying an oxidizing gas from a plurality of supply holes 420 a opened in the nozzle 420 .

[0060] When the term "wafer" is used in this specification, it sometimes means the wafer itself, and sometimes means a stack of a wafer and a predetermined layer or film formed on its surface. When the term "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 forming a predetermined layer directly on the surface of the wafer itself, and sometimes means forming a predetermined layer on a layer, etc. formed on the wafer. When the term "substrate" is used in this specification, it is also synonymous with the term "wafer".

[0061] (Wafer filling and wafer boat loading) (Steps S101, S102)

[0062] A plurality of wafers 200 are loaded (wafer filling) into the wafer boat 217 (step S101). The shutter is moved by a shutter opening and closing mechanism (not shown) to open the lower end opening of the manifold 209 (the shutter is opened). Then, as shown in FIG. Figure 1 As shown, the boat 217 containing 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 220 .

[0063] (Pressure and temperature adjustment) (Step S103)

[0064] The vacuum pump 246 performs vacuum exhaust so that the space in the processing chamber 201, that is, the space where the wafer 200 exists, 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 is feedback-controlled (pressure regulated) based on the measured pressure information. The vacuum pump 246 is always in operation until at least the processing of the wafer 200 is completed. In addition, the processing chamber 201 is heated to a desired temperature by the heater 207. At this time, the amount of power supplied to the heater 207 is feedback-controlled (temperature regulated) based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 reaches the desired temperature distribution. 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 wafer boat 217 and the wafer 200 is started by the rotation mechanism 267. The rotation of the wafer boat 217 and the wafer 200 by the rotation mechanism 267 is continued at least until the processing of the wafer 200 is completed.

[0065] (Film Forming Process) (Step S110)

[0066] Then, the raw gas supply step (step S111), the residual gas removal step (step S112), the oxidation gas supply step (step S113), and the residual gas removal step (step S114) are sequentially performed a predetermined number of times non-simultaneously.

[0067] [Raw material gas supply step] (step S111)

[0068] The valve 314 is opened to allow the raw material gas to flow to the gas supply pipe 310. The raw material gas is flow-regulated by the MFC 312 and supplied to the wafer 200 from the supply hole 410a opened in the nozzle 410. That is, the wafer 200 is exposed to the raw material gas. The raw material gas supplied from the supply hole 410a is exhausted from the exhaust pipe 231. At the same time, the valve 514 is opened to allow the inert gas to flow into the gas supply pipe 510 as a carrier gas. The inert gas is flow-regulated by the MFC 512 and supplied to the processing chamber 201 from the supply hole 410a of the nozzle 410 together with the raw material gas, and is exhausted from the exhaust pipe 231.

[0069] It should be noted that, as the inert gas, for example, rare gases such as nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This is also the same in each step described later.

[0070] In order to prevent the raw material gas from entering the nozzle 420 (prevent backflow), the valve 524 is opened to allow the inert gas to flow into the gas supply pipe 520. The inert gas is supplied (purged) into the processing chamber 201 through the gas supply pipe 520 and the nozzle 420, and is exhausted from the exhaust pipe 231.

[0071] At this time, the APC valve 243 is appropriately adjusted to set the pressure in the processing chamber 201 to, for example, 1 to 1000Pa, preferably 1 to 100Pa, and more preferably a pressure in the range of 10 to 50Pa. It should be noted that in this specification, when a numerical range is recorded as 1 to 1000Pa, for example, it means 1Pa or more and 1000Pa or less. That is, 1Pa and 1000Pa are included in the numerical range. 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 the raw material gas controlled by MFC312 is, for example, set to 10 to 2000sccm, preferably set to 50 to 1000sccm, and more preferably set to a flow rate in the range of 100 to 500sccm. The supply flow rate of the inactive gas controlled by MFC512 is, for example, set to 1 to 30slm, preferably set to 1 to 20slm, and more preferably set to a flow rate in the range of 1 to 10slm. The time for supplying the source gas to the wafer 200 is set in the range of, for example, 1 to 60 seconds, preferably 1 to 20 seconds, and more preferably 2 to 15 seconds.

[0072] The heater 207 heats so that the temperature of the wafer 200 reaches a predetermined temperature within a range of, for example, room temperature to 450°C, preferably 350 to 420°C. When the temperature is less than 350°C, a practical oxidation rate due to the oxidizing gas may not be obtained, and when the temperature is above 420°C, the step coverage of the film forming process may decrease due to thermal decomposition of the raw material gas, etc. By setting the temperature to be above 350°C and below 420°C, a practical oxidation rate can be easily obtained while maintaining the step coverage. The higher the temperature, the greater the deactivation rate of the oxidizing gas (especially O3 gas) used in the oxidizing gas supply step (step S113) described later, and therefore the temperature of the wafer 200 is preferably set to be below 450°C.

[0073] As a raw material gas, for example, a gas containing aluminum (Al) as a predetermined element is supplied into the processing chamber 201 under the above-mentioned conditions, thereby forming an Al-containing layer as the first layer on the outermost surface of the wafer 200. The Al-containing layer may contain carbon (C) and hydrogen (H) contained in the raw material gas in addition to the Al layer. The Al-containing layer is formed by physically adsorbing the raw material gas or chemically adsorbing a substance formed by decomposition of a part of the raw material gas on the outermost surface of the wafer 200, and depositing Al by thermally decomposing the raw material gas. That is, the Al-containing layer may be an adsorption layer (physical adsorption layer, chemical adsorption layer) of a raw material gas or a substance formed by decomposition of a part of the raw material gas, or may be a stack of Al (Al layer).

[0074] In addition, as a raw material gas, for example, an organic Al-containing gas such as trimethylaluminum ((CH3)3Al, TMA) gas, which is a gas containing Al as a prescribed element, can be used. In addition, as an Al-containing gas, a halogen-based Al-containing gas such as aluminum chloride (AlCl3) gas can be used. In addition, a gas containing other metal elements as a prescribed element can be used. For example, as a raw material gas, an organic Hf-containing gas such as tetraethylmethylaminohafnium ([(CH3)(C2H5)N]4Hf, TEMAH) gas, which is a gas containing hafnium (Hf), and a halogen-based Hf-containing gas such as hafnium chloride (HfCl4) gas can be used. In addition, for example, as a raw material gas, an organic Zr-containing gas such as tetraethylmethylaminozirconium ((NCH3C2H5)4, TEMAZ) gas, which is a gas containing zirconium (Zr), and a halogen-based Zr-containing gas such as zirconium chloride (ZrCl4) gas can be used. In addition, as the raw material gas, a gas containing a metal element such as titanium (Ti), tantalum (Ta), molybdenum (Mo), tungsten (W), or a semiconductor element such as silicon (Si) as a predetermined element can be used.

[0075] [Residual Gas Removal Step] (Step S112)

[0076] After the Al-containing layer is formed, the valve 314 is closed to stop the supply of the raw material 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 raw material gas that has not reacted or contributed to the formation of the Al-containing layer remaining in the processing chamber 201 is removed from the processing chamber 201. Valves 514 and 524 are opened to maintain the supply of inert gas to the processing chamber 201. The inert gas acts as a purge gas, which can improve the effect of removing the raw material gas that has not reacted or contributed to the formation of the Al-containing layer remaining in the processing chamber 201 from the processing chamber 201. It should be noted that the inert gas from valves 514 and 524 can flow continuously during the residual gas removal step, or it can be supplied intermittently (pulsed).

[0077] [Oxidation Gas Supply Step] (Step S113)

[0078] After the residual gas in the processing chamber 201 is removed, the valve 324 is opened to allow the oxygen-containing gas as the oxidizing gas (reactive gas) to flow into the gas supply pipe 320. The oxidizing 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 oxidizing gas. At this time, the valve 524 is opened to allow the inactive gas to flow into the gas supply pipe 520. The inactive gas is flow-regulated by the MFC 522, supplied to the processing chamber 201 together with the oxidizing gas, and exhausted from the exhaust pipe 231. At this time, in order to prevent the oxidizing gas from invading the nozzle 410 (preventing backflow), the valve 514 is opened to allow the inactive gas to flow into the gas supply pipe 510. The inactive 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.

[0079] At this time, the APC valve 243 is appropriately adjusted to set the pressure in the processing chamber 201 to, for example, 1 to 1000 Pa, preferably 1 to 100 Pa, and more preferably 10 to 40 Pa. The supply flow rate of the oxidizing gas controlled by the MFC 322 is set to, for example, 5 to 40 slm, preferably 5 to 30 slm, and more preferably 10 to 20 slm. The other processing conditions are the same as those in the above-mentioned raw material gas supply step.

[0080] As the oxidizing gas, oxygen (O2) gas, ozone (O3) gas, plasma-excited O2 (O2 * ) gas, O2 gas + hydrogen (H2) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas and other oxygen (O) containing gases. As the oxidizing gas, one or more of these can be used.

[0081] At this time, the gas flowing into the processing chamber 201 is only the oxidizing gas and the inert gas. The oxidizing 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 first layer, i.e., the Al-containing layer, is oxidized to form an aluminum oxide layer (Al oxide layer) containing Al and O as a metal oxide layer. That is, the Al-containing layer is modified into an Al oxide layer.

[0082] [Residual Gas Removal Step] (Step S114)

[0083] After the Al oxide layer is formed, the valve 324 is closed to stop the supply of the oxidizing gas. At this time, the APC valve 243 is kept open, and the valves 514 and 524 are kept open to supply the inactive gas (purge) into the processing chamber 201. The oxidizing gas and reaction byproducts that have not reacted or contributed to the formation of the Al oxide layer remaining in the processing chamber 201 are removed from the processing chamber 201 through the same processing steps as the residual gas removal step after the raw material gas supply step.

[0084] [Perform the prescribed number of times] (Step S115)

[0085] By sequentially performing the above-mentioned raw gas supply step, residual gas removal step, oxidation gas supply step, and residual gas supply step in a non-simultaneous cycle more than once (predetermined number of times), an oxide film (Al oxide film) containing a predetermined element, i.e., Al, is formed on the wafer 200. The number of cycles can be appropriately selected according to the film thickness required in the oxide film finally formed, and the cycle is preferably repeated multiple times. The thickness (film thickness) of the oxide film is, for example, set to 0.1 to 150 nm, preferably set to 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.

[0086] (Post-Purge·Atmospheric Pressure Restoration) (Steps S121, S122)

[0087] If the film forming process is completed, the valves 514 and 524 are opened, and the inert gas is supplied from the gas supply pipes 310 and 320 to the processing chamber 201, and the gas is exhausted from the exhaust pipe 231. The inert gas acts as a purge gas to remove the gas and reaction byproducts remaining in the processing chamber 201 from the processing chamber 201 (post-purge) (step S121). Then, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery) (step S122).

[0088] (Wafer boat unloading and wafer removal) (steps S123, S124)

[0089] Then, the sealing cover 219 is lowered by the wafer boat elevator 115, the lower end of the manifold 209 is opened, and the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (step S123). Then, the shutter (not shown) is moved, and the lower end opening of the manifold 209 is sealed by the shutter (not shown) via an O-ring (not shown). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is removed from the wafer boat 217 (step S124).

[0090] The inventors of the present application have found that in the above-mentioned oxidation gas supply step (step S113), when the time for supplying oxidation gas to the wafer 200 is short, an oxide film is formed on the wafer 200 in a convex shape (distribution in which the film thickness at the center of the wafer is relatively larger than the film thickness outside the center of the wafer), and by extending the time for supplying oxidation gas to the wafer 200, the oxide film formed on the wafer 200 changes from the convex shape to a concave shape (distribution in which the film thickness at the center of the wafer is relatively smaller than the film thickness outside the center of the wafer). Furthermore, the inventors of the present application have found that, as a result, by controlling the time for supplying oxidation gas to the wafer 200, the film thickness distribution of the oxide film formed on the wafer having a pattern formed on the surface can be controlled, thereby improving the in-plane uniformity of the film thickness.

[0091] Here, the surface area of ​​the wafer with a pattern (i.e., the pattern wafer) is larger than that of the wafer without a pattern (i.e., the bare wafer), so the gas consumption is larger. In addition, in the above-mentioned substrate processing device 10, a plurality of wafers 200 are arranged in multiple layers on the wafer boat 217 at a predetermined interval, and the gas is supplied from the outer peripheral side of the wafer 200 to the inner surface, so in the raw material gas supply step, the oxidizing gas reacts with at least a portion of the Al-containing layer formed on the wafer 200 from the outer peripheral side of the wafer 200.

[0092] When the time for supplying the oxidizing gas to the wafer 200 is short, the oxidizing gas supplied from the outer peripheral side is consumed from the outer peripheral side of the wafer, and cannot be fully oxidized (reacted) to the center of the wafer 200. Therefore, it is presumed that although the oxidizing gas reacts with at least a portion of the Al-containing layer to form an oxide layer, adsorption sites such as OH groups for adsorption of the raw material gas are redundantly formed on the surface of the oxide layer at the center of the wafer that is insufficiently oxidized due to insufficient oxidation, so more raw material gas is adsorbed, and the film thickness at the center of the wafer that is insufficiently oxidized increases compared to the film thickness at the outer peripheral side of the wafer, and an oxide film is formed on the wafer 200 in a convex shape.

[0093] In addition, if the time for supplying the oxidizing gas to the wafer 200 is extended, oxidation continues to occur, and the oxidizing gas supplied from the outer peripheral side oxidizes (reacts) from the outer peripheral side to the center of the wafer. Therefore, it is speculated that when the oxidizing gas reacts with at least a portion of the Al-containing layer to form an oxide layer, no extra adsorption sites such as OH groups are formed, and an oxide film is formed in the center of the wafer in the same manner as on the outer peripheral side of the wafer, and the film thickness of the oxide film is reduced compared to the case of insufficient oxidation. Furthermore, it is speculated that if the oxidation further proceeds and the oxidation in the oxide layer is saturated, the base (interface) of the oxide layer is oxidized, the volume of the interface increases, and the film thickness of the outer peripheral side of the wafer that is oxidized earlier than the center of the wafer increases, and an oxide film is formed on the wafer 200 in a manner that changes from a convex shape to a concave shape. It is speculated that the film increase caused by insufficient oxidation is likely to occur significantly, especially when a raw material gas having a hydrocarbon group (such as an alkyl group, a methyl group, an ethyl group, etc.) is used.

[0094] Therefore, the time for supplying the oxidizing gas to the wafer 200 is selected in such a way that the thickness distribution of the oxide film in the wafer surface becomes a predetermined distribution. By selecting a longer supply time of the oxidizing gas, the thickness distribution of the oxide film in the wafer 200 surface can be adjusted from a convex shape to a concave shape. In addition, by setting the supply time of the oxidizing gas to the time when the film thickness distribution in the surface changes from a convex shape to a substantially uniform shape, and making the time for changing to a concave shape shorter, the film thickness distribution in the surface of the wafer can be made uniform. In addition, by setting the supply time of the oxidizing gas to be shorter than the time when the film thickness distribution in the surface changes to a concave shape, the oxidation of the base (interface) of the oxide film from the periphery of the wafer can be suppressed.

[0095] That is, data associating the oxidation gas supply time with the in-plane thickness distribution of the oxide film is stored in the storage device 121c or the external storage device 123, and the oxidation gas supply time is selected so that the in-plane thickness distribution becomes a predetermined distribution, thereby executing this step.

[0096] In other words, the supply time of the oxidizing gas is selected so that the thickness distribution of the oxide film in the wafer surface becomes a predetermined distribution and the length of the supply time is longer than the supply time of the oxidizing gas when the thickness distribution of the oxide film in the wafer surface 200 becomes a convex shape. In addition, the supply time of the oxidizing gas is selected so that the thickness distribution of the oxide film in the wafer surface becomes a predetermined distribution and the length of the supply time is shorter than the supply time of the oxidizing gas when the thickness distribution of the oxide film in the wafer surface 200 becomes a concave shape. In addition, the length of the supply time of the oxidizing gas is selected so that the thickness distribution of the oxide film in the wafer surface becomes uniform and the length is selected so that the in-plane uniformity of the thickness of the oxide film in the wafer surface 200 becomes, for example, less than 10%. Here, the in-plane uniformity is calculated by (maximum film thickness - minimum film thickness) / average film thickness.

[0097] In addition, based on the predetermined interval between the wafers 200, that is, the wafer spacing, the supply time of the oxidizing gas is selected in such a way that the thickness distribution in the plane of the oxide film becomes a predetermined distribution. The narrower the wafer spacing is, the stronger the convex shape of the film thickness distribution in the plane caused by the supply time of the oxidizing gas is. Therefore, by extending the supply time of the oxidizing gas, the film thickness distribution in the plane can be made close to uniform. That is, the supply time of the oxidizing gas is selected so that the narrower the wafer spacing is, the longer the supply time is. The wafer spacing is, for example, 50 to 3 mm. The larger the wafer spacing is, the more the uniformity of the film thickness in the plane of the wafer can be improved. In order to obtain the effect of being able to control the film thickness distribution in the plane of the wafer by adjusting the oxidizing gas supply time, it is preferably less than 50 mm. In the case of exceeding 50 mm, this effect may not be fully obtained. In addition, when the wafer spacing is less than 3 mm, when the oxidizing gas supply time is extended to make the film thickness distribution in the plane approach a uniform shape from a convex shape, the increase of the oxide film thickness on the outer peripheral side of the wafer may occur before the film thickness on the central side of the wafer decreases. Therefore, the wafer spacing is preferably 3 mm or more.

[0098] In addition, the supply time of the oxidizing gas is selected based on the surface area of ​​the upper surface of the wafer 200 so that the thickness distribution in the plane of the oxide film becomes a predetermined distribution. The larger the surface area of ​​the upper surface of the wafer, the stronger the convex shape of the film thickness distribution in the plane caused by the supply time of the oxidizing gas. Therefore, by extending the supply time of the oxidizing gas, the film thickness distribution in the plane can be made close to uniform. In other words, the supply time of the oxidizing gas is selected so that the larger the surface area of ​​the upper surface of the wafer 200, the longer the supply time.

[0099] (3) Effects of this embodiment

[0100] According to this embodiment, one or more of the following effects can be obtained.

[0101] (a) The in-plane film thickness distribution of an oxide film formed on a substrate can be controlled.

[0102] (b) The in-plane uniformity of the thickness of the oxide film formed on the substrate can be improved.

[0103] (c) By selecting the supply timing of the oxidizing gas in accordance with the in-plane film thickness distribution, productivity can be improved.

[0104] (d) By making the in-plane film thickness distribution uniform, oxidation of the base (interface) of the oxide film can be suppressed.

[0105] <Other embodiments>

[0106] The embodiments of the present invention have been specifically described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

[0107] In the above embodiment, TMA gas is used as the raw material gas containing the predetermined element. However, the present invention is not limited to this. As the raw material gas containing the predetermined element, a gas having a hydrocarbon group such as an alkyl group, a methyl group, or an ethyl group can be used.

[0108] In addition, in the above-mentioned embodiment, an example of forming an AlO film containing Al is used as an example of an oxide film containing a specified element, but it is not limited to this. It can also be appropriately applied when an oxide film such as a silicon oxide (SiO) film, a hafnium oxide (HfO) film, a zirconium oxide (ZrO) film, a titanium oxide (TiO) film, a tantalum oxide (TaO) film, a molybdenum oxide (MoO) film, a tungsten oxide (WO) film, etc. is formed as an oxide film containing a specified element.

[0109] In addition, in the above-mentioned embodiment, an example of supplying gas from the periphery of the chip 200 toward the in-plane (center) is used for explanation, but it is not limited to this. It can also be appropriately applied when gas is supplied from the periphery of the chip 200 to the in-plane (center) of the chip 200 through diffusion.

[0110] It should be noted that the process for substrate processing is preferably prepared separately according to the processing content, and is stored in advance in the storage device 121c via the electrical communication line and the external storage device 123. In addition, when starting the substrate processing, it is preferred that the CPU 121a appropriately selects a suitable process from the multiple processes stored in the storage device 121c according to the processing content. In this way, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility by one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and the substrate processing can be started quickly.

[0111] The above process is not limited to the case of newly making, and can be prepared by, for example, changing an existing process already installed in a substrate processing device. When changing a process, the changed process can be installed in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing process already installed in the substrate processing device.

[0112] When the above-mentioned substrate processing apparatus is used, a film forming process can be performed with the same processing steps and processing conditions as those in the above-mentioned embodiment, and the same effects as those in the above-mentioned embodiment can be obtained.

[0113] [Example 1]

[0114] In this embodiment, use Figure 1 The substrate processing device 10 shown in FIG. 1 is on a wafer boat 217. Figure 5As shown, a monitoring wafer 300 is placed between the wafers 200 with the patterned surface at the bottom. Figure 4 The supply time of the oxidizing gas in the oxidizing gas supply step (step S113) in the order shown is controlled, and the in-plane film thickness distribution of the oxide film formed on the upper and lower surfaces of the monitoring wafer 300 is evaluated. The surface of the wafer 200 with a pattern formed has a surface area 50 times that of the bare wafer. The film thickness of the oxide film formed on the upper surface of the monitoring wafer 300, that is, the surface 300A opposite to the surface of the wafer 200 with a pattern formed (hereinafter, referred to as the pattern surface 300A), is set to be equal to the film thickness of the oxide film formed on the wafer with a pattern formed, and the film thickness of the oxide film formed on the lower surface of the monitoring wafer 300, that is, the surface 300B opposite to the surface of the wafer 200 without a pattern formed (hereinafter, referred to as the bare surface 300B) is set to be equal to the film thickness of the oxide film formed on the bare wafer without a pattern formed, thereby performing the evaluation.

[0115] First, the relationship between the surface area of ​​the wafer, the distance between the wafers, the oxidizing gas supply time and the in-plane film thickness distribution was evaluated. It should be noted that in this embodiment, as an example, TMA gas is used as the raw material gas and O3 gas is used as the oxidizing gas.

[0116] Figure 6 (A) is a diagram showing the relationship between the film thickness distribution of the oxide film formed on the bare surface 300B and the supply time of the oxidizing gas when the interval P between wafers is the first distance (16 mm), Figure 6 (B) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the pattern surface 300A and the supply time of the oxidizing gas when the interval P between the wafers is the first distance. Figure 7 (A) is a diagram showing the relationship between the film thickness distribution of the oxide film formed on the bare surface 300B and the supply time of the oxidizing gas when the interval P between the wafers is the second distance (8 mm), Figure 7 (B) is a graph showing the relationship between the film thickness distribution of the oxide film formed on the pattern surface 300A and the supply time of the oxidizing gas when the pitch P between wafers is the second distance.

[0117] like Figure 6 (A) and Figure 7 As shown in (A), for the oxide film formed on the bare surface 300B, the film thickness distribution in the plane is substantially uniform. If the oxidizing gas supply time is extended, the film thickness increases while the film thickness distribution in the plane is substantially uniform.

[0118] In contrast, Figure 6As shown in (B), for the oxide film formed on the pattern surface 300A when the wafer spacing is the first distance, when the supply time of the oxidizing gas is 20 seconds, the result is a convex film thickness distribution in the center of the wafer, and when the supply time of the oxidizing gas is 50 seconds, the film thickness in the center of the wafer decreases, and the film thickness distribution in the surface becomes a nearly uniform distribution. In addition, if the supply time of the oxidizing gas is further extended, the film thickness on the outer peripheral side of the wafer increases and becomes a concave film thickness distribution.

[0119] in addition, Figure 7 As shown in (B), for the oxide film formed on the pattern surface 300A when the wafer spacing is the second distance, when the supply time of the oxidizing gas is 20 seconds, the film thickness distribution becomes convex, when the supply time of the oxidizing gas is 50 seconds, the film thickness at the center of the wafer decreases, and when the supply time of the oxidizing gas is 100 seconds, the film thickness at the center of the wafer further decreases, and the film thickness distribution in the plane is close to uniform. In addition, if the supply time of the oxidizing gas is further extended, the film thickness on the outer peripheral side of the wafer increases, and the film thickness distribution becomes concave.

[0120] That is, it was confirmed that the in-plane film thickness distribution of the formed oxide film differs depending on the surface area of ​​the upper surface of the wafer and the distance between the wafers. In addition, it was confirmed that the larger the surface area of ​​the upper surface of the wafer, the more the in-plane film thickness distribution can be changed from a convex shape to a distribution close to uniform by extending the supply time of the oxidizing gas, and the shape can be changed to a concave shape by further extending the supply time of the oxidizing gas. In addition, it was confirmed that the narrower the distance between the wafers, the more the in-plane film thickness distribution can be changed from a convex shape to a distribution close to uniform by extending the supply time of the oxidizing gas, and the shape can be changed to a concave shape by further extending the supply time of the oxidizing gas.

[0121] Next, the change in film thickness at the center of each of the bare surface 300B and the pattern surface 300A when the wafer pitch is the second distance is compared with the change in film thickness at the center of each of the bare surface 300B and the pattern surface 300A when the wafer pitch is the first distance. Figure 8 1 is a diagram showing the relationship between the film thickness of the oxide film formed at the center of each of the bare surface 300B and the pattern surface 300A, the supply time of the oxidizing gas, and the wafer pitch P.

[0122] like Figure 8 As shown in the figure, it is confirmed that at the center of the bare surface 300B, the film thickness of the oxide film is increased by extending the supply time of the oxidizing gas regardless of whether the wafer spacing is the second distance or the first distance. In addition, the film thickness increase when the wafer spacing is the second distance is smaller than the film thickness increase when the wafer spacing is the first distance.

[0123] On the other hand, it was confirmed that at the center of the pattern surface 300A, the thickness of the oxide film was reduced by extending the supply time of the oxidizing gas regardless of whether the wafer spacing was the second distance or the first distance. In addition, the film thickness at the center of the wafer when the wafer spacing was the second distance was greater than the film thickness at the center of the wafer when the wafer spacing was the first distance. If the supply time of the oxidizing gas was extended to about 150 seconds, the film thickness at the center of the wafer when the wafer spacing was the first distance with a wide wafer spacing became greater than the film thickness at the center of the wafer when the wafer spacing was the second distance. That is, it was confirmed that when the wafer spacing was wide, the film thickness increased due to the progress of oxidation.

[0124] That is, it was confirmed that the center of the chip with a pattern formed thereon has a convex shape due to insufficient oxidation. If oxidation is carried out by extending the supply time of the oxidizing gas, the film thickness at the center of the chip decreases. However, if oxidation is further carried out by extending the supply time of the oxidizing gas, the film thickness increases.

[0125] Next, the relationship between the film thickness projection (0-150) from the center of the wafer to the position of 150 mm (wafer end), the film thickness projection (0-100) from the center of the wafer to the position of 100 mm, and the supply time of the oxidizing gas is compared. Fig. 9 It is a graph showing the relationship between the film thickness projection from the center of the wafer to 150 mm, the film thickness projection from the center of the wafer to 100 mm, and the supply time of the oxidizing gas.

[0126] like Fig. 9 As shown in FIG. 1 , the difference in film thickness from the center to the end of the wafer, i.e., the film thickness convexity (0-150), is about 0.01% when the supply time of the oxidizing gas is 20 seconds. Furthermore, if the supply time of the oxidizing gas is extended, the film thickness convexity becomes smaller. When the supply time of the oxidizing gas is 100 seconds, the film thickness convexity becomes close to 0. Furthermore, when the supply time of the oxidizing gas is 150 seconds, the film thickness convexity becomes

[0127] In addition, the difference in film thickness from the center of the wafer to the position of 100 mm, that is, the film thickness convexity (0-100), is about 0.1% when the supply time of the oxidizing gas is 20 seconds. Furthermore, if the supply time of the oxidizing gas is prolonged, the film thickness convexity becomes smaller. When the supply time of the oxidizing gas is 150 seconds, the film thickness convexity becomes approximately

[0128] That is, it was confirmed that the film thickness distribution of the oxide film changes from a convex shape to a concave shape by extending the supply time of the oxidizing gas.

[0129] <Preferred Embodiments of the Invention>

[0130] Hereinafter, preferred embodiments of the present invention will be described.

[0131] (Note 1)

[0132] According to one embodiment of the present invention, there is provided a method for manufacturing a semiconductor device, wherein an oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times:

[0133] (a) a step of supplying a raw material gas containing a predetermined element from the periphery of a substrate having a pattern formed on its surface into a surface of the substrate, thereby forming a first layer containing the predetermined element on the surface;

[0134] (b) supplying an oxidizing gas from the outer periphery of the substrate into the surface of the substrate to oxidize the first layer, thereby forming an oxide layer containing the predetermined element on the surface of the substrate,

[0135] In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a predetermined distribution.

[0136] (Note 2)

[0137] The method as described in Supplementary Note 1 is preferably such that in (b), the supply time of the oxidizing gas is selected to be longer, thereby adjusting the thickness distribution of the oxide film in the substrate surface from a convex shape to a concave shape.

[0138] (Note 3)

[0139] As described in Supplementary Note 1, the supply time of the oxidizing gas is preferably selected so as to be longer than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes convex.

[0140] (Note 4)

[0141] As described in Supplementary Note 1, the length of the supply time is preferably selected to be a length that makes the thickness distribution of the oxide film in the surface of the substrate uniform.

[0142] (Note 5)

[0143] As described in Supplementary Note 4, the length of the supply time is preferably selected to be a length that allows the thickness uniformity of the oxide film within the substrate surface to reach a predetermined value or less.

[0144] (Note 6)

[0145] As described in Supplementary Note 1, the supply time of the oxidizing gas is preferably selected so as to be shorter than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes concave.

[0146] (Note 7)

[0147] In the method according to Supplementary Note 1, preferably, in (b), the oxidizing gas is supplied from the outer periphery to the center of the substrate.

[0148] (Note 8)

[0149] In the method according to Supplementary Note 7, preferably, in (b), the oxidizing gas is supplied from a supply port arranged at the outer periphery of the substrate toward the center of the substrate.

[0150] (Note 9)

[0151] As described in Supplementary Note 7, in (b), it is preferred that the oxidizing gas is supplied into the surface of the substrate by diffusion from the periphery of the substrate.

[0152] (Note 10)

[0153] As described in Supplementary Note 1, it is preferred that the substrate is composed of a plurality of substrates arranged in multiple layers at predetermined intervals.

[0154] (Note 11)

[0155] As described in Supplementary Note 10, it is preferred that the supply time of the oxidizing gas is selected based on the predetermined interval so that the thickness distribution of the oxide film within the substrate surface becomes a predetermined distribution.

[0156] (Note 12)

[0157] As described in Supplementary Note 11, it is preferable that the supply time of the oxidizing gas be selected such that the narrower the predetermined interval, the longer the supply time.

[0158] (Note 13)

[0159] As described in Supplementary Note 1, the supply time of the oxidizing gas is selected based on the surface area of ​​the upper surface of the substrate so that the thickness distribution of the oxide film within the surface of the substrate becomes a predetermined distribution.

[0160] (Note 14)

[0161] As described in Supplementary Note 13, the supply time of the oxidizing gas is selected such that the supply time becomes longer as the surface area of ​​the upper surface of the substrate becomes larger.

[0162] (Note 15)

[0163] According to another embodiment of the present invention, a substrate processing apparatus is provided, which comprises: a processing chamber; a raw material gas supply system, which supplies a raw material gas containing a specified element from the outer periphery of the substrate to the inner surface of the substrate with respect to a substrate having a pattern formed on the surface in the aforementioned processing chamber; an oxidizing gas supply system, which supplies an oxidizing gas from the outer periphery of the substrate to the inner surface of the substrate in the aforementioned processing chamber; and a control unit, which is configured to be able to control the raw material gas supply system and the oxidizing gas supply system so as to perform each treatment (each process) in Note 1 on the aforementioned substrate in the aforementioned processing chamber.

[0164] (Note 16)

[0165] According to still another aspect of the present invention, there is provided a program for causing a substrate processing apparatus to execute the steps (processes) in Supplementary Note 1 by a computer, or a computer-readable recording medium recording the program.

Claims

1. A substrate processing method, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film within the substrate surface becomes a specified distribution, wherein the supply time of the oxidizing gas is selected in a manner that becomes longer, thereby adjusting the thickness distribution of the oxide film within the substrate surface from a convex shape to a concave shape.

2. The substrate processing method according to claim 1, wherein: The length of the supply time is selected so that the thickness distribution of the oxide film in the substrate surface becomes uniform.

3. The substrate processing method according to claim 2, wherein: The length of the supply time is selected so that the in-plane uniformity of the thickness of the oxide film in the substrate surface becomes equal to or less than a predetermined value.

4. The substrate processing method according to claim 1, wherein: In (b), the oxidizing gas is supplied from the outer periphery to the center of the substrate.

5. The substrate processing method according to claim 4, wherein: In (b), the oxidizing gas is supplied toward the center of the substrate from a supply port arranged at the outer periphery of the substrate.

6. The substrate processing method according to claim 4, wherein: In (b), the oxidizing gas is supplied into the surface of the substrate by diffusion from the outer periphery of the substrate.

7. The substrate processing method according to claim 1, wherein: The substrate is composed of a plurality of substrates arranged in multiple layers at predetermined intervals.

8. The substrate processing method according to claim 7, wherein: Based on the predetermined interval, the supply time of the oxidizing gas is selected so that the thickness distribution of the oxide film in the substrate surface becomes a predetermined distribution.

9. The substrate processing method according to claim 7, wherein: The supply time of the oxidizing gas is selected such that the supply time becomes longer as the predetermined interval becomes narrower.

10. The substrate processing method according to claim 1, wherein: The supply time of the oxidizing gas is selected based on the surface area of ​​the upper surface of the substrate so that the thickness distribution of the oxide film within the substrate surface becomes a predetermined distribution.

11. The substrate processing method according to claim 10, wherein: The supply time of the oxidizing gas is selected such that the supply time becomes longer as the surface area of ​​the upper surface of the substrate becomes larger.

12. A substrate processing method, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the substrate surface becomes a specified distribution, wherein the thickness distribution of the oxide film in the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected in a manner that is longer than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes a convex shape.

13. A substrate processing method, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the substrate surface becomes a specified distribution, wherein the thickness distribution of the oxide film in the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected in a manner that is shorter than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes concave.

14. A substrate processing device comprising: Processing room; a raw material gas supply system for supplying a raw material gas containing a predetermined element from the periphery of the substrate to the inside of the surface of the substrate with a pattern formed on the surface in the processing chamber; an oxidizing gas supply system for supplying an oxidizing gas from an outer periphery of the substrate to an inner surface of the substrate with respect to the substrate in the processing chamber; and A control unit configured to control the raw material gas supply system and the oxidizing gas supply system to perform the following process on the substrate in the processing chamber, that is, to form an oxide film containing the specified element on the substrate by performing the following (a) and (b) non-simultaneously for a specified number of times: (a) supplying the raw material gas to form a first layer including the predetermined element on the surface of the substrate; (b) supplying the oxidizing gas to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a predetermined distribution, wherein: By selecting the supply time of the oxidizing gas to be longer, the thickness distribution of the oxide film in the substrate surface is adjusted from a convex shape to a concave shape.

15. A substrate processing device comprising: Processing room; a raw material gas supply system for supplying a raw material gas containing a predetermined element from the periphery of the substrate to the inside of the surface of the substrate with a pattern formed on the surface in the processing chamber; an oxidizing gas supply system for supplying an oxidizing gas from an outer periphery of the substrate to an inner surface of the substrate with respect to the substrate in the processing chamber; and A control unit configured to control the raw material gas supply system and the oxidizing gas supply system to perform the following process on the substrate in the processing chamber, that is, to form an oxide film containing the specified element on the substrate by performing the following (a) and (b) non-simultaneously for a specified number of times: (a) supplying the raw material gas to form a first layer including the predetermined element on the surface of the substrate; (b) supplying the oxidizing gas to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a predetermined distribution, wherein: The thickness distribution of the oxide film within the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected so that the thickness distribution of the oxide film within the substrate surface becomes convex compared to the supply time of the oxidizing gas.

16. A substrate processing apparatus comprising: Processing room; a raw material gas supply system for supplying a raw material gas containing a predetermined element from the outer periphery of the substrate to the inside of the surface of the substrate with respect to the substrate having a pattern formed on the surface in the processing chamber; an oxidizing gas supply system for supplying an oxidizing gas from an outer periphery of the substrate to an inner surface of the substrate with respect to the substrate in the processing chamber; and A control unit configured to control the raw material gas supply system and the oxidizing gas supply system to perform the following process on the substrate in the processing chamber, that is, to form an oxide film containing the specified element on the substrate by performing the following (a) and (b) non-simultaneously for a specified number of times: (a) supplying the raw material gas to form a first layer including the predetermined element on the surface of the substrate; (b) supplying the oxidizing gas to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the surface of the substrate becomes a predetermined distribution, wherein: The thickness distribution of the oxide film within the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected so that it becomes shorter than the supply time of the oxidizing gas at which the thickness distribution of the oxide film within the substrate surface becomes concave.

17. A computer-readable recording medium having a program recorded thereon, the program causing a substrate processing apparatus to execute the following steps through a computer, namely, forming an oxide film containing a predetermined element on a substrate by performing the following (a) and (b) non-simultaneously a predetermined number of times: (a) supplying a raw material gas containing a predetermined element from the periphery of the substrate into the surface of the substrate with a pattern formed on the surface of the substrate, thereby forming a first layer containing the predetermined element on the surface of the substrate; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface; In (b), a step of selecting a supply time of the oxidizing gas to the substrate so that the thickness distribution of the oxide film within the surface of the substrate becomes a predetermined distribution, wherein: By selecting the supply time of the oxidizing gas to be longer, the thickness distribution of the oxide film in the substrate surface is adjusted from a convex shape to a concave shape.

18. A computer-readable recording medium having a program recorded thereon, the program causing a substrate processing apparatus to execute the following steps through a computer, namely, forming an oxide film containing a predetermined element on a substrate by performing the following (a) and (b) non-simultaneously a predetermined number of times: (a) supplying a raw material gas containing a predetermined element from the periphery of the substrate into the surface of the substrate with a pattern formed on the surface of the substrate, thereby forming a first layer containing the predetermined element on the surface of the substrate; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface; In (b), a step of selecting a supply time of the oxidizing gas to the substrate so that the thickness distribution of the oxide film within the surface of the substrate becomes a predetermined distribution, wherein: The thickness distribution of the oxide film within the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected so that the thickness distribution of the oxide film within the substrate surface becomes convex compared to the supply time of the oxidizing gas.

19. A computer-readable recording medium having a program recorded thereon, the program causing a substrate processing apparatus to execute the following steps through a computer, namely, forming an oxide film containing a predetermined element on a substrate by performing the following (a) and (b) non-simultaneously a predetermined number of times: (a) supplying a raw material gas containing a predetermined element from the periphery of the substrate into the surface of the substrate with a pattern formed on the surface of the substrate, thereby forming a first layer containing the predetermined element on the surface of the substrate; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface; In (b), a step of selecting a supply time of the oxidizing gas to the substrate so that the thickness distribution of the oxide film within the surface of the substrate becomes a predetermined distribution, wherein: The thickness distribution of the oxide film within the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected so that it becomes shorter than the supply time of the oxidizing gas at which the thickness distribution of the oxide film within the substrate surface becomes concave.

20. A method for manufacturing a semiconductor device, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film within the substrate surface becomes a specified distribution, wherein the supply time of the oxidizing gas is selected in a manner that becomes longer, thereby adjusting the thickness distribution of the oxide film within the substrate surface from a convex shape to a concave shape.

21. A method for manufacturing a semiconductor device, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the substrate surface becomes a specified distribution, wherein the thickness distribution of the oxide film in the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected in a manner that is longer than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes a convex shape.

22. A method for manufacturing a semiconductor device, wherein: An oxide film containing a predetermined element is formed on a substrate by performing the following (a) and (b) non-simultaneously for a predetermined number of times: (a) a step of supplying a raw material gas containing the predetermined element from the periphery of the substrate into the surface of the substrate, with respect to the substrate having a pattern formed on the surface, thereby forming a first layer containing the predetermined element on the surface; (b) supplying an oxidizing gas from the periphery of the substrate into the surface of the substrate to oxidize the first layer and form an oxide layer containing the predetermined element on the surface of the substrate, In (b), the supply time of the oxidizing gas to the substrate is selected so that the thickness distribution of the oxide film in the substrate surface becomes a specified distribution, wherein the thickness distribution of the oxide film in the substrate surface changes from a convex shape to a concave shape as the supply time of the oxidizing gas becomes longer, and the supply time is selected in a manner that is shorter than the supply time of the oxidizing gas at which the thickness distribution of the oxide film in the substrate surface becomes concave.

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