Substrate processing method, semiconductor device manufacturing method, recording medium, and substrate processing apparatus

Abstract

This invention enables the formation of films with film continuity. The invention comprises: a step of preparing a substrate on which a metal-containing film is formed on its surface, and a step of thinning the metal-containing film by pulsed supply of a halogen-containing gas to the substrate.

Description

Technical Field

[0001] This disclosure relates to a substrate processing method, a method for manufacturing a semiconductor device, a recording medium, and a substrate processing apparatus. Background Technology

[0002] In NAND flash memory with a 3D structure, a tungsten (W) film is used, for example, in the control gate, and tungsten hexafluoride (WF6) gas containing W is used in the deposition of the W film. Furthermore, a titanium nitride (TiN) film, for example, is provided as a barrier film between the W film and the insulating film (see, for example, Patent Document 1). This TiN film not only improves the adhesion between the W film and the insulating film but also prevents the diffusion of fluorine (F) contained in the W film into the insulating film. From the viewpoint of reducing wiring resistance, a thin film is desirable.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-66263 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, if formed on the insulating film In the following thin films, the TiN film will form islands, resulting in poor adhesion to the W film. Furthermore, the F contained in the W film will diffuse into the insulating film through the portions where the TiN film has not formed.

[0008] The purpose of this disclosure is to provide a technique for forming membranes with membrane continuity.

[0009] Methods for solving problems

[0010] According to one aspect of this disclosure, a technique is provided comprising: a step of preparing a substrate on which a metal-containing film is formed on the surface, and a step of thinning the metal-containing film by pulse supplying a halogen-containing gas to the substrate.

[0011] Invention Effects

[0012] According to this disclosure, it is possible to form a membrane with membrane continuity. Attached Figure Description

[0013] Figure 1 This is a schematic longitudinal cross-sectional view showing a longitudinal processing furnace of a substrate processing apparatus in one embodiment of the present disclosure.

[0014] Figure 2 yes Figure 1 A rough cross-sectional view of the middle AA line.

[0015] Figure 3 This is a schematic configuration diagram of the controller of the substrate processing apparatus in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller.

[0016] Figure 4 This is a diagram showing a film-forming process in one embodiment of the present disclosure.

[0017] Figure 5 In the image, (A) shows the film-forming process that, through the above-described film-forming steps, forms a film on the substrate. Schematic diagrams of the TiN film formation process are shown in (B) and (C), illustrating the film formation and thinning steps performed on the substrate through the aforementioned film formation process. A schematic diagram of the TiN film.

[0018] Figure 6 This is a diagram showing a modified example of the film-forming process in a film-forming process according to an embodiment of the present disclosure.

[0019] Figure 7 This is a diagram showing a variation of the thinning step in the film formation process of one embodiment of the present disclosure.

[0020] Figure 8 This is a diagram showing a variation of the thinning step in the film formation process of one embodiment of the present disclosure.

[0021] Figure 9 (A) and (B) are schematic longitudinal cross-sectional views showing the processing furnace of the substrate processing apparatus in other embodiments of the present disclosure. Detailed Implementation

[0022] The following is for reference Figures 1-4 Please provide an explanation.

[0023] (1) Composition of substrate processing device

[0024] The substrate processing apparatus 10 includes a processing furnace 202 equipped with a heater 207, which serves as a heating unit (heating mechanism, heating system). The heater 207 is cylindrical in shape and is vertically mounted, supported by a heater base (not shown) that serves as a holding plate.

[0025] An outer tube 203 constituting a reaction vessel (processing vessel) is arranged concentrically with the heater 207 inside the heater 207. The outer tube 203 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. 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 open upper and lower ends. An O-ring 220a, serving 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, allowing the outer tube 203 to be installed vertically.

[0026] Inside the outer tube 203, an inner tube 204 constituting the reaction vessel is disposed. The inner tube 204 is made of heat-resistant materials such as quartz (SiO2) or SiC, and is formed into a cylindrical shape with a closed upper end and an open lower end. The processing vessel (reaction vessel) 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 part of the processing vessel (inside the inner tube 204).

[0027] The processing chamber 201 is configured to accommodate the wafer 200, which serves as a substrate, in a state in which the wafer cassette 217, described later, is arranged in a horizontal orientation and in multiple segments in the vertical direction.

[0028] Inside the processing chamber 201, nozzles 410, 420, 430, 440, and 450 are installed to penetrate the side wall of the manifold 209 and the inner pipe 204. The nozzles 410, 420, 430, 440, and 450 are connected to gas supply pipes 310, 320, 330, 340, and 350, respectively. However, the processing furnace 202 in this embodiment is not limited to the above-described manner.

[0029] In gas supply pipes 310, 320, 330, 340, and 350, mass flow controllers (MFCs) 312, 322, 332, 342, and 352, serving as flow controllers (flow control units), are sequentially installed from the upstream side. Additionally, valves 314, 324, 334, 344, and 354, serving as on / off valves, are installed in gas supply pipes 310, 320, 330, 340, and 350, respectively. Downstream of valves 314, 324, 334, 344, and 354 in gas supply pipes 310, 320, 330, 340, and 350, gas supply pipes 510, 520, 530, 540, and 550, respectively, are connected to supply inactive gases. In the gas supply pipes 510, 520, 530, 540, and 550, starting from the upstream side, MFCs 512, 522, 532, 542, and 552, which serve as flow controllers (flow control units), and valves 514, 524, 534, 544, and 554, which serve as switching valves, are installed sequentially.

[0030] Nozzles 410, 420, 430, 340, and 350 are connected to the front ends of gas supply pipes 310, 320, 330, 340, and 450, respectively. Nozzles 410, 420, 430, 440, and 450 are configured as L-shaped nozzles, with their horizontal portions extending through the side wall of manifold 209 and inner tube 204. The vertical portions of nozzles 410, 420, 430, 440, and 450 are disposed inside a preparation chamber 201a, which is formed in a groove shape (groove shape) that protrudes radially outward from the inner tube 204 and extends vertically. Within the preparation chamber 201a, nozzles are positioned upward along the inner wall of the inner tube 204 (above the wafer 200 alignment direction).

[0031] Nozzles 410, 420, 430, 440, and 450 are configured to extend from the lower region to the upper region of the processing chamber 201, and multiple gas supply holes 410a, 420a, 430a, 440a, and 450a are respectively provided at positions opposite to the wafer 200. Thus, processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a, 440a, and 450 of the nozzles 410, 420a, 430a, 440a, and 450a. Multiple gas supply holes 410a, 420a, 430a, 440a, and 450a are provided from the lower to the upper part of the inner tube 204, each having the same opening area and thus the same opening spacing. However, the gas supply holes 410a, 420a, 430a, 440a, and 450a are not limited to the above configuration. For example, the opening area can gradually increase from the bottom to the top of the inner tube 204. This makes the flow rate of gas supplied from the gas supply holes 410a, 420a, 430a, 440a, and 450a more uniform.

[0032] Gas supply holes 410a, 420a, 430a, 440a, and 450a of nozzles 410, 420, 430, 440, and 450a are provided at a height from the lower part to the upper part of the wafer cassette 217 (described later). Therefore, the processing gas supplied to the processing chamber 201 from the gas supply holes 410a, 420a, 430a, 440a, and 450a of nozzles 410, 420, 430, 440a, and 450a can supply the entire area of ​​the wafer 200 contained from the lower part to the upper part of the wafer cassette 217. Nozzles 410, 420, 430, 440, and 450 can be configured to extend from the lower region to the upper region of the processing chamber 201, but are preferably configured to extend to near the top of the wafer cassette 217.

[0033] A raw material gas containing a metal element (containing metal gas) is supplied to the processing chamber 201 from the gas supply pipe 310 via MFC 312, valve 314, and nozzle 410. For example, titanium tetrachloride (TiCl4) containing titanium (Ti) as a metal element and being a halogen-based raw material (halide, halogen-based titanium raw material) is used.

[0034] A reducing gas, used as the processing gas, is supplied from gas supply pipe 320 to processing chamber 201 via MFC 322, valve 324, and nozzle 420. The reducing gas can be, for example, a silane-based gas (e.g., SiH4) containing silicon (Si) and hydrogen (H) and free of halogens. SiH4 acts as a reducing agent.

[0035] The reaction gas, which is used as the processing gas, is supplied from the gas supply pipe 330 to the processing chamber 201 via MFC 332, valve 334, and nozzle 430. As the reaction gas, for example, ammonia (NH3) gas containing nitrogen (N) can be used.

[0036] Oxygen-containing gas, used as the treatment gas, is supplied from gas supply pipe 340 to treatment chamber 201 via MFC 342, valve 344, and nozzle 440. Examples of oxygen-containing gas that can be used include oxygen (O2), ozone (O3), and water vapor (H2O).

[0037] A halogenated gas containing a metal element, used as the processing gas, is supplied from gas supply pipe 350 to processing chamber 201 via MFC 352, valve 354, and nozzle 450. The metal element is, for example, tungsten fluoride (WF). Other halogenated gases that can be used include tungsten hexafluoride (WF6), nitrogen trifluoride (NF3), chlorine trifluoride (ClF3), fluorine (F2), and hydrogen fluoride (HF).

[0038] Inert gases, such as nitrogen (N2), are supplied to the processing chamber 201 from gas supply pipes 510, 520, 530, 540, and 550 via MFCs 512, 522, 532, 542, and 552, valves 514, 524, 534, 544, and 554, and nozzles 410, 420, 430, 440, and 450, respectively. Hereinafter, N2 gas will be used as an example of an inert gas, but in addition to N2 gas, other inert gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can also be used.

[0039] The processing gas supply system mainly consists of gas supply pipes 310, 320, 330, 340, and 350, MFCs 312, 322, 332, 342, and 352, valves 314, 324, 334, 344, and 354, and nozzles 410, 420, 430, 440, and 450. Alternatively, nozzles 410, 420, 430, 440, and 450 can be considered as the processing gas supply system alone. The processing gas supply system can also be simply referred to as the gas supply system. When raw material gas flows into the gas supply pipe 310, the raw material gas supply system mainly consists of gas supply pipe 310, MFC 312, and valve 314, but nozzle 410 can also be included in the raw material gas supply system. Similarly, when reducing gas flows into the gas supply pipe 320, the reducing gas supply system mainly consists of gas supply pipe 320, MFC 322, and valve 324, but nozzle 420 can also be included in the reducing gas supply system. Furthermore, when the reaction gas flows into the gas supply pipe 330, the reaction gas supply system mainly consists of the gas supply pipe 330, MFC 332, and valve 334; however, nozzle 430 can also be incorporated into the reaction gas supply system. When nitrogen-containing gas, which serves as the reaction gas, is supplied from the gas supply pipe 330, the reaction gas supply system can also be referred to as a nitrogen-containing gas supply system. Similarly, when oxygen-containing gas flows into the gas supply pipe 340, the oxygen-containing gas supply system mainly consists of the gas supply pipe 340, MFC 342, and valve 344; however, nozzle 440 can also be incorporated into the oxygen-containing gas supply system. Likewise, when halogen-containing gas flows into the gas supply pipe 350, the halogen-containing gas supply system mainly consists of the gas supply pipe 350, MFC 352, and valve 354; however, nozzle 450 can also be incorporated into the halogen-containing gas supply system. In addition, the inactive gas supply system mainly consists of gas supply pipes 510, 520, 530, 540, 550, MFCs 512, 522, 532, 542, 552, and valves 514, 524, 534, 544, 554.

[0040] In the gas supply method of this embodiment, gas is transported via nozzles 410, 420, 430, 440, and 450 arranged within a preparation chamber 201a, which is located within an annular longitudinal space defined by the inner wall of the inner tube 204 and the ends of multiple wafers 200. Furthermore, gas is ejected into the inner tube 204 from multiple gas supply holes 410a, 420a, 430a, 440a, and 450a located opposite the wafers in the nozzles 410, 420, 430, 440, and 450. More specifically, raw material gas, etc., is ejected in a direction parallel to the surface of the wafer 200 through the gas supply holes 410a of nozzle 410, 420a of nozzle 420, 430a of nozzle 430, 440a of nozzle 440, and 450a of nozzle 450.

[0041] The exhaust port (exhaust outlet) 204a is a through-hole formed on the side wall of the inner tube 204 at a position opposite to the nozzles 410, 420, 430, 440, 450. For example, it is a slit-like through-hole that is elongated in the vertical direction. Gas supplied from the gas supply holes 410a, 420a, 430a, 440a, 450a of the nozzles 410, 420, 430, 440a, 450a to the processing chamber 201 and flowing on the surface of the wafer 200 flows through the exhaust port 204a into the exhaust path 206 formed by the gap between the inner tube 204 and the outer tube 203. Furthermore, the gas flowing into the exhaust path 206 flows into the exhaust pipe 231 and is discharged outside the processing furnace 202.

[0042] Exhaust vents 204a are disposed at multiple locations opposite to the multiple wafers 200. Gas supplied from gas supply holes 410a, 420a, 430a, 440a, and 450a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally and then flows into the exhaust path 206 through the exhaust vents 204a. The exhaust vents 204a are not limited to being configured as slit-shaped through holes; they may also be composed of multiple holes.

[0043] In the manifold 209, an exhaust pipe 231 is provided for venting the atmosphere inside the processing chamber 201. From the upstream side, the exhaust pipe 231 is sequentially connected to a pressure sensor 245 (a pressure detector, or pressure sensing unit) for detecting the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 (a vacuum venting device). The APC valve 243 can be opened and closed while the vacuum pump 246 is operating, allowing for vacuum venting and stopping of vacuum venting within the processing chamber 201. Furthermore, by adjusting the valve opening while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted. The exhaust system mainly consists of an exhaust port 204a, an exhaust path 206, an exhaust pipe 231, an APC valve 243, and a pressure sensor 245. Including the vacuum pump 246 in the exhaust system is also an option.

[0044] Below the manifold 209, a sealing cap 219, serving as a furnace opening cover, is provided to airtightly seal the lower opening of the manifold 209. The sealing cap 219 is configured to abut against the lower end of the manifold 209 from a vertical downward direction. The sealing cap 219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the sealing cap 219, an O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209. On the side of the sealing cap 219 opposite to the processing chamber 201, a rotation mechanism 267 is provided to rotate the wafer cassette 217 containing the wafer 200. The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cap 219 and is connected to the wafer cassette 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer cassette 217. The sealing cap 219 is configured to move vertically upwards and downwards via a wafer cassette lift 115, which is vertically mounted outside the reaction tube 203 and serves as a lifting mechanism. The wafer cassette lift 115 is configured to move the wafer cassette 217 into and out of the processing chamber 201 by raising and lowering the sealing cap 219. The wafer cassette lift 115 is configured as a transport device (transport mechanism) for moving the wafer cassette 217 and the wafers 200 contained within it into and out of the processing chamber 201.

[0045] The wafer cassette 217, serving as a substrate support, is configured to hold multiple wafers 200, for example, 25 to 200 wafers 200, arranged horizontally and centered relative to each other, with intervals in the vertical direction. The wafer cassette 217 is made of heat-resistant materials such as quartz or SiC. At the lower part of the wafer cassette 217, a heat insulation plate 218 made of heat-resistant materials such as quartz or SiC is supported in multiple sections (not shown). This configuration makes it difficult for heat from the heater 207 to be transferred to the sealing cap 219 side. However, this embodiment is not limited to the above method. For example, the heat insulation plate 218 may not be provided at the lower part of the wafer cassette 217, and instead a heat insulation cylinder made of a cylindrical component made of heat-resistant materials such as quartz or SiC may be provided.

[0046] like Figure 2 As shown, the configuration is such that by installing a temperature sensor 263 as a temperature detector inside the inner tube 204, the electrical current supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby enabling the temperature inside the processing chamber 201 to achieve the desired temperature distribution. The temperature sensor 263, like the nozzles 410, 420, 430, 440, and 450, is configured in an L-shape and is installed along the inner wall of the inner tube 204.

[0047] like Figure 3As shown, the controller 121, serving as the control unit (control unit), is configured as a computer having a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, storage device 121c, and I / O interface 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, such as a touch panel.

[0048] The storage device 121c is composed of, for example, flash memory or an HDD (Hard Disk Drive). The storage device 121c stores control programs that control the operation of the substrate processing apparatus, and contains process recipes, such as the process and conditions of the semiconductor device manufacturing method described later, which can be read. The process recipes combine the various steps in the semiconductor device manufacturing method described later so that they are executed by the controller 121 to obtain a predetermined result, thus functioning as a program. Hereinafter, these process recipes, control programs, etc., will be simply referred to as programs. When using the term "program" in this specification, sometimes only the process recipe is included, sometimes only the control program is included, and sometimes both are included. RAM 121b is configured as a storage area (working area) for temporarily storing programs, data, etc., read by the CPU 121a.

[0049] I / O interface 121d is connected to the aforementioned MFC312, 322, 332, 342, 352, 512, 522, 532, 542, 552, valves 314, 324, 334, 344, 354, 514, 524, 534, 544, 554, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, wafer cell lift 115, etc.

[0050] CPU 121a is configured to read and execute control programs from storage device 121c, and simultaneously read recipes from storage device 121c in response to input of operation instructions from input / output device 122. CPU121a is also configured to control, according to the read recipe, various gas flow adjustment actions performed by MFC312, 322, 332, 342, 352, 512, 522, 532, 542, 552; opening and closing actions of valves 314, 324, 334, 344, 354, 514, 524, 534, 544, 554; opening and closing actions of APC valve 243; pressure adjustment actions performed by APC valve 243 based on pressure sensor 245; temperature adjustment actions of heater 207 based on temperature sensor 263; starting and stopping of vacuum pump 246; rotation and rotation speed adjustment actions of wafer cassette 217 performed by rotating mechanism 267; lifting and lowering actions of wafer cassette 217 performed by wafer cassette elevator 115; and the accommodating action of wafer 200 into wafer cassette 217.

[0051] The controller 121 can be configured to install the aforementioned program stored in an external storage device (e.g., magnetic tape, floppy disk, hard disk, CD, DVD, MO, USB memory, memory card, etc.) 123 into a computer. The storage device 121c and the external storage device 123 constitute a recording medium that can be read by a computer. Hereinafter, these will be simply referred to collectively as a recording medium. The recording medium in this specification may sometimes include only the storage device 121c, sometimes only the external storage device 123, or sometimes both. Providing the program to the computer may also be done without using the external storage device 123, but rather via communication methods such as the Internet or a dedicated line.

[0052] (2) Substrate processing process

[0053] As a step in the manufacturing process of a semiconductor device, for example, in the process of forming a metal film, such as a gate electrode, on a wafer 200, the following steps are used: Figure 4 The process of forming the metal 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.

[0054] The substrate processing step (semiconductor device manufacturing step) according to this embodiment includes a preparation step and a thinning step. In the preparation step, a wafer 200 on which a TiN film containing a metal is formed on its surface is prepared. In the thinning step, the TiN film is thinned by pulsed supply of WF6 gas, a halogen-containing gas, to the wafer 200 on which the TiN film is formed. Here, thinning refers to making the metal-containing film thinner by etching.

[0055] In addition, during the thinning process, before the pulse supply of WF6 gas, O2 gas, which is an oxygen-containing gas, is supplied, and O2 gas and WF6 gas are supplied alternately.

[0056] Here, "pulse supply" means intermittent gas supply.

[0057] In this specification, the term "wafer" is used in two ways: as "the wafer itself" and as "a laminate of a wafer and a predetermined layer, film, etc., formed on its surface." Similarly, the term "wafer surface" is used in two ways: as "the surface of the wafer itself" and "the surface of a predetermined layer or film formed on the wafer." The term "substrate" is used in the same way as "wafer."

[0058] (Wafer loading)

[0059] After multiple wafers 200 are loaded into wafer cassette 217 (wafer loading), as follows Figure 1 As shown, the wafer cassette 217, which supports multiple wafers 200, is lifted by the wafer cassette elevator 115 and moved into the processing chamber 201 (wafer cassette mounting). In this state, the lower end of the reaction tube 203 is closed by the sealing cap 219 via the O-ring 220.

[0060] (Pressure and temperature adjustments)

[0061] Vacuum pump 246 performs vacuum exhaust, bringing the processing chamber 201 to the desired pressure (vacuum level). The pressure within the processing chamber 201 is then measured by pressure sensor 245, and the APC valve 243 is controlled based on this pressure information (pressure adjustment). Vacuum pump 246 continues to operate continuously, at least until the processing of wafer 200 is complete. Additionally, heater 207 heats the processing chamber 201 to the desired temperature. The power supply to heater 207 is controlled based on temperature information detected by temperature sensor 263, resulting in a desired temperature distribution within the processing chamber 201 (temperature adjustment). Heating of the processing chamber 201 by heater 207 continues at least until the processing of wafer 200 is complete.

[0062] [Film Forming Process]

[0063] (Supply TiCl4 gas, first step)

[0064] Valve 314 is opened, allowing TiCl4 gas, used as the raw material gas, to flow into the gas supply pipe 310. The flow rate of the TiCl4 gas is adjusted by MFC 312, and it is supplied to the processing chamber 201 through the gas supply port 410a of nozzle 410, and exhausted through exhaust pipe 231. At this time, TiCl4 gas is supplied to wafer 200. Simultaneously, valve 514 is opened, allowing inactive gases such as N2 gas to flow into the gas supply pipe 510. The flow rate of the N2 gas flowing into the gas supply pipe 510 is adjusted by MFC 512, and it is supplied to the processing chamber 201 along with the TiCl4 gas, and exhausted through exhaust pipe 231. At this time, to prevent TiCl4 gas from entering nozzles 420, 430, 440, and 450, valves 524, 534, 544, and 554 are opened, allowing N2 gas to flow into the gas supply pipes 520, 530, 540, and 550, respectively. N2 gas is supplied to the treatment chamber 201 through gas supply pipes 320, 330, 340, 350 and nozzles 420, 430, 440, 450, and is exhausted through exhaust pipe 231.

[0065] At this point, APC valve 243 is adjusted to bring the pressure inside processing chamber 201 to, for example, a range of 1 to 3990 Pa. The supply flow rate of TiCl4 gas controlled by MFC 312 is set to, for example, a range of 0.1 to 2.0 slm. The supply flow rates of N2 gas controlled by MFCs 512, 522, 532, 542, and 552 are each set to, for example, a range of 0.1 to 20 slm. At this point, the temperature of heater 207 is set to a temperature that brings the temperature of wafer 200 to, for example, a range of 300 to 500°C.

[0066] At this point, the gases flowing in processing chamber 201 are only TiCl4 gas and N2 gas. By supplying TiCl4 gas, a Ti-containing layer is formed on wafer 200 (the substrate film on the surface). The Ti-containing layer can be a Ti layer containing Cl, an adsorbed TiCl4 layer, or both.

[0067] (Removal of residual gas, second step)

[0068] After a predetermined time elapsed since the start of TiCl4 gas supply, for example, 0.01 to 10 seconds, valve 314 is closed to stop the TiCl4 gas supply. At this time, APC valve 243 of exhaust pipe 231 remains open, and vacuum pump 246 vents the processing chamber 201, removing any unreacted TiCl4 gas remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer. Meanwhile, valves 514, 524, 534, 544, and 554 remain open, continuing the supply of N2 gas to the processing chamber 201. N2 gas acts as a purging gas, enhancing the removal of unreacted TiCl4 gas remaining in the processing chamber 201 or contributing to the formation of the Ti-containing layer.

[0069] (Supply NH3 gas, third step)

[0070] After removing residual gas from processing chamber 201, valve 334 is opened, allowing NH3 gas, used as a reaction gas, to flow into gas supply pipe 330. The flow rate of NH3 gas is adjusted by MFC 332, and it is supplied to processing chamber 201 from gas supply port 430a of nozzle 430, and exhausted from exhaust pipe 231. At this time, NH3 gas is supplied to wafer 200. Simultaneously, valve 534 is opened, allowing N2 gas to flow into gas supply pipe 530. The flow rate of N2 gas flowing in gas supply pipe 530 is adjusted by MFC 532. N2 gas and NH3 gas are supplied together to processing chamber 201 and exhausted from exhaust pipe 231. To prevent NH3 gas from entering nozzles 410, 420, 440, and 450, valves 514, 524, 544, and 554 are opened, allowing N2 gas to flow into gas supply pipes 510, 520, 540, and 550, respectively. N2 gas is supplied to the treatment chamber 201 through gas supply pipes 310, 320, 340, 350 and nozzles 410, 420, 440, 450, and is exhausted through exhaust pipe 231.

[0071] At this point, APC valve 243 is adjusted to bring the pressure inside processing chamber 201 to, for example, a range of 1 to 3990 Pa. The supply flow rate of NH3 gas controlled by MFC 332 is set to, for example, a range of 0.1 to 30 slm. The supply flow rates of N2 gas controlled by MFCs 512, 522, 532, 542, and 552 are each set to, for example, a range of 0.1 to 30 slm. The time for supplying NH3 gas to wafer 200 is set to, for example, a range of 0.01 to 30 seconds. The temperature of heater 207 is set to the same temperature as in the TiCl4 gas supply step.

[0072] At this point, the gases flowing within the processing chamber 201 are only NH3 and N2 gases. The NH3 gas undergoes a displacement reaction with at least a portion of the Ti-containing layer formed on the wafer 200 in the first step. During the displacement reaction, the Ti contained in the Ti-containing layer combines with the N contained in the NH3 gas to form a TiN layer on the wafer 200.

[0073] (Removal of residual gas, fourth step)

[0074] After the TiN layer is formed, valve 334 is closed to stop the supply of NH3 gas. Then, following the same process as described above for removing residual gas, unreacted NH3 gas or reaction byproducts remaining in the treatment chamber 201 or contributing to the formation of the TiN layer are removed from the treatment chamber 201.

[0075] (Number of scheduled implementations)

[0076] By repeating the first to fourth steps of the above process a predetermined number of times (n times), a predetermined thickness (e.g., greater than) is formed on wafer 200. A thick TiN film with membrane continuity.

[0077] [Thinning process]

[0078] (Supplying O2 gas, step 5)

[0079] Valve 344 is opened, allowing O2 gas, which contains oxygen, to flow into the gas supply pipe 340. The O2 gas flow rate is adjusted by MFC 342 and supplied to the processing chamber 201 through the gas supply orifice 440a of nozzle 440, and exhausted through exhaust pipe 231. At this time, O2 gas is supplied to wafer 200. Simultaneously, valve 544 is opened, allowing inactive gases such as N2 gas to flow into the gas supply pipe 540. The N2 gas flowing in the gas supply pipe 540 has its flow rate adjusted by MFC 542 and is supplied to the processing chamber 201 along with the O2 gas, and exhausted through exhaust pipe 231. At this time, valves 514, 524, 534, and 554 are closed, stopping the supply of N2 gas from nozzles 410, 420, 430, and 450.

[0080] At this point, APC valve 243 is adjusted to bring the pressure inside processing chamber 201 to, for example, a range of 0.1 to 3990 Pa. The supply flow rate of O2 gas, controlled by MFC 342, is set to, for example, a range of 0.1 to 10 slm. The supply flow rate of N2 gas, controlled by MFC 542, is set to, for example, a range of 0.1 to 20 slm. At this point, the temperature of heater 207 is set to, for example, a range of 300 to 500°C, the same as the film deposition temperature used in the film deposition process, and is kept stable. It should be noted that the temperature in this process can also be set differently from the film deposition temperature.

[0081] At this time, the gas flowing in the processing chamber 201 is O2 gas. By supplying O2 gas, the TiN film on the wafer 200 (the substrate film on the surface) is oxidized, and titanium oxynitride (TiNO) is formed on the surface of the TiN film.

[0082] (Remove residual gas, step six)

[0083] After a predetermined time has elapsed since the start of O2 gas supply, valve 344 is closed, stopping the O2 gas supply. At this time, APC valve 243 of exhaust pipe 231 remains open, and vacuum pump 246 vents the processing chamber 201, removing any unreacted O2 gas remaining in the processing chamber 201 or that contributed to the formation of the TiNO layer. Then, valve 544 remains open, and valves 514, 524, 534, and 554 are opened to begin supplying N2 gas into the processing chamber 201. N2 gas acts as a purging gas, enhancing the removal of unreacted O2 gas remaining in the processing chamber 201 or that contributed to the formation of the TiNO layer.

[0084] (Supply WF6 gas, step seven)

[0085] After removing residual gas from processing chamber 201, valve 354 is opened, allowing WF6 gas (containing halogen) to flow into gas supply pipe 350. The flow rate of WF6 gas is adjusted by MFC 352, and it is supplied to processing chamber 201 from gas supply port 450a of nozzle 450, and exhausted from exhaust pipe 231. At this time, WF6 gas is supplied to wafer 200. Simultaneously, valve 554 is opened, allowing inactive gases such as N2 gas to flow into gas supply pipe 550. The flow rate of N2 gas flowing in gas supply pipe 550 is adjusted by MFC 552, and it is supplied to processing chamber 201 along with WF6 gas, and exhausted from exhaust pipe 231. At this time, valves 514, 524, 534, and 544 are closed, stopping the supply of N2 gas from nozzles 410, 420, 430, and 440.

[0086] At this point, adjust APC valve 243 to bring the pressure inside processing chamber 201 to, for example, a range of 0.1 to 6650 Pa. The supply flow rate of WF6 gas, controlled by MFC352, is set to, for example, a range of 0.01 to 10 slm. The supply flow rate of N2 gas, controlled by MFC552, is set to, for example, a range of 0.1 to 30 slm. The time for supplying WF6 gas to wafer 200 is set to, for example, a range of 0.01 to 30 seconds.

[0087] At this point, the gas flowing in the processing chamber 201 is WF6 gas. By supplying WF6 gas, the TiNO layer formed on the wafer 200 in the fifth step is etched.

[0088] (Remove residual gas, step eight)

[0089] After a predetermined time has elapsed since the start of WF6 gas supply, valve 354 is closed to stop the supply of WF6 gas.

[0090] Then, following the same process as the removal of residual gases described above, the unreacted WF6 gas remaining in the treatment chamber 201 or contributing to the formation of the TiN layer, and the TiWF gas as a reaction byproduct, will be removed. x O y It will be discharged from the treatment chamber 201.

[0091] (Number of scheduled implementations)

[0092] By repeating steps 5 through 8 above at least once (a predetermined number of times (m times)), the TiNO layer on wafer 200 is etched to form a predetermined thickness (e.g., 5 to less than). TiN film. The above cycle is preferably repeated multiple times.

[0093] That is, by alternately pulse-supplying O2 gas and WF6 gas, the reaction of TiWF, which is a byproduct of the reaction between WF6 gas and TiN layer, can be improved. x O y The removal efficiency is high. Furthermore, the amount of thinning (etching) can be controlled via pulse supply.

[0094] [Number of scheduled implementations]

[0095] By sequentially performing the above-described film formation process (steps 1 to 4) and the thinning process (steps 5 to 8) at least once (a predetermined number of times (1 time)), a TiN film of predetermined thickness with film continuity can be formed on wafer 200. It should be noted that the film formation process can also be performed multiple times to form the TiN film together, followed by the thinning process.

[0096] (Post-purge and atmospheric pressure recovery)

[0097] N2 gas is supplied to the processing chamber 201 through gas supply pipes 510-550, and exhaust gas is discharged through exhaust pipe 231. The N2 gas acts as a purging gas, thereby purging the processing chamber 201 with this inactive gas to remove residual gases and byproducts (post-purging). Then, the atmosphere in the processing chamber 201 is replaced with the inactive gas (inactive gas replacement), and the pressure in the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0098] (Wafer removal)

[0099] Then, the wafer cassette lifter 115 lowers the sealing cap 219, opening the lower end of the reaction tube 203. Next, the processed wafer 200, supported by the wafer cassette 217, is moved from the lower end of the reaction tube 203 to the outside of the reaction tube 203 (wafer cassette disassembly). Finally, the processed wafer 200 is removed from the wafer cassette 217 (wafer unloading).

[0100] (3) Examples

[0101] Figure 5 (A) shows the use of the above-described substrate processing apparatus 10 through the above-described Figure 4 The film deposition process was formed on wafer 200. A schematic diagram of the TiN film. Figure 5 (B) and Figure 5 (C) shows the use of the above-described substrate processing apparatus 10 through the above-described Figure 4 The film deposition and thinning processes are formed on wafer 200. A schematic diagram of the TiN film.

[0102] like Figure 5 As shown in (A), if a film is formed on wafer 200 solely through a film deposition process... The TiN film, when discontinuously formed as islands on the wafer 200, achieves a surface coverage of 27.8%. On the other hand, as... Figure 5 As shown in (B), a film is formed on wafer 200 through a film deposition process. After the TiN film (100% surface coverage) is applied, as follows: Figure 5 As shown in (C), a thinning process is performed to form Thus, a TiN film is continuously formed. Moreover, the surface coverage remains at 100% in this case.

[0103] That is, forming on wafer 200 When forming thin films on the left and right sides, it is possible to form them on wafer 200. After etching the relatively thick TiN film on the left and right sides, a film continuity is formed. The TiN film is about the thickness of a thin film.

[0104] That is, according to this embodiment, after forming a TiN film of a predetermined thickness (a thicker film thickness with film continuity) on the wafer 200, etching is performed until a predetermined thickness (a thinner film thickness with film continuity) is reached. This reduces the resistivity of the TiN film and improves the adhesion between the W film and the insulating film, preventing fluorine (F) contained in the W film from diffusing into the insulating film.

[0105] (4) Effects based on this embodiment

[0106] According to this embodiment, one or more of the following effects can be obtained.

[0107] (a) It can form TiN films with membrane continuity.

[0108] (b) It can improve the adhesion between the W film and the insulating film.

[0109] (c) It can prevent the fluorine (F) contained in the W film from diffusing into the insulating film.

[0110] (d) It can reduce resistivity.

[0111] (5) Variations

[0112] (Variation Example 1)

[0113] The difference between Modified Example 1 and the above embodiment lies in the film-forming process. Specifically, in the first step of the film-forming process of the above embodiment, SiH4 gas is supplied during the TiCl4 gas supply process. Figure 6 This is a graph showing the timing of gas supply during the film-forming process in Modified Example 1, which is applicable to this embodiment. In the following modifications, only the differences from the above embodiment will be described in detail.

[0114] [Film Forming Process]

[0115] (Supply TiCl4 gas, first step)

[0116] TiCl4 gas is supplied into the processing chamber 201 through the same process as the first step of the film formation process in the above embodiment. At this time, the gas flowing in the processing chamber 201 is only TiCl4 gas and N2 gas. By supplying TiCl4 gas, a Ti-containing layer is formed on the substrate film on the wafer 200 (the surface).

[0117] (Supplying SiH4 gas)

[0118] After a predetermined time elapsed since the start of TiCl4 gas supply, for example, 0.01 to 5 seconds, valve 324 is opened, allowing SiH4 gas, used as a reducing gas, to flow into gas supply pipe 320. The SiH4 gas flow rate is adjusted by MFC 322 and supplied from the gas supply port 420a of nozzle 420 into processing chamber 201, and exhausted from exhaust pipe 231. Simultaneously, valve 524 is opened, allowing inactive gases such as N2 gas to flow into gas supply pipe 520. The N2 gas flowing in gas supply pipe 520 is adjusted by MFC 522 and supplied to processing chamber 201 along with SiH4 gas, and exhausted from exhaust pipe 231. At this time, to prevent TiCl4 gas and SiH4 gas from entering nozzles 430, 440, and 450, valves 534, 544, and 554 are opened, allowing N2 gas to flow into gas supply pipes 530, 540, and 550. At this point, the wafer 200 is simultaneously supplied with TiCl4 gas, SiH4 gas, and N2 gas. That is, there is at least one point in time when TiCl4 gas and SiH4 gas are supplied simultaneously.

[0119] At this point, adjust APC valve 243 to bring the pressure inside processing chamber 201 to, for example, a range of 130–3990 Pa. If the pressure inside processing chamber 201 is below 130 Pa, Si contained in the SiH4 gas will enter the Ti-containing layer, increasing the Si content in the TiN film and potentially transforming it into a TiSiN film. The same applies when the pressure inside processing chamber 201 is above 3990 Pa; Si contained in the SiH4 gas will enter the Ti-containing layer, increasing the Si content in the TiN film and potentially transforming it into a TiSiN film. Therefore, excessively low or high pressure inside processing chamber 201 will alter the elemental composition of the film to be formed. The supply flow rate of SiH4 gas controlled by MFC 322 is set to, for example, a range of 0.1–5 slm. The supply flow rates of N2 gas controlled by MFCs 512, 522, 532, 542, and 552 are set to, for example, a range of 0.01–20 slm. At this point, the temperature of heater 207 is set to the same temperature as the step of supplying TiCl4 gas.

[0120] After a predetermined time elapsed since the start of TiCl4 gas supply, for example, 0.01 to 10 seconds, valve 314 of gas supply pipe 310 is closed, stopping the supply of TiCl4 gas. At this time, to prevent SiH4 gas from entering nozzle 410, valve 514 remains open, allowing N2 gas to flow into gas supply pipes 510, 530, 540, and 550. N2 gas is supplied to processing chamber 201 via gas supply pipes 310, 330, 340, and 350 and nozzles 410, 430, 440, and 450, and is exhausted from exhaust pipe 231. At this point, both SiH4 gas and N2 gas are supplied to wafer 200.

[0121] (Removal of residual gas, second step)

[0122] After a predetermined time elapsed since the start of SiH4 gas supply, for example, 0.01 to 60 seconds, valve 324 is closed to stop the SiH4 gas supply. At this time, APC valve 243 of exhaust pipe 231 remains open, and vacuum pump 246 performs vacuum venting of the processing chamber 201, removing any unreacted TiCl4 gas or SiH4 gas remaining in the processing chamber 201 that contributes to the formation of the Ti-containing layer. Meanwhile, valves 514, 524, 534, 544, and 554 remain open, maintaining the supply of N2 gas to the processing chamber 201. N2 gas acts as a purging gas, enhancing the removal of any remaining unreacted TiCl4 gas or SiH4 gas from the processing chamber 201. Here, HCl, a growth hindrance, reacts with SiH4, being discharged from the processing chamber 201 as silicon tetrachloride (SiCl4) and H2.

[0123] (Supply NH3 gas, third step)

[0124] After removing the residual gas in the treatment chamber 201, NH3 gas is supplied to the treatment chamber 201 according to the same process as the third step in the film formation process of the above embodiment.

[0125] (Removal of residual gas, fourth step)

[0126] After a predetermined time has elapsed since the start of NH3 gas supply, valve 334 is closed to stop the NH3 gas supply. At this time, APC valve 243 of exhaust pipe 231 remains open, and vacuum pump 246 performs vacuum exhaust in processing chamber 201. Through the same processing procedure as the fourth step in the film formation process of the above embodiment, unreacted NH3 gas or reaction byproducts remaining in processing chamber 201 or contributing to the formation of TiN layer are removed from processing chamber 201.

[0127] (Number of scheduled implementations)

[0128] By repeating the first to fourth steps of the above process a predetermined number of times (n times), a predetermined thickness (e.g., greater than) is formed on wafer 200. A thick TiN film with membrane continuity.

[0129] Furthermore, in this modified example, by performing the thinning process in the same manner as in the above-described embodiment, a result similar to [the previous embodiment] can also be obtained. Figure 4 The film-forming process shown achieves the same effect.

[0130] (Variation Example 2)

[0131] The difference between Modified Example 2 and the above-described embodiment lies in the thinning process. Specifically, the fifth step of supplying O2 gas and the sixth step of removing residual gas in the thinning process of the above-described embodiment are omitted. Figure 7 This is a graph showing the timing of gas supply during the thinning process of Modified Example 2 applicable in this embodiment.

[0132] (Supply WF6 gas, step seven)

[0133] After removing residual gas from processing chamber 201, valve 354 is opened, allowing WF6 gas (containing halogen) to flow into gas supply pipe 350. The flow rate of WF6 gas is adjusted by MFC 352, and it is supplied to processing chamber 201 from gas supply port 450a of nozzle 450, and exhausted from exhaust pipe 231. At this time, WF6 gas is supplied to wafer 200. Simultaneously, valve 554 is opened, allowing inactive gases such as N2 gas to flow into gas supply pipe 550. The flow rate of N2 gas flowing in gas supply pipe 550 is adjusted by MFC 552, and it is supplied to processing chamber 201 along with WF6 gas, and exhausted from exhaust pipe 231. At this time, valves 514, 524, 534, and 544 are closed, stopping the supply of N2 gas from nozzles 410, 420, 430, and 440.

[0134] At this time, the gas flowing in the processing chamber 201 is WF6 gas. By supplying WF6 gas, the TiN film formed on the wafer 200 through the film deposition process is etched.

[0135] (Remove residual gas, step eight)

[0136] After a predetermined time has elapsed since the start of WF6 gas supply, valve 354 is closed to stop the supply of WF6 gas.

[0137] Then, through the same treatment process as step eight in the above-mentioned thinning process, the unreacted WF6 gas remaining in the treatment chamber 201 or contributing to the formation of the TiN layer, and the TiWF gas as a reaction byproduct, will be removed.x It will be discharged from the treatment chamber 201.

[0138] (Number of scheduled implementations)

[0139] By repeating steps seven and eight above at least once (a predetermined number of times (m times)), the TiN layer on wafer 200 is etched to form a predetermined thickness (e.g., 5 to less than). TiN film. The above cycle is preferably repeated multiple times.

[0140] That is, by pulsed supply of WF6 gas, the reaction of TiWF, which is a byproduct of the reaction between WF6 gas and TiN layer, can be improved. x The efficiency of removal. Furthermore, by using pulse supply, the amount of thinning (etching) can be controlled, resulting in... Figure 4 The film-forming process shown achieves the same effect.

[0141] (Variation Example 3)

[0142] The difference between Modified Example 3 and the above-described embodiment lies in the thinning process. Specifically, the above-described process is performed in overlapping steps. Figure 4 The O2 gas supply in the fifth step and the WF6 gas supply in the seventh step of the film formation process shown are in the thinning step of the film formation process. Figure 8 This is a graph showing the timing of gas supply during the thinning process of Modified Example 3 applicable in this embodiment.

[0143] That is, by using the timing of gas supply in this modified example, we can also obtain the result related to... Figure 4 The same film formation process shown applies to etching the TiNO layer on wafer 200 to form a predetermined thickness (e.g., 5 to less than). TiN film. It should be noted that O2 gas and WF6 gas can be supplied simultaneously.

[0144] That is, by supplying O2 gas and WF6 gas in an overlapping manner, and by pulsedly supplying WF6 gas, it is possible to improve the reaction yield of TiWF6, which is a reaction byproduct of WF6 gas and TiN layer. x O y The removal efficiency is high. Furthermore, the amount of thinning (etching) can be controlled via pulse supply.

[0145] It should be noted that in the above embodiments, the use of WF6 gas as the halogen-containing gas containing halogen elements and metallic elements in the thinning process was described. However, this disclosure is not limited to this, and it is also applicable when using halogen-containing gases that do not contain metallic elements. Examples of halogen-containing gases that do not contain metallic elements include NF3 gas, ClF3 gas, F2 gas, and HF gas. It should be noted that the halogen elements are Cl, F, Br, etc., and the metallic elements are W, Ti, Ta, Mo, Zr, Hf, Al, Si, Ge, Ga, etc. Gases containing these elements can be applied. It should also be noted that the halogen-containing gas can be a gas that further contains oxygen (O). For example, MoO2Cl2, MoOCl4, etc.

[0146] Furthermore, in the above embodiments, O2 gas was described as the oxygen-containing gas used in the thinning process, but this disclosure is not limited to this and can also be applied when using oxygen-containing gases such as O3 gas and H2O gas.

[0147] Furthermore, while the above embodiments have described the process of thinning a TiN film as an example, this method is also applicable to metal films other than TiN films. For example, the metal elements used are W, Ta, Mo, Zr, Hf, Al, Si, Ge, Ga, or elements from the same group as these elements, and transition metals. Films of these elemental substances, films of these metals compounded with nitrogen (nitride films), and films of these metals compounded with oxygen (oxide films) are also applicable. For these films, only steps seven and five and seven of the above embodiments need to be performed. The gas supplied in steps seven and five can be appropriately selected based on the desired film.

[0148] Furthermore, the above embodiments were described using a substrate processing apparatus for forming films using a batch-type vertical assembly that processes multiple substrates at a time. However, this disclosure is not limited to this; for example, it can also be appropriately applied when forming films using a single-piece substrate processing apparatus that processes one or more substrates at a time. Additionally, the above embodiments were described using a substrate processing apparatus with a hot-wall type furnace for forming thin films. However, this disclosure is not limited to this; it can also be appropriately applied when forming thin films using a substrate processing apparatus with a cold-wall type furnace. The processing conditions in these cases can be, for example, the same as those in the above embodiments.

[0149] For example, in the use of having Figure 9When forming a film using the substrate processing apparatus of the processing furnace 302 shown in (A), this disclosure can also be suitably applied. The processing furnace 302 includes: a processing container 303 for forming a processing chamber 301, a dispersion nozzle 303s for supplying gas into the processing chamber 301 in a spray manner, a support platform 317 for supporting one or more wafers 200 in a horizontal orientation, a rotation shaft 355 for supporting the support platform 317 from below, and a heater 307 disposed in the support platform 317. The inlet (gas inlet) of the dispersion nozzle 303s is connected to a gas supply interface 332a for supplying the raw material gas, a gas supply interface 332b for supplying the reaction gas, and a gas supply interface 332c for supplying the halogen-containing gas. The gas supply interface 332a is connected to the same raw material gas supply system as the raw material gas supply system of the above embodiment. The gas supply interface 332b is connected to the same reaction gas supply system as the reaction gas supply system of the above embodiment. Gas supply interface 332c is connected to the same gas supply system as the halogen-containing gas supply system described above. A gas dispersion plate is provided at the outlet (gas exhaust port) of the dispersion nozzle 303s to supply gas into the processing chamber 301 in a spray pattern. An exhaust interface 331 for venting gas from the processing chamber 301 is provided in the processing container 303. The exhaust interface 331 is connected to the same exhaust system as the exhaust system described in the above embodiment.

[0150] Additionally, for example, when using a device with Figure 9 When forming a film using the substrate processing apparatus of the processing furnace 402 shown in (B), this disclosure can also be suitably applied. The processing furnace 402 includes: a processing container 403 forming a processing chamber 401; a support stage 417 supporting one or more wafers 200 in a horizontal orientation; a rotation axis 455 supporting the support stage 417 from below; a heating lamp 407 irradiating the wafers 200 in the processing container 403; and a quartz window 403w through which light passes through the heating lamp 407. The processing container 403 is connected to a gas supply interface 432a for supplying the raw material gas, a gas supply interface 432b for supplying the reaction gas, and a gas supply interface 432c for supplying the halogen-containing gas. Gas supply interface 432a is connected to the same raw material gas supply system as the raw material gas supply system of the above embodiment. Gas supply interface 432b is connected to the same reaction gas supply system as the reaction gas supply system of the above embodiment. Gas supply interface 432c is connected to the same gas supply system as the halogen-containing gas supply system of the above embodiment. The processing container 403 is provided with an exhaust port 431 for venting exhaust from the processing chamber 401. The exhaust port 431 is connected to an exhaust system that is the same as the exhaust system in the above embodiment.

[0151] Alternatively, TiN films can also be formed using a CVD (Chemical Vapor Deposition) apparatus, which is an example of a substrate processing device.

[0152] When using these substrate processing devices, film formation can also be performed using the same process and processing conditions as described in the above embodiments.

[0153] The process formulations (programs describing the processing procedures, processing conditions, etc.) used for forming these various thin films are preferably prepared individually (multiple formulations) according to the substrate processing requirements (film type, composition ratio, film quality, film thickness, processing procedures, processing conditions, etc.). Furthermore, it is preferable to select a suitable process formulation from among the multiple formulations at the start of substrate processing, based on the substrate processing requirements. Specifically, it is preferable to pre-store (install) the multiple process formulations prepared individually according to the substrate processing requirements in the storage device 121c of the substrate processing apparatus via a communication circuit and a recording medium (external storage device 123) for recording the process formulations. Moreover, it is preferable that at the start of substrate processing, the CPU 121a of the substrate processing apparatus selects a suitable process formulation from the multiple process formulations stored in the storage device 121c according to the substrate processing requirements. With this configuration, thin films of various film types, composition ratios, film qualities, and film thicknesses can be formed universally and reproducibly using a single substrate processing apparatus. In addition, it can reduce the operator's workload (the burden of inputting processing procedures, processing conditions, etc.), avoid operational errors, and enable the rapid start of substrate processing.

[0154] Furthermore, this disclosure can also be implemented, for example, by changing the process recipe of an existing substrate processing apparatus. When changing the process recipe, the process recipe involved in this disclosure can be installed in an existing substrate processing apparatus via a communication circuit or a recording medium recording the process recipe, or the input / output device of an existing substrate processing apparatus can be operated to change the process recipe itself to the process recipe involved in this disclosure.

[0155] The above describes various typical embodiments of this disclosure, but this disclosure is not limited to these embodiments and can be applied in appropriate combinations.

[0156] Symbol Explanation

[0157] 10: Substrate processing apparatus, 121: Controller, 200: Wafer (substrate), 201: Processing chamber.

Claims

1. A substrate processing method, comprising: The process of preparing a substrate on which a continuous metal nitride film has been formed on the surface, and The metal nitride film is thinned by pulsedly supplying a gas containing metal and halogen to the metal nitride film instead of supplying oxygen-containing gas. The gas containing metals and halogens contains tungsten hexafluoride.

2. The method according to claim 1, wherein, Prior to the process of thinning the metal nitride film, the following process is performed: A process of forming a metal nitride film on a substrate by supplying a gas containing metal and halogen and a nitrogen-containing gas a predetermined number of times, or by supplying a gas containing metal and halogen, a silane-based gas, and a nitrogen-containing gas a predetermined number of times.

3. The method according to claim 1, wherein, The process further includes the formation of the metal nitride film on the substrate on which the insulating film is formed.

4. The method according to claim 3, wherein, The metal nitride film The following thickness forms islands when it is formed on the insulating film.

5. The method according to claim 3, wherein, When the metal nitride film is formed on the substrate on which the insulating film is formed, the metal nitride film is formed to a thickness that allows for film continuity.

6. The method according to claim 4, wherein, When the metal nitride film is formed on the substrate on which the insulating film is formed, the metal nitride film is formed to a thickness that allows for film continuity.

7. The method according to claim 1, wherein, The metal nitride film is not subjected to oxidation treatment.

8. The method according to claim 1, wherein, The metal nitride film does not contain oxygen.

9. The method according to claim 1, wherein, The metal nitride film is a titanium nitride film.

10. The method according to claim 9, wherein, Remove TiWFx generated during the thinning process by pulse supplying the metal nitride film with a gas containing metal and halogen.

11. A method for manufacturing a semiconductor device, comprising: The process of preparing a substrate on which a continuous metal nitride film has been formed on the surface, and The metal nitride film is thinned by pulsedly supplying a gas containing metal and halogen to the metal nitride film instead of supplying oxygen-containing gas. The gas containing metals and halogens contains tungsten hexafluoride.

12. A computer-readable recording medium having a program that causes a substrate processing apparatus to perform the following processes via a computer: The process of preparing a substrate with a continuous metal nitride film formed on its surface, and The process of thinning the metal nitride film involves pulsely supplying a gas containing tungsten hexafluoride (THF) to the metal nitride film instead of oxygen-containing gas. This THF-containing gas is a gas containing both metal and halogen.

13. A substrate processing apparatus comprising: A gas supply system for supplying gas to a substrate, and The control unit is configured to achieve the following control: by controlling the gas supply system, instead of supplying oxygen-containing gas to the continuous metal nitride film, a gas containing metal and halogen is pulsedly supplied to the metal nitride film, thereby thinning the metal nitride film. The gas containing metals and halogens contains tungsten hexafluoride.

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