Semiconductor device manufacturing method, program and substrate processing device

Abstract

The present invention relates to a method for manufacturing a semiconductor device, a program and a substrate processing apparatus. The method can improve the characteristics of a metal-containing film. The method comprises: (a) accommodating a substrate in a processing container, (b) supplying a gas containing an organic ligand to the substrate, (c) supplying a metal-containing gas to the substrate, and (d) supplying a first reducing gas to the substrate, and after (b), performing (c) and (d) respectively one or more times to form a metal-containing film on the substrate.

Description

Technical Field

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

[0002] As a word line of a NAND flash memory or DRAM having a three-dimensional structure, for example, a low-resistance tungsten (W) film is used. In addition, between the W film and the insulating film, for example, a titanium nitride (TiN) film is used as a barrier film (for example, see Patent Documents 1 and 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-66263

[0006] Patent Document 2: International Publication No. 2019 / 058608 Pamphlet Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, the buried width of the groove for forming the W film becomes fine, and if the TiN film is not flat, the volume of the W film decreases, making it difficult to reduce the resistance of the W film.

[0009] An object of the present invention is to provide a technology capable of improving the characteristics of a metal-containing film.

[0010] Means for solving problems

[0011] According to one aspect of the present invention, the following technology is provided, which includes:

[0012] (a) a step of placing a substrate in a processing container;

[0013] (b) supplying a gas containing an organic ligand to the substrate;

[0014] (c) supplying a metal-containing gas to the substrate; and

[0015] (d) supplying a first reducing gas to the substrate,

[0016] The technique includes the step of performing (c) and (d) one or more times respectively after (b) to form a metal-containing film on the substrate.

[0017] Effects of the Invention

[0018] According to the present invention, the characteristics of the metal-containing film can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic longitudinal sectional view showing a vertical processing furnace of a substrate processing apparatus according to one embodiment of the present invention.

[0020] Figure 2 for Figure 1 AA schematic transverse cross-sectional view.

[0021] Figure 3 This is a schematic diagram of the configuration of a controller of a substrate processing apparatus according to one embodiment of the present invention, and is a diagram showing a control system of the controller in the form of a block diagram.

[0022] Figure 4 A diagram showing a substrate processing procedure in one embodiment of the present invention.

[0023] Figure 5 middle Figure 5 (A)~ Figure 5 (C) is used to illustrate Figure 4 Schematic diagram of the state of the substrate surface during the substrate processing sequence shown.

[0024] Figure 6 middle Figure 6 (A) shows the use of Figure 4 FIG. 1 is a TEM image of a TiN film surface formed on a substrate by the substrate processing sequence shown in FIG. Figure 6 (B) is a diagram showing a TEM image of the surface of a TiN film formed on a substrate by the substrate processing sequence in the comparative example.

[0025] Figure 7 A diagram showing a modified example of a substrate processing sequence in one embodiment of the present invention.

[0026] Figure 8 A diagram showing a modified example of a substrate processing sequence in one embodiment of the present invention.

[0027] Fig. 9 middle Fig. 9 (A)~ Fig. 9 (D) is used to illustrate Figure 8 Schematic diagram of the state of the substrate surface during the substrate processing sequence shown.

[0028] Fig.10 A diagram showing a modified example of a substrate processing sequence in one embodiment of the present invention.

[0029] Fig.11 A diagram showing a modified example of a substrate processing sequence in one embodiment of the present invention.

[0030] Fig.12 A diagram showing a modified example of a substrate processing sequence in one embodiment of the present invention.

[0031] Fig.13 middle Fig.13 (A) and Fig.13 (B) is a schematic longitudinal sectional view showing a processing furnace of a substrate processing apparatus according to another embodiment of the present invention.

[0032] Fig.14 The figures show for comparison TEM images of TiN films formed on the substrates of samples 1 to 4 using different substrate processing sequences.

[0033] Description of Reference Numerals

[0034] 10 Substrate processing device

[0035] 121 Controller

[0036] 200 Wafer (substrate)

[0037] 201 Processing Room DETAILED DESCRIPTION

[0038] Below, refer to Figures 1 to 5 It should be noted that the drawings used in the following description are schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings are not necessarily consistent with the actual situation. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings are not necessarily consistent.

[0039] (1) Configuration of substrate processing apparatus

[0040] The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate.

[0041] On the inner side of the heater 207, an outer tube 203 constituting a processing container is arranged concentrically with the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) and silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (inlet flange) 209 is arranged concentrically with the outer 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. An O-ring 220a as a sealing member is provided between the upper end of the manifold 209 and the outer tube 203. The manifold 209 is supported by the heater base, so that the outer tube 203 is installed vertically.

[0042] An inner tube 204 constituting a processing container is disposed inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. The processing container is mainly composed of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow portion of the processing container (inside the inner tube 204).

[0043] The processing chamber 201 is configured to accommodate wafers 200 as substrates arranged in multiple layers in a horizontal posture in the vertical direction using a wafer boat 217 to be described later.

[0044] In the processing chamber 201, nozzles 410, 420, 430 are provided to penetrate the side wall of the manifold 209 and the inner tube 204. Gas supply pipes 310, 320, 330 are connected to the nozzles 410, 420, 430, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned form.

[0045] Mass flow controllers (MFCs) 312, 322, 332 as flow controllers (flow control units) are provided in order from the upstream side, respectively, on the gas supply pipes 310, 320, 330. In addition, valves 314, 324, 334 as opening and closing valves are provided in the gas supply pipes 310, 320, 330, respectively. Gas supply pipes 510, 520, 530 for supplying inert gas are connected to the downstream side of the valves 314, 324, 334 of the gas supply pipes 310, 320, 330, respectively. MFCs 512, 522, 532 as flow controllers (flow control units) and valves 514, 524, 534 as opening and closing valves are provided in order from the upstream side, respectively, on the gas supply pipes 510, 520, 530, respectively.

[0046] Nozzles 410, 420, 430 are connected to the front ends of the gas supply pipes 310, 320, 330, respectively. The nozzles 410, 420, 430 are configured as L-shaped nozzles, and their horizontal portions are provided to penetrate the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, 430 are provided inside the preliminary chamber 201a having a channel shape (groove shape) formed so as to protrude radially outward of the inner tube 204 and extend in the vertical direction, and are provided in the preliminary chamber 201a so as to face upward (above the arrangement direction of the wafers 200) along the inner wall of the inner tube 204.

[0047] The nozzles 410, 420, 430 are arranged in a manner extending from the lower region of the processing chamber 201 to the upper region of the processing chamber 201, and a plurality of gas supply holes 410a, 420a, 430a are respectively arranged at positions opposite to the wafer 200. Thus, the processing gas is respectively supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430. The gas supply holes 410a, 420a, 430a are arranged in a plurality in the range from the lower part to the upper part of the inner tube 204, each having the same opening area, and are arranged at the same opening pitch. However, the gas supply holes 410a, 420a, 430a are not limited to the above manner. For example, the opening area can be gradually increased from the lower part to the upper part of the inner tube 204. Thus, the flow rate of the gas supplied from the gas supply holes 410a, 420a, 430a can be made more uniform.

[0048] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in a plurality of height positions from the lower part to the upper part of the wafer boat 217 described later. Therefore, the processing gas supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 into the processing chamber 201 is supplied to the entire area of ​​the wafers 200 accommodated from the lower part to the upper part of the wafer boat 217. The nozzles 410, 420, 430 may be provided in a manner extending from the lower area to the upper area of ​​the processing chamber 201, but are preferably provided in a manner extending to the vicinity of the top of the wafer boat 217.

[0049] As a processing gas, a metal-containing gas is supplied from a gas supply pipe 310 into the processing chamber 201 via an MFC 312 , a valve 314 , and a nozzle 410 .

[0050] As the processing gas, a gas containing an organic ligand, that is, an organic ligand-containing gas is supplied from a gas supply pipe 320 into the processing chamber 201 via an MFC 322 , a valve 324 , and a nozzle 420 .

[0051] As the processing gas, a reducing gas is supplied from the gas supply pipe 330 into the processing chamber 201 via the MFC 332 , the valve 334 , and the nozzle 430 .

[0052] As an inert gas, nitrogen (N2) gas, for example, is supplied from gas supply pipes 510, 520, 530 into the processing chamber 201 via MFCs 512, 522, 532, valves 514, 524, 534, and nozzles 410, 420, 430, respectively. Hereinafter, an example in which N2 gas is used as the inert gas will be described, but as the inert gas, in addition to N2 gas, for example, a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas may also be used.

[0053] The processing gas supply system is mainly composed of gas supply pipes 310, 320, 330, MFC312, 322, 332, valves 314, 324, 334, and nozzles 410, 420, 430, but only nozzles 410, 420, 430 can also be considered as the processing gas supply system. The processing gas supply system can also be simply referred to as the gas supply system. When the metal-containing gas flows out from the gas supply pipe 310, the metal-containing gas supply system is mainly composed of the gas supply pipe 310, MFC312, and valve 314, and the nozzle 410 can also be considered as being included in the metal-containing gas supply system. In addition, when the gas containing organic ligands flows out from the gas supply pipe 320, the organic ligand-containing gas supply system is mainly composed of the gas supply pipe 320, MFC322, and valve 324, but the nozzle 420 can also be considered as being included in the organic ligand-containing gas supply system. In addition, when the reducing gas flows out from the gas supply pipe 330, the reducing gas supply system is mainly composed of the gas supply pipe 330, MFC332, and valve 334, but the nozzle 430 can also be considered as being included in the reducing gas supply system. When the N-containing gas is supplied from the gas supply pipe 330 as the reducing gas, the reducing gas supply system can also be called the N-containing gas supply system. In addition, the inactive gas supply system is mainly composed of the gas supply pipes 510, 520, 530, MFC512, 522, 532, and valves 514, 524, 534.

[0054] In the gas supply method of this embodiment, the gas is transported through the nozzles 410, 420, and 430 disposed in the preparatory chamber 201a in the annular longitudinal space defined by the inner wall of the inner tube 204 and the ends of the plurality of wafers 200. Then, the gas is ejected into the inner tube 204 from the plurality of gas supply holes 410a, 420a, and 430a provided at positions facing the wafers of the nozzles 410, 420, and 430. More specifically, the processing gas and the like are ejected in a direction parallel to the surface of the wafer 200 by the gas supply holes 410a of the nozzle 410, the gas supply holes 420a of the nozzle 420, and the gas supply holes 430a of the nozzle 430.

[0055] The exhaust hole (exhaust port) 204a is a through hole formed at a position opposite to the nozzles 410, 420, 430 on the side wall of the inner tube 204, and is, for example, a slit-shaped through hole that is elongated in the vertical direction. The gas supplied from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 into the processing chamber 201 and flowing on the surface of the wafer 200 flows into the exhaust path 206 formed by the gap formed between the inner tube 204 and the outer tube 203 through the exhaust hole 204a. Then, the gas flowing into the exhaust path 206 flows in the exhaust pipe 231 and is exhausted to the outside of the processing furnace 202.

[0056] The exhaust hole 204a is provided at a position opposite to the plurality of wafers 200, and the gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafers 200 in the processing chamber 201 flows in the horizontal direction and then flows into the exhaust path 206 through the exhaust hole 204a. The exhaust hole 204a is not limited to being a slit-shaped through hole, and may be composed of a plurality of holes.

[0057] An exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is provided on the manifold 209. On the exhaust pipe 231, connected in sequence from the upstream side are: a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 as a vacuum exhaust device. For the APC valve 243, by opening and closing the valve while the vacuum pump 246 is in operation, the vacuum exhaust in the processing chamber 201 and the vacuum exhaust stop can be performed. In addition, by adjusting the valve opening 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 hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243 and the pressure sensor 245. The vacuum pump 246 can be considered to be included in the exhaust system.

[0058] A sealing cover 219 as a furnace port cover that can hermetically seal 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 made of a metal such as SUS and is formed in a disc shape. An O-ring 220b as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 that rotates the wafer boat 217 that accommodates the wafer 200 is provided on the opposite side of the sealing cover 219 from the processing chamber 201. 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 raised and lowered in the vertical direction by a boat elevator 115 as an elevating mechanism vertically provided outside the outer tube 203. The boat elevator 115 is configured to be able 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 system) that transports the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

[0059] The wafer boat 217 as a substrate support is configured to arrange a plurality of wafers 200 (for example, 25 to 200 wafers) in a horizontal position and at intervals in the vertical direction in a state where the centers are aligned with each other. 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 218 composed of, for example, a heat-resistant material such as quartz or SiC is supported in a horizontal position in multiple layers (not shown). With such a configuration, the heat from the heater 207 is not easily transferred to the sealing cover 219 side. However, the present embodiment is not limited to the above method. For example, instead of providing the heat insulation plate 218 at the lower part of the wafer boat 217, a heat insulation cylinder composed of a heat-resistant material such as quartz or SiC and in the form of a cylindrical member may be provided.

[0060] like Figure 2 As shown, a temperature sensor 263 as a temperature detector is provided in the inner tube 204, and the amount of current supplied 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 L-shaped like the nozzles 410, 420, and 430, and is provided along the inner wall of the inner tube 204.

[0061] like Figure 3 As shown, the controller 121 as a control unit (control means) is configured in the form of 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. An input / output device 122 configured in the form of, for example, a touch panel is connected to the controller 121.

[0062] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. In the storage device 121c, the following are stored in a readable manner: a control program for controlling the operation of the substrate processing device; a process that records the steps, conditions, etc. of the manufacturing method of the semiconductor device described later, etc. The process is a combination of the controller 121 to execute each process (step) in the manufacturing method of the semiconductor device described later and to obtain a specified result, and it functions as a program. Hereinafter, the above-mentioned process, control program, etc. are also collectively referred to as programs. In this specification, when the term "program" is used, sometimes only the process is included alone, sometimes only the control program is included alone, or sometimes a combination of the process and the control program is included. RAM121b is constructed in the form of a storage area (working area) to temporarily hold programs, data, etc. read by CPU121a.

[0063] The I / O port 121d is connected to the above-mentioned MFC312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, wafer boat elevator 115, etc.

[0064] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in accordance with an 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 recipe, flow rate adjustment operations of various gases by the MFCs 312, 322, 332, 512, 522, 532, opening and closing operations of the valves 314, 324, 334, 514, 524, 534, opening and closing operations of the APC valve 243 and pressure adjustment operations by the APC valve 243 using the pressure sensor 245, temperature adjustment operations of the heater 207 using the temperature sensor 263, start and stop of the vacuum pump 246, rotation of the wafer boat 217 and rotation speed adjustment operations by the rotation mechanism 267, lifting and lowering operations of the wafer boat 217 by the wafer boat elevator 115, and storage operations of the wafers 200 in the wafer boat 217.

[0065] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (such as 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, a memory card, etc.) 123 in a computer. The storage device 121c and the external storage device 123 are constructed in the form of a computer-readable recording medium. Hereinafter, they are also collectively referred to as recording media. In this specification, the recording medium sometimes includes only the storage device 121c alone, sometimes includes only the external storage device 123 alone, or sometimes includes both. Providing the program to the computer can be done without using the external storage device 123, but using communication means such as the Internet and dedicated lines.

[0066] (2) Substrate processing step

[0067] As one example of a process for manufacturing a semiconductor device, a TiN film as a metal-containing film is formed on a wafer 200 using Figure 4 and Figure 5 The process of forming a TiN film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 121 .

[0068] In the substrate processing step (semiconductor device manufacturing step) using this embodiment, the following steps are included:

[0069] (a) a step of placing the wafer 200 in a processing container,

[0070] (b) a step of supplying a gas containing an organic ligand to the wafer 200,

[0071] (c) a step of supplying a metal-containing gas to the wafer 200,

[0072] (d) a step of supplying a first reducing gas to the wafer 200,

[0073] After (b), (c) and (d) are each performed one or more times to form a metal-containing film on the wafer 200 .

[0074] When the term "wafer" is used in this specification, it may mean "the wafer itself" or "a laminate of a wafer and a predetermined layer, film, etc. formed on the surface thereof". When the term "surface of a wafer" is used in this specification, it may mean "the surface of the wafer itself" or "the surface of a predetermined layer, film, etc. formed on the wafer". When the term "substrate" is used in this specification, it has the same meaning as when the term "wafer" is used.

[0075] (Wafer loading)

[0076] After a plurality of wafers 200 are loaded into the wafer boat 217 (wafer loading), Figure 1 As shown, the wafer boat 217 supporting the plurality of wafers 200 is lifted by the wafer boat elevator 115 and carried into the processing chamber 201 (wafer boat loading), and is stored in the processing container. In this state, the sealing cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0077] (Pressure regulation and temperature regulation)

[0078] 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 maintains a state of normal operation at least until the processing of the wafer 200 is completed. In addition, the heater 207 heats the processing chamber 201 in such a manner that the desired temperature is reached. 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 in such a manner that the desired temperature distribution is achieved in the processing chamber 201. The heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing of the wafer 200 is completed.

[0079] [Pre-process] (gas supply containing organic ligand)

[0080] The valve 324 is opened to allow the organic ligand-containing gas to flow into the gas supply pipe 320. The organic ligand-containing gas is flow-regulated by the MFC 322, supplied from the gas supply hole 420a of the nozzle 420 to the processing chamber 201, and exhausted from the exhaust pipe 231. At the same time, the valve 524 may be opened to allow an inactive gas such as N2 gas to flow into the gas supply pipe 520. In addition, in order to prevent the organic ligand-containing gas from invading the nozzles 410 and 430, the valves 514 and 534 may be opened to allow an inactive gas to flow into the gas supply pipes 510 and 530.

[0081] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 becomes, for example, a pressure in the range of 1 to 3990 Pa. The supply flow rate of the organic ligand-containing gas controlled by the MFC322 becomes, for example, a flow rate in the range of 0.01 to 5.0 slm. Hereinafter, the temperature of the heater 207 is set so that the temperature of the chip 200 reaches a temperature in the range of, for example, 300 to 550°C. It should be noted that the expression of a numerical range such as "1 to 3990 Pa" in the present invention indicates that the lower limit and the upper limit are included in the range. For example, the so-called "1 to 3990 Pa" means "above 1 Pa and below 3990 Pa". The same applies to other numerical ranges.

[0082] At this time, a gas containing an organic ligand is supplied to the wafer 200. As the gas containing an organic ligand, a gas containing a hydrocarbon group (CH-), for example, a gas containing an alkyl group, for example, a gas containing a methyl group, and a gas containing a metal element, for example, trimethylaluminum ((CH3)3Al) gas (hereinafter referred to as TMA gas) can be used. As the gas containing an organic ligand, when TMA gas is used, by supplying the gas containing an organic ligand, such as Figure 5 As shown in (A), a methyl group (-CH3) which is a hydrocarbon group or an alkyl group is adsorbed on the wafer 200 (the base film on the surface). Figure 5 As shown in (A), Al atoms in a state of being bonded with methyl groups are also adsorbed on the chip 200 (the base film on the surface). In any case, the surface of the chip 200 is terminated with methyl groups by supplying a gas containing an organic ligand. It should be noted that in the present invention, the so-called "termination" and "adsorption" may also include a state in which the surface of the chip 200 is not completely covered. Depending on the gas supply conditions and the surface state of the chip 200, there may be a situation in which the surface of the chip 200 is not completely covered. In addition, there is a situation in which the surface of the chip 200 is not completely covered due to self-limiting cessation of the reaction.

[0083] Here, the metal element contained in the gas containing organic ligands is a non-transition metal element, preferably an element different from the metal element contained in the metal-containing gas in the film forming process described later. For example, as illustrated in this embodiment, when the metal-containing film to be formed is a TiN film, a gas containing Al is used as the gas containing organic ligands.

[0084] [Film forming step (including metal film forming step)]

[0085] After the organic ligand-containing gas is supplied onto the wafer 200 through the above-mentioned pre-process, the following steps 1 to 4 are repeatedly performed. That is, after the organic ligand-containing gas is supplied, the following steps 1 to 4 are repeatedly performed without supplying the purge gas. That is, in a state where the organic ligand is adsorbed on the wafer 200, the following steps 1 to 4 are repeatedly performed on the wafer 200 with the organic ligand exposed.

[0086] (Metal-containing gas supply, step 1)

[0087] The valve 314 is opened to allow the metal-containing gas to flow into the gas supply pipe 310. The metal-containing gas is flow-regulated by the MFC 312, supplied to the processing chamber 201 from the gas supply hole 410a of the nozzle 410, and exhausted from the exhaust pipe 231. At the same time, the valve 514 may be opened to allow an inactive gas such as N2 gas to flow into the gas supply pipe 510. At this time, in order to prevent the metal-containing gas from intruding into the nozzles 420 and 430, the valves 524 and 534 may be opened to allow N2 gas to flow into the gas supply pipes 520 and 530.

[0088] At this time, the APC valve 243 is adjusted so that the pressure in the processing chamber 201 is, for example, in the range of 1 to 3990 Pa. The supply flow rate of the metal-containing gas controlled by the MFC 312 is, for example, in the range of 0.1 to 2.0 slm. Next, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 reaches, for example, a temperature in the range of 300 to 550° C. The time for supplying the metal-containing gas to the wafer 200 is set to, for example, a time in the range of 0.01 to 30 seconds.

[0089] At this time, the metal-containing gas is supplied to the wafer 200 on which the organic ligand from the organic ligand-containing gas, i.e., the methyl group, is adsorbed, i.e., the wafer 200 whose surface is terminated by the methyl group. Here, as the metal-containing gas, for example, titanium tetrachloride (TiCl4) gas, which is a gas containing titanium (Ti) and halogen (chlorine), can be used. When the TiCl4 gas is used as the metal-containing gas, Figure 5 That is, TiCl4 gas is supplied to the wafer 200 in which the methyl group as the organic ligand is exposed. By supplying TiCl4 gas, Figure 5 As shown in (B), the halogen (Cl) contained in the TiCl4 gas reacts with the methyl groups present on the wafer 200, and the TiCl x (x is less than 4) is adsorbed on the wafer 200. That is, since the TiCl4 molecule is smaller in size than the TiCl4 molecule, x adsorbed on the wafer 200, the steric hindrance is reduced compared to the case of TiCl4 adsorption. xThe Ti-containing layer is adsorbed on the wafer 200 (the base film on the surface), and the adsorption density of the Ti element on the wafer 200 is increased, so that a Ti-containing layer with a high content of the Ti element can be formed. It should be noted that at this time, methyl chloride (CH3Cl) is generated as a by-product. Most of the by-product is detached from the wafer 200.

[0090] (Purge, Step 2)

[0091] After a predetermined time (e.g., 0.1 to 10 seconds) has passed since the start of the supply of the metal-containing gas, the valve 314 is closed to stop the supply of the metal-containing gas. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove residual gas from the wafer 200, and the unreacted metal-containing gas and reaction byproducts remaining in the processing chamber 201 are discharged from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open to maintain the supply of the inert gas as a purge gas into the processing chamber 201. The inert gas acts as a purge gas and can remove residual gas from the wafer 200, thereby improving the effect of removing the unreacted metal-containing gas and reaction byproducts remaining in the processing chamber 201 from the processing chamber 201. The supply flow rate of the inert gas controlled by the MFCs 512, 522, and 532 is set to, for example, 0.1 to 10 slm, respectively.

[0092] (First reducing gas supply, third step)

[0093] After a predetermined time (e.g., 0.1 to 10 seconds) has passed since the start of the purge, the valves 514, 524, and 534 are closed to stop the supply of the inert gas into the processing chamber 201. At this time, the valve 334 is opened to allow the first reducing gas to flow into the gas supply pipe 330. The first reducing gas is also referred to as a nitrogen-containing gas. The first reducing gas can be flow-regulated by the MFC 332, supplied to the processing chamber 201 from the gas supply hole 430a of the nozzle 430, and exhausted from the exhaust pipe 231. At this time, the first reducing gas is supplied to the wafer 200. It should be noted that the valve 534 can be opened at the same time to allow the inert gas to flow into the gas supply pipe 530. In addition, in order to prevent the first reducing gas from invading the nozzles 410 and 420, the valves 514 and 524 can also be opened to allow the inert gas to flow into the gas supply pipes 510 and 520.

[0094] At this time, the APC valve 243 is adjusted, and the pressure in the processing chamber 201 is set to a pressure in the range of, for example, 1 to 3990 Pa. The supply flow rate of the first reducing gas controlled by the MFC 332 is set to a flow rate in the range of, for example, 0.1 to 30 slm. The time for supplying the first reducing gas to the wafer 200 is set to a time in the range of, for example, 0.01 to 30 seconds.

[0095] At this time, the first reducing gas is supplied to the wafer. Here, as the first reducing gas, for example, ammonia (NH3) gas, which is a N-containing gas containing nitrogen (N), can be used. The reaction when NH3 gas is used as the first reducing gas is shown in FIG. Figure 5 (C). Figure 5 As shown in (C), the NH3 gas undergoes a substitution reaction with at least a portion of the Ti-containing layer formed on the wafer 200. During the substitution reaction, Ti contained in the Ti-containing layer is bonded with N contained in the NH3 gas to form a TiN layer on the wafer 200. In addition, during the substitution reaction, reaction byproducts such as HCl, NH4Cl, and H2 are generated.

[0096] (Purge, Step 4)

[0097] After a predetermined time (e.g., 0.01 to 60 seconds) has passed since the supply of the first reducing gas started, the valve 334 is closed to stop the supply of the first reducing gas. At this time, the APC valve 243 of the exhaust pipe 231 is kept open, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246 to remove residual gas from the wafer 200, and the first reducing gas and reaction byproducts that have not reacted or contributed to the formation of the metal-containing layer remaining in the processing chamber 201 are discharged from the processing chamber 201. At this time, the valves 514, 524, and 534 are kept open to maintain the supply of the inert gas as a purge gas into the processing chamber 201. The inert gas acts as a purge gas to remove the residual gas from the wafer 200, thereby improving the effect of removing the unreacted first reducing gas and the above-mentioned reaction byproducts from the processing chamber 201. The supply flow rate of the inert gas controlled by the MFCs 512, 522, and 532 is set to, for example, 0.1 to 10 slm, respectively.

[0098] That is, the first reducing gas and the reaction byproducts that remain in the processing chamber 201 and have not reacted or have contributed to the formation of the metal-containing layer are exhausted from the processing chamber 201. The inert gas functions as a purge gas.

[0099] (Specified number of implementations)

[0100] By performing the above-mentioned first to fourth steps in sequence for a predetermined number of times (N times) or more, a metal-containing layer having a predetermined thickness is formed on the wafer 200 to form a metal-containing film. Here, a TiN film is formed as the metal-containing film.

[0101] (Post-purge and atmospheric pressure recovery)

[0102] An inert gas is supplied from each of the gas supply pipes 510 to 530 to the processing chamber 201, and the gas is exhausted from the exhaust pipe 231. The inert gas acts as a purge gas, thereby purging the processing chamber 201 with the inert gas, and removing the gas and reaction byproducts remaining in the processing chamber 201 from the processing chamber 201 (post-purge). After that, 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).

[0103] (Wafer removal)

[0104] After that, the sealing cover 219 is lowered by the wafer boat elevator 115 to open the lower end of the outer tube 203. Then, the processed wafer 200 is carried out from the lower end of the outer tube 203 to the outside of the outer tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After that, the processed wafer 200 is removed from the wafer boat 217 (wafer removal).

[0105] Figure 6 (A) is a diagram showing a TEM image of a TiN film formed on a wafer 200 using the above-mentioned substrate processing sequence, which is projected using a transmission electron microscope (TEM). Figure 6 (B) is a diagram showing a TEM image of the surface of a TiN film formed on a wafer 200 using the substrate processing sequence involved in the comparative example. Thick TiN film.

[0106] In the substrate processing sequence involved in the comparative example, the above-mentioned pre-process is not performed before the film forming process is performed on the wafer 200. Figure 6 As shown in (B), for a TiN film formed by the substrate processing sequence involved in the comparative example without supplying a gas containing an organic ligand, when formed on a SiO2 film, The thin films on the left and right did not form a continuous film but grew in an island shape. That is, the adsorption of TiCl4 onto the wafer 200 was insufficient, and the coverage was poor.

[0107] In contrast, Figure 6 As shown in (A), compared with the TiN film formed by the substrate processing sequence according to the comparative example, the TiN film formed by the substrate processing sequence according to the present embodiment has small crystal grains, is continuously formed at a high density, and has a high coverage.

[0108] That is, by supplying a gas containing an organic ligand before the film forming process, the adsorption of TiCl4 onto the wafer 200 can be promoted, the adsorption density of the Ti element can be increased, and it is confirmed that a TiN film with a high content of the Ti element can be formed. In other words, it is confirmed that the resistance of the W film formed on the surface of the TiN film can be reduced.

[0109] (3) Effects of this embodiment

[0110] According to the present embodiment, one or more of the following effects can be obtained.

[0111] (a) The properties of the metal-containing film can be improved.

[0112] (b) The metal-containing film can be grown continuously. Here, the term "continuously" means that the crystals of the material of the metal-containing film are connected and the intervals between the crystals are small.

[0113] (c) A high-density and flat metal-containing film can be formed.

[0114] (d) The coverage can be improved, and the resistivity of another metal-containing film formed on the metal-containing film can be reduced.

[0115] (e) The adsorption density of the metal element in the metal-containing gas can be increased.

[0116] (4) Other Implementation Methods

[0117] 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 spirit and scope of the present invention.

[0118] In the above-mentioned embodiment, an example in which an organic ligand-containing gas is continuously supplied as a pre-process is described, but the present invention is not limited to this and can also be applied to a case in which a different gas is used.

[0119] (Variant 1)

[0120] Figure 7 A variation of the substrate processing sequence in one embodiment of the present invention is shown. In this variation, as a pre-process, the second reducing gas is supplied before the gas containing organic ligands is supplied. That is, before the film forming process is performed, as pre-processes, a process of supplying the second reducing gas to the wafer 200 and a process of supplying the gas containing organic ligands are performed. At this time, a purge gas is not supplied between the supply of the second reducing gas and the supply of the gas containing organic ligands, and between the pre-process and the film forming process. In this case, the same effect as described above can also be obtained. Figure 4 It should be noted that in this modification, the first reducing gas and the second reducing gas use the same type of gas.

[0121] As shown in this variation, before supplying the gas containing organic ligands (for example, TMA gas) in the previous process, a second reducing gas (for example, NH3 gas) is supplied to the chip 200, thereby forming at least one of an NH bond (NH termination) and an H bond (H termination) on the chip 200. By generating any of the above bonds, the adsorption amount of the gas containing organic ligands on the chip 200 can be increased. And thereby, the amount of methyl groups adsorbed as organic ligands on the chip 200 is increased, and the metal-containing gas is supplied to the chip 200 on which the methyl groups as organic ligands are adsorbed. That is, the metal-containing gas is supplied to the chip 200 on which the methyl groups as organic ligands are exposed. Here, in the case where the metal-containing gas is TiCl4 gas, through the supply of TiCl4 gas, the halogen (Cl) contained in the TiCl4 gas reacts with the methyl groups present on the chip 200, and the TiCl x (x is less than 4) is adsorbed on the wafer 200. That is, compared with the case of TiCl4 adsorption, TiCl4 with less steric hindrance x By being adsorbed on the wafer 200 (the base film on the surface), the adsorption density of the Ti element on the wafer 200 can be increased, and a Ti-containing layer with a high content of the Ti element can be formed. In addition, by using the same NH3 gas as the first reducing gas in the film forming process as the second reducing gas in the previous process, the number of gas supply pipes connected to the processing container can be reduced.

[0122] (Variant 2)

[0123] Figure 8 Another variation of the substrate processing sequence in one embodiment of the present invention is shown. In this variation, as a pre-process, a second reducing gas is supplied before or after the supply of the gas containing an organic ligand, and the supply of the organic ligand gas and the supply of the second reducing gas are each performed more than once, and then the above-mentioned film forming process is performed. That is, before the film forming process is performed, as a pre-process, after the process of supplying the second reducing gas to the chip 200, the process of supplying the organic ligand gas and the process of supplying the second reducing gas are performed a predetermined number of times (M times) and more than once. At this time, the purge gas is not supplied between the supply of the second reducing gas and the supply of the organic ligand gas, and between the pre-process and the film forming process. In this case, the same effect as described above can also be obtained. Figure 4 The same effect is achieved in the order of substrate processing shown.

[0124] In this variation, if Fig. 9As shown in (A), before supplying TMA gas as the organic ligand-containing gas to the wafer 200 in the previous process, NH3 gas as the second reducing gas is supplied, thereby forming at least one of NH bond (NH termination) and H bond (H termination) on the wafer 200. By forming NH termination and H termination, the adsorption amount of the organic ligand-containing gas molecule (TMA) on the wafer 200 can be increased. That is, the organic ligand on the wafer 200 can be increased.

[0125] And, if Fig. 9 (B) and Fig. 9 As shown in (C), NH3 gas is supplied to the wafer 200 on which TMA is adsorbed. As a result, at least one of NH bonds (NH termination) and H bonds (H termination) is formed on the unbound sites on the wafer 200. In addition, part of the organic ligands formed on the wafer 200 react with NH3 to form Al-(CH3) x Removing a portion of the organic ligand (for example, removing CH3) can generate an organic ligand with a smaller molecular weight. For example, Al-(CH3) y Here, y is smaller than x. For example, x=2, y=1. It should be noted that due to the reaction of TMA with NH3, a part of it is converted into AlN.

[0126] As shown in this modification, in the previous process, after the process of supplying NH3 gas to the wafer 200, the process of supplying TMA gas and the process of supplying NH3 gas are performed a predetermined number of times (M times) and more than one time, thereby increasing the number of organic ligands, NH bonds, and H bonds on the wafer 200. In addition, organic ligands with a small number of molecules can be generated. Here, organic ligands with a small number of molecules are also referred to as low-molecular-number organic ligands, specifically, ligands with 3 or less hydrocarbon groups (CH-), preferably ligands with 2 or less hydrocarbon groups (CH-).

[0127] In addition, by supplying TiCl4 gas to the wafer 200 in such a surface state, Fig. 9 As shown in (D), Cl contained in the TiCl4 gas reacts with the NH bonds and organic ligands present on the chip 200, and TiCl4 in a state where Cl is reduced compared to TiCl4 is adsorbed on the chip 200. x (x is less than 4). Therefore, compared with the case of TiCl4 adsorption, TiCl xFormed on the wafer 200 (the base film on the surface), the adsorption density of the Ti element on the wafer 200 can be increased, and a Ti-containing layer with a high content of the Ti element can be formed. In addition, as the second reducing gas in the previous process, the same NH3 gas as the first reducing gas in the film forming process is used, thereby reducing the number of gas supply pipes connected to the processing container. In addition, here, since an organic ligand with a small number of molecules is generated on the wafer 200, it is possible to suppress the organic ligand itself from becoming a steric hindrance, which can promote the TiCl x adsorption.

[0128] (Variant 3)

[0129] Fig.10 Another variation of the substrate processing sequence in one embodiment of the present invention is shown. In this variation, in the previous process, the gas containing the organic ligand is supplied in a time-sharing manner. That is, as a previous process, after the gas containing the organic ligand is supplied in a time-sharing manner, the purge gas is not supplied and the above-mentioned film forming process is performed. By supplying the gas in a time-sharing manner, the organic ligand can be adsorbed on the wafer 200 without gaps. In this case, the same effect as described above can also be obtained. Figure 4 The same effect is achieved in the order of substrate processing shown.

[0130] (Variant 4)

[0131] Fig.11 Another variation of the substrate processing sequence in one embodiment of the present invention is shown. In this variation, in the previous process, an amine-containing organic ligand gas (also referred to as amine-containing gas in the present invention) is supplied as an organic ligand-containing gas. The amine-containing gas is a gas containing an organic ligand having an amino group (NH-), for example, tri(dimethylamino)silane (((CH3)2N)3SiH) gas (hereinafter referred to as TDMAS gas) is supplied. After the amine-containing gas is supplied as a previous process, the purge gas is not supplied, and the above-mentioned film forming process is performed. In this case, the same as the above-mentioned can also be obtained. Figure 4 The same effect is achieved in the order of substrate processing shown.

[0132] In this modification, in the previous step, as the gas containing organic ligands, by using a gas containing organic ligands having amine groups, it is possible to increase the amine groups, i.e., NH bonds, on the wafer 200. Furthermore, TiCl4 gas is supplied to the wafer 200 on which the NH bonds are adsorbed. By supplying the TiCl4 gas, Cl contained in the TiCl4 gas reacts with the NH bonds (NH termination) existing on the wafer 200, and the TiCl4 gas is x (x is less than 4) is adsorbed on the wafer 200. That is, TiCl4, which has a smaller number of molecules and less steric hindrance than TiCl4, xA continuous TiN film with a large amount of Ti adsorbed is formed on the wafer 200 (underlayer on the surface). It should be noted that for a gas containing an organic ligand, in the case of a polymer material, the organic ligand functions as a steric hindrance, so a low molecular weight material is preferred.

[0133] In addition, as organic ligand-containing gases, there are materials containing elements of the IVA group such as Si. Among these materials, in materials in which the IVA group element and the hydrocarbon group (CH-) are directly bonded, it is believed that the bond energy between the hydrocarbon group (CH-) and the IVA group element is greater than the bond energy between the metal element (non-transition metal element) and the hydrocarbon group as described above, and it is sometimes difficult to obtain the effect of the present invention. For example, in -Si-(CH3) x In such an organic ligand, it is believed that the bond between Si and CH3 is not easily cut, and even if TiCl4 gas is supplied, it will not react with -Si-(CH3) x reaction. Therefore, as a gas containing an organic ligand, a gas containing a metal element as described above is preferred. More preferably, a gas containing an organic ligand containing a non-transition metal element is used as described above. That is, by using a gas containing an organic ligand containing a metal element (non-transition metal element), the above-mentioned effect can be further obtained. In addition, it is ideal that the metal element is not a transition metal, but a non-transition metal. In the case of using a gas containing an element such as Hf, Zr, etc. as a transition metal, it is considered that a dielectric with a high dielectric constant is formed in the previous process. In the case of forming such a dielectric, it is possible to affect the characteristics of the semiconductor device. In addition, in a transition metal such as Ti, the effects described later can be considered.

[0134] In addition, in the above-mentioned embodiment, a method is described in which the metal element contained in the gas containing the organic ligand used in the previous process is different from the metal element contained in the metal-containing gas in the film forming process. By using a gas containing a different metal element in this way, it is possible to suppress the metal-containing film formed in the film forming process from being affected by the characteristics of the metal-containing layer formed in the previous process. For example, in the previous process, in the case of the same gas containing Ti as in the film forming process, a TiN film with poor characteristics is formed, and it is considered that the characteristics of the TiN film formed in the film forming process are deteriorated. Therefore, it is ideal that the metal element contained in the gas used in the film forming process and the previous process is a different element.

[0135] In addition, in the above-mentioned embodiment, the case where the same NH3 gas is used as the second reducing gas used in the previous process and the first reducing gas used in the film forming process is described, but the present invention is not limited to this. The second reducing gas used in the previous process and the first reducing gas used in the film forming process may use different gases.

[0136] In addition, in the above-mentioned embodiment, a mode in which a purge process is not performed between the pre-process and the film forming process is shown, but the present invention is not limited thereto, and a purge process may be performed between the pre-process and the film forming process as appropriate. By performing a purge process between the pre-process and the film forming process, byproducts and excess gases present in the processing chamber 201 can be removed, and the characteristics of the film formed in the film forming process can be improved.

[0137] (Variant 5)

[0138] For example, Fig.12 As shown, as a pre-process, the process of supplying a gas containing an organic ligand and the process of supplying a second reducing gas are respectively performed more than once, and then as a film forming process, the process of supplying molybdenum dioxide dichloride (MoO2Cl2) gas as a metal-containing gas and the process of supplying hydrogen (H2) gas as a first reducing gas are respectively performed more than once. When a Mo film is formed on the chip 200 as a metal-containing film, the above-mentioned Figure 4 The same effect is achieved in the order of substrate processing shown.

[0139] In addition, in the above-mentioned embodiment, the case where TMA gas containing a hydrocarbon group, an alkyl group, or a methyl group is used as the gas containing an organic ligand in the previous process is described, but the present invention is not limited to this. As the gas containing an organic ligand, it can also be suitably applied when a gas containing at least any one of ethyl, propyl, butyl, isopropyl, and isobutyl groups as an alkyl group is used.

[0140] In addition, in the above-mentioned embodiment, the case of using TiCl4 gas containing Ti and Cl as the metal-containing gas is used for illustration, but the present invention is not limited to this and can also be appropriately applied to the case of using a gas containing molybdenum (Mo), ruthenium (Ru), copper (Cu), tungsten (W) and the like and halogen as the metal-containing gas.

[0141] In addition, in the above embodiment, the case of forming a TiN film as a metal-containing film is described, but the present invention is not limited to this and can also be appropriately applied to the case of forming a Mo film, Ru film, Cu film, W film, titanium silicon nitride (TiSiN) film, etc. as a metal-containing film.

[0142] In addition, in the above-mentioned embodiment, an example of using a batch-type vertical device, i.e., a substrate processing device, to perform film formation is described, but the present invention is not limited to this and can also be suitably applied to the case where film formation is performed using a single-wafer substrate processing device that processes one or several substrates at a time.

[0143] For example, when using Fig.13The present invention can also be preferably applied to the case where a film is formed by using a substrate processing device of a processing furnace 302 shown in (A). The processing furnace 302 includes: a processing container 303 forming a processing chamber 301; a shower head 303s for supplying gas into the processing chamber 301 in a shower-like manner; a support table 317 for supporting one or more wafers 200 in a horizontal posture; a rotating shaft 355 for supporting the support table 317 from below; and a heater 307 provided on the support table 317. A gas supply port 332a for supplying the above-mentioned metal-containing gas, a gas supply port 332b for supplying the above-mentioned reducing gas, and a gas supply port 332c for supplying the above-mentioned gas containing organic ligand are connected to the inlet (gas inlet) of the shower head 303s. A metal-containing gas supply system similar to the metal-containing gas supply system of the above-mentioned embodiment is connected to the gas supply port 332a. A reducing gas supply system similar to the reducing gas supply system of the above-mentioned embodiment is connected to the gas supply port 332b. The gas supply port 332c is connected to a gas supply system similar to the above-mentioned gas supply system containing organic ligands. A gas dispersion plate for supplying gas in a shower-like manner into the processing chamber 301 is provided at the outlet (gas exhaust port) of the shower head 303s. An exhaust port 331 for exhausting the processing chamber 301 is provided on the processing container 303. An exhaust system similar to the exhaust system of the above-mentioned embodiment is connected to the exhaust port 331.

[0144] In addition, for example, when using Fig.13 The present invention can also be suitably applied to the case where a film is formed by using a substrate processing device of a processing furnace 402 shown in (B). The processing furnace 402 includes: a processing container 403 forming a processing chamber 401; a support table 417 supporting one or more wafers 200 in a horizontal posture; a rotating shaft 455 supporting the support table 417 from below; a lamp heater 407 for irradiating light toward the wafer 200 in the processing container 403; and a quartz window 403w for transmitting light from the lamp heater 407. A gas supply port 432a for supplying the above-mentioned metal-containing gas, a gas supply port 432b for supplying the above-mentioned reducing gas, and a gas supply port 432c for supplying the above-mentioned gas containing organic ligands are connected to the processing container 403. A metal-containing gas supply system similar to the metal-containing gas supply system of the above-mentioned embodiment is connected to the gas supply port 432a. A reducing gas supply system similar to the reducing gas supply system of the above-mentioned embodiment is connected to the gas supply port 432b. The gas supply port 432c is connected to a gas supply system similar to the organic ligand-containing gas supply system of the above embodiment. The processing container 403 is provided with an exhaust port 431 for exhausting the processing chamber 401. The exhaust port 431 is connected to an exhaust system similar to the exhaust system of the above embodiment.

[0145] Even when the above-described substrate processing apparatus is used, film formation can be performed in the same procedure and processing conditions as those in the above-described embodiment.

[0146] Preferably, the process recipes (programs recording the processing steps, processing conditions, etc.) for forming the above-mentioned various thin films are prepared separately (preparing multiple processes) according to the content of the substrate processing (film type, composition ratio, film quality, film thickness, processing steps, processing conditions, etc. of the thin film to be formed). And, preferably, when starting the substrate processing, a suitable process recipe is appropriately selected from multiple process recipes according to the content of the substrate processing. Specifically, it is preferred that multiple process recipes prepared separately according to the content of the substrate processing are pre-stored (installed) in the storage device 121c possessed by the substrate processing device via an electrical communication line and a recording medium (external storage device 123) recording the process recipes. And, preferably, when starting the substrate processing, the CPU 121a possessed by the substrate processing device appropriately selects a suitable process recipe from the multiple process recipes stored in the storage device 121c according to the content of the substrate processing. Through such a configuration, thin films of various film types, composition ratios, film qualities, and film thicknesses can be formed universally and with good reproducibility by one substrate processing device. In addition, the operation burden on operators (such as the burden of inputting processing steps and processing conditions) can be reduced, operation errors can be avoided, and substrate processing can be started quickly.

[0147] In addition, the present invention can also be realized by, for example, changing the process of an existing substrate processing device. When changing the process, the process involved in the present invention is installed in the existing substrate processing device via an electrical communication line or a recording medium recording the process, or the input and output device of the existing substrate processing device can be operated to change the process itself to the process involved in the present invention.

[0148] Furthermore, the present invention can be used for example in a word line portion of a NAND flash memory, DRAM, or the like having a three-dimensional structure.

[0149] As mentioned above, although various typical embodiments of the present invention have been described, the present invention is not limited to the above-mentioned embodiments, and can be used in appropriate combination.

[0150] Hereinafter, examples will be described.

[0151] [Example 1]

[0152] Using the above-mentioned substrate processing apparatus 10, the following samples were prepared: Figure 4 The substrate processing sequence is formed on the SiO2 substrate. Sample 1 is made of a TiN film with a thickness of Figure 7The substrate processing sequence is formed on the SiO2 substrate Sample 2 made of a TiN film with a thickness of Figure 8 The substrate processing sequence is formed on the SiO2 substrate Thickness TiN film formed by sample 3; and in accordance with the substrate processing sequence before the film forming step without performing the pre-process, formed on the SiO2 substrate Sample 4 is made of a TiN film with a thickness of . Fig.14 The diagram shows transmission electron microscope (TEM) images of the surfaces of the TiN films of Samples 1 to 4 projected using a TEM.

[0153] like Fig.14 As shown, it was confirmed that the TiN films of samples 1 to 3 had a higher particle ratio and a higher density of TiN on the SiO2 substrate than the TiN film of sample 4. That is, in the case of a TiN film formed by performing a pre-process before forming the TiN film and supplying a gas containing an organic ligand to the substrate and then performing a film forming process, the TiN on the SiO2 substrate had a higher particle ratio and a higher density and had flatness than the TiN film formed without performing the pre-process.

[0154] That is, it was confirmed that by supplying a gas containing an organic ligand before forming a TiN film, adsorption of the Ti element onto the wafer surface can be promoted, and a TiN film with a thin film and a high coverage can be formed.

Claims

1. A substrate processing method, comprising: (a) supplying a gas containing an organic ligand to a substrate so that the surface of the substrate is terminated with an alkyl group contained in the organic ligand; (b) supplying a metal-containing gas to the substrate whose surface is blocked with the alkyl group so that the halogen contained in the metal-containing gas reacts with the alkyl group contained in the organic ligand; and (c) supplying a first reducing gas to the substrate, The substrate processing method includes the step of forming a metal-containing film on the substrate by performing (b) and (c) respectively one or more times after (a). No purge gas is supplied between (a) and (b). The gas containing organic ligands contains a non-transition metal element, The non-transition metal element contained in the gas containing the organic ligand is different from the metal element contained in the metal-containing gas.

2. The substrate processing method according to claim 1, wherein: The alkyl group includes at least any one of an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group.

3. The substrate processing method according to claim 1, wherein: The organic ligand comprises an amine group.

4. The substrate processing method according to claim 1, further comprising: (d) A step of supplying a second reducing gas to the substrate before step (a).

5. The substrate processing method according to claim 1, further comprising: (e) After step (a), a step of supplying a second reducing gas to the substrate.

6. The substrate processing method according to claim 1, comprising: (f) a step of supplying a second reducing gas to the substrate before step (a); and (g) after step (a), supplying the second reducing gas to the substrate, In the substrate processing method, (a) and (g) are performed multiple times.

7. The substrate processing method according to claim 4, wherein: The second reducing gas is a gas different from the first reducing gas.

8. The substrate processing method according to claim 4, wherein: The second reducing gas is the same gas as the first reducing gas.

9. The substrate processing method according to claim 1, wherein: In (a), a gas containing an organic ligand is supplied to the substrate in a time-division manner.

10. The substrate processing method according to claim 1, wherein: In (b), the metal-containing gas is supplied to the substrate on which the organic ligand is exposed.

11. A substrate processing device comprising: a processing container for receiving a substrate; a gas supply system for supplying a metal-containing gas, a first reducing gas, and a gas containing an organic ligand into the processing container; and A control unit configured to control the gas supply system in such a manner as to perform the following process, the process comprising: (a) supplying a gas containing an organic ligand to the substrate so that the surface of the substrate is terminated with an alkyl group contained in the organic ligand; (b) a process of supplying a metal-containing gas to the substrate whose surface is blocked with the alkyl group so that a halogen contained in the metal-containing gas reacts with the alkyl group contained in the organic ligand; and (c) supplying a first reducing gas to the substrate, After (a), (b) and (c) are performed one or more times to form a metal-containing film on the substrate. No purge gas is supplied between (a) and (b). The gas containing organic ligands contains a non-transition metal element, The non-transition metal element contained in the gas containing the organic ligand is different from the metal element contained in the metal-containing gas.

12. A method for manufacturing a semiconductor device, comprising: (a) supplying a gas containing an organic ligand to a substrate so that the surface of the substrate is terminated with an alkyl group contained in the organic ligand; (b) supplying a metal-containing gas to the substrate whose surface is blocked with the alkyl group so that the halogen contained in the metal-containing gas reacts with the alkyl group contained in the organic ligand; and (c) supplying a first reducing gas to the substrate, The manufacturing method includes the step of forming a metal-containing film on the substrate by performing (b) and (c) respectively one or more times after (a). No purge gas is supplied between (a) and (b). The gas containing organic ligands contains a non-transition metal element, The non-transition metal element contained in the gas containing the organic ligand is different from the metal element contained in the metal-containing gas.

13. A computer-readable recording medium having a program recorded thereon for causing a substrate processing apparatus to execute the following steps through a computer, the steps comprising: (a) supplying a gas containing an organic ligand to a substrate so that the surface of the substrate is terminated with an alkyl group contained in the organic ligand; (b) a step of supplying a metal-containing gas to the substrate whose surface is blocked with the alkyl group so that a halogen contained in the metal-containing gas reacts with the alkyl group contained in the organic ligand; and (c) supplying a first reducing gas to the substrate, After (a), (b) and (c) are performed one or more times to form a metal-containing film on the substrate. No purge gas is supplied between (a) and (b). The gas containing organic ligands contains a non-transition metal element, The non-transition metal element contained in the gas containing the organic ligand is different from the metal element contained in the metal-containing gas.

Images