Film post-processing method and substrate processing device

Abstract

The occurrence of metal contamination and the attachment of particles to a zirconium film formed on a substrate are suppressed. A post-film deposition method is provided, comprising a processing space in which a processing gas containing zirconium chloride is supplied while the substrate is contained to perform a film deposition process for forming a film composed of zirconium on the substrate, and a chamber in which at least a portion exposed to the processing space is composed of a material containing aluminum, wherein the processing gas discharge process for stopping the supply of the processing gas and discharging the processing gas from the processing space after the film deposition process, and a hydrogen nitride-based gas supply process for supplying a hydrogen nitride-based gas into the processing space after the processing gas discharge process.

Description

Technology Field

[0001] The present disclosure relates to a film post-processing method and a substrate processing apparatus. Background Technology

[0002] For example, in logic ICs as semiconductor devices, titanium (Ti) silicide or nickel (Ni) silicide is used as the source or drain contact material. However, with the miniaturization of devices in recent years, the contact portion is also reduced, so the resistance of the contact portion tends to increase. Therefore, in order to lower the resistance of the contact portion, it is being considered to use zirconium (Zr) silicide, a low-resistance metal, as the contact material.

[0003] Such zirconium silicide is formed by performing heat treatment on a zirconium film formed by spatter, deposition, or ion plating on a wafer, which is a silicon-based semiconductor substrate (see, for example, Patent Document 1). This zirconium film is formed on the wafer by, for example, supplying a source gas that serves as a raw material for the zirconium film into a chamber made of aluminum and generating plasma from the source gas inside the chamber. Prior art literature

[0004] International Publication No. 2007 / 063908 The problem to be solved

[0005] The technology according to the present disclosure suppresses the occurrence of metal contamination and the attachment of particles to a zirconium film formed on a substrate. means of solving the problem

[0006] One aspect of the technology according to the present disclosure is a post-film deposition method having a processing space in which a processing gas containing zirconium chloride is supplied while a substrate is contained to perform a film deposition process for forming a film composed of zirconium on said substrate, and a chamber having at least a portion of which exposed to said processing space composed of a material containing aluminum, wherein the processing gas discharge process for stopping the supply of said processing gas and discharging said processing gas from said processing space, and a hydrogen nitride-based gas supply process for supplying a hydrogen nitride-based gas into said processing space after said film deposition process. Effects of the invention

[0007] According to the present disclosure, the occurrence of metal contamination and the attachment of particles to a zirconium film formed on a substrate can be suppressed. Brief explanation of the drawing

[0008] FIG. 1 is a schematic vertical cross-sectional view showing an example of a substrate processing apparatus according to the present disclosure. FIG. 2 is a block diagram illustrating an example of the hardware configuration of a substrate processing device shown in FIG. 1. Figure 3 is a graph showing an example of a comparison of the occurrence of metal contamination in a substrate processing device shown in Figure 1 and a conventional substrate processing device. Figure 4 is a graph showing an example of a comparison of the number of particles attached to a wafer in a substrate processing device shown in Figure 1 and a conventional substrate processing device. Figure 5 is a graph showing an example of the relationship between the partial pressure of the hydrogen nitride-based gas and the supply time of the hydrogen nitride-based gas in the substrate processing apparatus shown in Figure 1, and the aluminum atomic distribution, which is an indicator of the occurrence of metal contamination. FIG. 6a is a flowchart showing an example of a process executed in a substrate processing apparatus shown in FIG. 1. FIG. 6b is a flowchart showing an example of a process executed in a substrate processing device shown in FIG. 1. FIG. 6c is a flowchart showing an example of a process executed in the substrate processing apparatus shown in FIG. 1. FIG. 6d is a flowchart showing an example of a process executed in a substrate processing apparatus shown in FIG. 1. Specific details for implementing the invention

[0009] As described above, in the technology of Patent Document 1, zirconium films are formed sequentially on a plurality of wafers. However, when zirconium chloride gas is used as the film-forming gas, chlorine may remain inside the chamber when the formation of zirconium films on each wafer is repeated. This chlorine reacts with the aluminum in the chamber to produce aluminum chloride, and there is a problem that metal contamination occurs, in which the aluminum chloride adheres to the zirconium film on the wafer as a metallic foreign substance. Furthermore, when the formation of zirconium films on each wafer is repeated, zirconium films or zirconium chloride films may also be formed on the inner wall of the chamber. There is also a problem in that if these films are finely broken and peeled off from the inner wall of the chamber, they adhere to the zirconium film on the wafer as particles.

[0010] In this regard, the technology of the present disclosure supplies a hydrogen nitride-based gas into the chamber after the formation of a zirconium film to suppress the occurrence of metal contamination and the attachment of particles to the zirconium film of the wafer.

[0011] Hereinafter, an embodiment of the technology relating to the present disclosure will be described with reference to the drawings. However, the configurations described in the following embodiments are merely examples and are not limited thereto. For example, each part included in this configuration may be replaced with any other part capable of performing a similar function. Additionally, any other component may be added.

[0012] FIG. 1 is a schematic vertical cross-sectional view illustrating an example of a substrate processing apparatus according to the present disclosure. The substrate processing apparatus (1) shown in FIG. 1 is an apparatus for performing a film deposition process to form a film composed of Zr (zirconium) on a wafer (substrate) (W). The substrate processing apparatus (1) is equipped with a Zr film deposition chamber (2), a loading platform (3), a shower head (4), a processing gas supply unit (5), a high-frequency power supply (6), and an exhaust system (7). The Zr film deposition chamber (2) is approximately cylindrical in shape, and the processing space (U), which is the internal space, is depressurized. Additionally, a wafer (W) is housed in the processing space (U). Then, within the processing space (U) in which the wafer (W) is housed, a Zr film deposition process is performed by plasma CVD. Additionally, the volume of the processing space (U) is preferably, for example, 15L or more and 30L or less, and more preferably 20L or more and 25L or less. By doing so, the installation space, such as a loading platform (3), and the entry space of an arm (not shown) for loading and unloading wafers (W) into and out of the processing space (U) can be secured without excess or deficiency. In addition, at least a portion of the Zr film deposition chamber (2) exposed to the processing space (U) (e.g., the cross-hatching portion in FIG. 1) is composed of a material containing Al (aluminum). Hereinafter, the portion composed of this material containing Al is referred to as the "aluminum component (23)." Furthermore, it is preferable that the temperature of the aluminum component (23) during film deposition be 200 degrees or lower, even if there is heat input from plasma, etc. By doing so, the aluminum component (23) can be prevented from softening during film deposition.

[0013] A loading platform (3) is positioned below the processing space (U). The loading platform (3) has a loading surface (31) on which a wafer (W) is loaded. A heater (32) is embedded in the loading platform (3). It is preferable to adjust the surface temperature of the loading surface (31) during film deposition processing by this heater (32) to, for example, 300 degrees or more and 500 degrees or less, and more preferable to adjust it to, for example, 420 degrees or more and 480 degrees or less. By doing so, the wafer (W) can be heated without excess or deficiency, for example, during film deposition processing, and accordingly, a Zr film can be reliably formed on the wafer (W). Additionally, the loading platform (3) may be configured to be movable in the up and down direction by a driving mechanism (not shown). A shower head (4) made of, for example, a metal material such as aluminum is positioned on the ceiling of the Zr film deposition room (2). In the processing space (U) between the loading platform (3) and the shower head (4), as described later, zirconium chloride (ZrCl4) gas as a processing gas is used to produce zirconium chloride (ZrCl4). x Plasma is generated.

[0014] In addition, the surface of the parts that are exposed in at least part to the processing space (U), such as the loading platform (3) and shower head (4), is preferably covered with an underlayer containing a material that does not contain oxygen, such as aluminum nitride (AlN). By doing so, oxidation of these parts can be prevented, or corrosion caused by chlorine (Cl2) gas, etc., described later can be prevented. Also, since the underlayer and the aluminum component (23) do not contain oxygen, even if the underlayer or the aluminum component (23) is etched by plasma, for example, oxygen is not released, and oxidation of the Zr film can be suppressed.

[0015] Additionally, on the side wall of the Zr film deposition chamber (2), an inlet / outlet port (21) for bringing in and taking out a wafer (W) into and out of the processing space (U), and a gate valve (22) for opening and closing the inlet / outlet port (21) are provided. An exhaust system (7) is disposed at the bottom of the Zr film deposition chamber (2). The exhaust system (7) includes a pump (not shown), such as a turbo molecular pump or a dry pump, for exhausting the inside of the processing space (U), and an exhaust valve (not shown), such as an APC (Auto Pressure Controller) valve, for controlling the pressure inside the processing space (U).

[0016] The shower head (4) is positioned facing the wafer (W) loaded on the loading platform (3). The shower head (4) has a gas diffusion chamber (41) formed inside and a plurality of gas holes (42) that communicate the gas diffusion chamber (41) with the processing space (U). Additionally, a processing gas supply unit (5) is connected to the shower head (4) via a pipe (51). The processing gas supply unit (5) supplies ZrCl4 gas as a processing gas to the gas diffusion chamber (41). The ZrCl4 gas supplied to the gas diffusion chamber (41) is introduced into the processing space (U) via each gas hole (42). Furthermore, the processing gas may contain ZrCl4 gas, and may also contain, for example, a diluent gas. Examples of diluent gases include Ar gas.

[0017] A high-frequency power supply (6) is connected to the shower head (4). The high-frequency power supply (6) can supply high-frequency power for plasma generation, for example, 450 kHz, to the shower head (4). By doing so, the shower head (4) functions as an upper electrode, and an electric field is generated in the processing space (U). The electric field generated in the processing space (U) excites and decomposes the ZrCl4 gas introduced into the processing space (U), thereby generating ZrCl4 plasma. This ZrCl4 plasma is attached to the wafer (W), and by simultaneously supplying H2 gas as a reducing gas to the attached ZrCl4, the excited H radicals generated undergo a reduction reaction, and chlorine (Cl) is removed from the ZrCl4, thereby forming a Zr film on the wafer (W). In addition, for the reducing gas, hydrogen halides such as HCl or SiH4, etc., may be used in addition to H2 gas.

[0018] FIG. 2 is a block diagram illustrating an example of the hardware configuration of a substrate processing device shown in FIG. 1. As shown in FIG. 2, the substrate processing device (1) is equipped with a control unit (10) that is connected to communicate with a processing gas supply unit (5), etc. The control unit (10) includes a computer having at least a CPU (11) and a memory (12), and the memory (12) has various recipes (programs) pre-recorded for performing film deposition processing or post-deposition processing described later.

[0019] As described above, the substrate processing device (1) is a device for forming a Zr film on a wafer (W) within a Zr film deposition chamber (2). Additionally, the Zr film deposition chamber (2) has an aluminum component (23) made of aluminum in at least a portion exposed to the processing space (U). When ZrCl4 gas is used as the processing gas for film deposition processing in the substrate processing device (1), if the formation of a Zr film on the wafer (W) is repeated, Cl2 gas may remain inside the Zr film deposition chamber (2). This Cl2 gas reacts with the aluminum component (23) of the Zr film deposition chamber (2) to form AlCl xIt produces (aluminum chloride). And AlCl x There is a risk that metal contamination may occur as a metallic foreign substance attached to the Zr film of the wafer (W). In addition, when the formation of the Zr film on the wafer (W) is repeated, the inner wall of the Zr film deposition chamber (2) may have Zr film or ZrCl x There are cases where a (zirconium chloride) film is formed. Over time, these films may break into fine fragments and peel off from the inner wall of the Zr film formation chamber (2). There is a risk that this peeled material may adhere to the Zr film of the wafer (W) as particles.

[0020] Therefore, the substrate processing device (1) is configured to suppress the occurrence of metal contamination and the attachment of particles to the Zr film on the wafer (W) by a post-deposition processing method that performs processing on the Zr film chamber (2) after film formation. The configuration and operation thereof will be explained below.

[0021] As shown in FIG. 1, the substrate processing device (1) is equipped with an NH3 gas supply unit (hydrogen nitride-based gas supply means) (8) and an N2 gas supply unit (9). In this substrate processing device (1), when performing a post-film formation method, the NH3 gas supply process (hydrogen nitride-based gas supply process) and the N2 gas supply process (nitrogen gas supply process) are performed separately. The NH3 gas supply process is a process of supplying NH3 (ammonia) gas into the processing space (U) from the NH3 gas supply unit (8). The N2 gas supply process is a process of supplying N2 (nitrogen) gas into the processing space (U) from the N2 gas supply unit (9).

[0022] In addition, in the substrate processing device (1), prior to the NH3 gas supply process, the wafer receiving process, the film deposition process, the ZrCl4 gas discharge process (processing gas discharge process), and the removal process are performed in sequence. The wafer receiving process is a process of receiving a wafer (W) before film deposition into the processing space (U). The film deposition process is a process of supplying ZrCl4 gas, which is a processing gas, into the processing space (U) to form a Zr film on the wafer (W). The ZrCl4 gas discharge process is a process of discharging ZrCl4 gas, which is a processing gas, from the processing space (U). The removal process is a process of removing the wafer (W) after film deposition from the processing space (U).

[0023] In the wafer loading process, first, the gate valve (22) is opened. Then, the wafer (W) is brought into the processing space (U) by the arm that loads and unloads the wafer (W) and is loaded onto the loading platform (3). Then, the arm is withdrawn from the processing space (U) and the gate valve (22) is closed. By doing so, the film deposition process in the next process becomes possible.

[0024] In the film deposition process, as described above, ZrCl4 gas is supplied into the processing space (U), and plasma is generated from the ZrCl4 gas to form a Zr film on the wafer (W). Also, as described above, as a film deposition condition at this time, it is preferable to adjust the surface temperature of the loading surface (31) to, for example, 400 degrees or higher and 450 degrees or lower. Also, it is preferable to lower the pressure of the processing space (U) to, for example, several tens of mTorr. Additionally, it is preferable to supply power to the shower head (4) to, for example, high-frequency power for plasma generation of 450 kHz. After continuing the film deposition process for a predetermined time, the supply of ZrCl4 gas is stopped, and the supply of high-frequency power, that is, the generation of plasma, is also stopped. This stopped state is maintained during the ZrCl4 gas discharge process and the N2 gas supply process.

[0025] In the ZrCl4 gas discharge process, gases such as ZrCl4 gas remaining in the treatment space (U) are discharged from the treatment space (U) by operating the exhaust system (7). In this embodiment, the exhaust system (7) functions not only as a pressure adjustment means for adjusting the pressure of the treatment space (U) during plasma generation, but also as a treatment gas discharge means for discharging ZrCl4 gas from the treatment space (U). Furthermore, in the ZrCl4 gas discharge process, it is preferable to make the pressure of the treatment space (U) equal to the pressure outside the gate valve (22) by discharging the ZrCl4 gas. By doing so, when the gate valve (22) is opened during the discharge process of the next process, an airflow is generated between the treatment space (U) and the outside of the gate valve (22), and, for example, dust or dirt can be suppressed or prevented from scattering within the treatment space (U).

[0026] In the removal process, first, the gate valve (22) is opened. Then, the wafer (W) on the loading platform (3) is removed from the processing space (U) by the arm. Then, the gate valve (22) is closed.

[0027] In the NH3 gas supply process, NH3 gas is supplied into the processing space (U) by the NH3 gas supply unit (8). The NH3 gas supply unit (8) is connected to the Zr film chamber (2) via a pipe (80). Additionally, a switching valve (81) for opening and closing the pipe (80) is provided in the middle of the pipe (80). Then, by opening the switching valve (81) and closing the switching valve (91) described later, NH3 gas can be supplied from the NH3 gas supply unit (8) to the Zr film chamber (2) (processing space (U)) via the pipe (80). By switching the switching valve (81) to a closed state, the supply of NH3 gas from the NH3 gas supply unit (8) to the Zr film chamber (2) can be stopped.

[0028] In the N2 gas supply process, N2 gas is supplied into the processing space (U) by the N2 gas supply unit (9). The N2 gas supply unit (9) is connected to a part downstream of the switching valve (81) of the pipe (80) via the pipe (90). A switching valve (91) that opens and closes the pipe (90) is arranged in the middle of the pipe (90). Then, by closing the aforementioned switching valve (81) and opening the switching valve (91), N2 gas can be supplied from the N2 gas supply unit (9) to the Zr film chamber (2) via the pipe (90) and the pipe (80) in sequence. The supplied N2 gas entrains the decomposition products described later that occur in the NH3 gas supply process, and together with them, is discharged from the inside of the Zr film chamber (2) by the exhaust system (7). In this embodiment, N2 gas or Ar gas functions as a purge gas and prevents decomposition products generated during the NH3 gas supply process from adhering to the wafer (W) or the structure of the Zr film-forming chamber (2). Additionally, by switching the switching valve (81) to a closed state, the supply of N2 gas from the N2 gas supply unit (9) to the Zr film-forming chamber (2) can be stopped.

[0029] However, as described above, when the formation of a Zr film on a wafer (W) is repeated, Cl2 gas may remain inside the Zr film deposition chamber (2), that is, in the processing space (U). The remaining Cl2 gas reacts with the aluminum component (23) of the Zr film deposition chamber (2) and AlCl2, which is the cause of metal contamination. x For example, on the surface of an aluminum component (23). Accordingly, NH3 gas is supplied into a processing space (U) by an NH3 gas supply process. At this time, within the processing space (U), at least one of the following chemical reaction equations (1) and (2) occurs.

[0030] NH3+AlCl x →AlN+NH y Cl z +H2···(1)

[0031] NH3+AlCl x →Al+NH y Cl z +H2···(2)

[0032] As a specific example of the chemical reaction formula (1), the following chemical reaction formula (3) can be cited.

[0033] 4NH3+AlCl3→AlN+3NH4Cl···(3)

[0034] As a specific example of the chemical reaction formula (2), the following chemical reaction formula (4) can be cited.

[0035] 6NH3+2AlCl3+3H2→2Al+6NH4Cl···(4)

[0036] As shown in these chemical reaction formulas (1) to (4), AlCl on the surface of the aluminum component (23) x Even if it was generated, due to the supply of NH3 gas, the said AlCl x It decomposes into aluminum (Al), aluminum nitride (AlN), ammonium chloride (NH4Cl), or hydrogen (H2) gas. That is, AlCl xSince AlCl does not exist inside the Zr membrane chamber (2), x It can be prevented from peeling off from the surface of the aluminum component (23) and adhering to the Zr film of the wafer (W) as a metallic foreign substance, thereby suppressing the occurrence of metal contamination. Additionally, on the right side of the chemical reaction equation (3), the “H2” corresponding to the “H2” on the right side of the chemical reaction equation (1) is missing, but there is no particular problem with this. Likewise, on the right side of the chemical reaction equation (4), the “H2” corresponding to the “H2” on the right side of the chemical reaction equation (2) is missing, but there is no particular problem with this.

[0037] Also, AlCl x Since the Al or AlN generated by the reaction with NH3 is chemically stable, it remains on the surface of the aluminum component (23) and does not peel off. In addition, the NH4Cl generated by the above reaction has a high vapor pressure, so it vaporizes easily and, like H2 gas, is discharged from the inside of the Zr film chamber (2) by the exhaust system (7). Therefore, AlCl x Since the decomposition products generated by the reaction of NH3 do not adhere to the Zr film of the wafer (W), the occurrence of contamination caused by these decomposition products can also be suppressed.

[0038] FIG. 3 is a graph showing an example of a comparison of the occurrence of metal contamination in a substrate processing apparatus shown in FIG. 1 and a conventional substrate processing apparatus. In this graph, AlCl x As an indicator of the occurrence of metal contamination caused by [the], the "aluminum atom distribution," which is the number of Al atoms (aluminum atoms) attached per unit area of ​​the wafer (W), is used. In addition, the aluminum atom distribution in a substrate processing device (1) that performs an NH3 gas supply process is indicated as "NH3 post-treatment present," and the aluminum atom distribution in a conventional substrate processing device that does not perform an NH3 gas supply process is indicated as "conventional."

[0039] As shown in the graph of Fig. 3, whether it is "with NH3 post-treatment" or "conventional," as the number of wafers (W) processed increases, the distribution density of Al atoms (aluminum atoms) tends to decrease. However, the distribution of aluminum atoms is significantly lower in "with NH3 post-treatment" compared to "conventional." Accordingly, it can be said that in the substrate processing apparatus (1), the NH3 gas supply process exerts an effect of suppressing the occurrence of metal contamination of Al.

[0040] In addition, it is thought that Cl2 gas that has not fully reacted with the aluminum component (23) exists inside the Zr film chamber (2). In the NH3 gas supply process, the Cl2 gas reacts with the NH3 gas to be converted into NH4Cl gas and H2 gas. Since these NH4Cl gas and H2 gas are discharged from inside the Zr film chamber (2) by the exhaust system (7), the Cl2 gas can also be removed by supplying NH3 gas.

[0041] In addition, as described above, when the formation of a Zr film on a wafer (W) is repeated, on the inner wall of the Zr film formation chamber (2), there may be a Zr film or ZrCl that can become particles. x There are cases where a film is formed. In this regard, NH3 gas is supplied into the treatment space (U) by an NH3 gas supply process. At this time, within the treatment space (U), at least one of the following chemical reaction equations (5) and (6) occurs.

[0042] 2NH3+2Zr→2ZrN+3H2···(5)

[0043] NH3+ZrCl x →Zr+NH y Cl z +H2···(6)

[0044] Specific examples of the chemical reaction formula (5) include the following chemical reaction formulas (7) to (9).

[0045] 2NH3+ZrCl→ZrN+NH4Cl+H2···(7)

[0046] 6NH3+2ZrCl2→2ZrN+4NH4Cl+H2···(8)

[0047] 6NH3+4ZrCl→4ZrN+2NH4Cl2+5H2···(9)

[0048] As shown in these chemical reaction formulas (5) to (9), a Zr film or ZrCl is formed on the inner wall of the Zr film chamber (2). x Even if a film has been formed, due to the supply of NH3 gas, the said AlCl x It decomposes into zirconium (Zr), zirconium nitride (ZrN), NH4Cl gas, or H2 gas. That is, Zr membrane or ZrCl x Since there is no case where the film remains formed, the film is finely broken and peeled off, thereby preventing it from adhering to the Zr film of the wafer (W) as particles.

[0049] Also, Zr, ZrCl x Since Zr or ZrN generated by the reaction with NH3 is chemically stable, it remains on the inner wall of the Zr film-forming chamber (2) and does not peel off. In addition, as described above, NH4Cl generated by the above reaction is easily vaporized and, like H2 gas, is discharged from the inside of the Zr film-forming chamber (2) by the exhaust system (7). Therefore, Zr, ZrCl x Since the decomposition products generated by the reaction of Zr and NH3 are peeled off from the inner wall of the Zr film chamber (2) and do not adhere to the Zr film of the wafer (W), the adhesion of particles caused by these decomposition products can also be suppressed. In addition, since ZrN is a stable inorganic compound, it can function as a protective film to protect the aluminum component (23).

[0050] FIG. 4 is a graph showing an example of a comparison of the number of particles attached to a wafer in a substrate processing device shown in FIG. 1 and a conventional substrate processing device. In this graph, the number of particles per wafer (W) in a substrate processing device (1) that performs an NH3 gas supply process is indicated as "NH3 post-processing present," and the number of particles per wafer (W) in a conventional substrate processing device that does not perform an NH3 gas supply process is indicated as "conventional."

[0051] As shown in the graph of Fig. 4, the number of particles per wafer (W) is significantly reduced compared to the "conventional" in the case of "with NH4 post-treatment." Specifically, the number of particles per wafer (W) in the case of "with NH4 post-treatment" is suppressed to 5 or fewer. Accordingly, it can be said that in the substrate processing device (1), the particle adhesion suppression effect is achieved by the NH3 gas supply process.

[0052] In the NH3 gas supply process, it is desirable to adjust the partial pressure of the NH3 gas and the supply time of the NH3 gas. Figure 5 is a graph showing an example of the relationship between the product of the partial pressure of the hydrogen nitride-based gas and the supply time of the hydrogen nitride-based gas in the substrate processing apparatus shown in Figure 1, and the aluminum atom distribution, which is an indicator of the occurrence of metal contamination. As shown in the graph of Figure 5, as the product of the partial pressure of the NH3 gas and the supply time of the NH3 gas increases, the aluminum atom distribution decreases. However, when the product of the partial pressure of the NH3 gas and the supply time of the NH3 gas is 25 Torr·sec or more, the decrease in the aluminum atom distribution saturates. Therefore, from the perspective of suppressing the occurrence of Al metal contamination, it is desirable to make the product of the partial pressure of the NH3 gas and the supply time of the NH3 gas 25 Torr·sec or more. By doing so, the occurrence of Al metal contamination can be suppressed. In addition, from the perspective of reducing NH3 gas usage or improving throughput, it is desirable for the product of the partial pressure of NH3 gas and the supply time of NH3 gas to be small. Therefore, it is desirable to keep the product at 25 Torr·sec or more and 40 Torr·sec or less. By doing so, it is possible to achieve both a reduction in NH3 gas usage and an improvement in throughput, as well as suppression of Al metal contamination.

[0053] In addition, when obtaining the relationship shown in FIG. 5, in the NH3 gas supply process, the flow rate of NH3 gas is set to 800 sccm or more and 10,000 sccm or less, the supply time of NH3 gas is set to 10 sec or more and 60 sec or less, and the pressure inside the processing space (U) is set to 1 Torr or more and 9 Torr or less. However, from the perspective of reducing the amount of NH3 gas used, it is desirable to set the flow rate of NH3 gas to 800 sccm or more and 4,000 sccm or less. In addition, from the perspective of improving throughput, it is desirable to set the supply time of NH3 gas to 10 sec or more and 40 sec or less. In addition, from the perspective of promoting the vaporization of NH4Cl, it is desirable to set the pressure inside the processing space (U) to 1 Torr or more and 9 Torr or less.

[0054] Additionally, in the NH3 gas supply process, the temperature of the aluminum component (23) in the Zr film-forming chamber (2) may be higher than the temperature of the aluminum component (23) during the film-forming process. By doing so, if dust or dirt is attached to the aluminum component (23), for example, these can be heat-shrinked and peeled off from the aluminum component (23), and quickly removed from the inside of the Zr film-forming chamber (2) together with NH4Cl gas or H2 gas. Also, in this case, it is preferable that the temperature be 200 degrees or lower to prevent the aluminum component (23) from softening.

[0055] In this embodiment, the NH3 gas supply process is performed with plasma generation stopped, but it is not limited to this and may be performed with plasma generation. The density of the plasma is high at the shower head (4) and its surroundings, and furthermore, since the NH3 plasma generated from the NH3 gas promotes the reactions of the chemical equations (5) to (9) described above, the Zr film or ZrCl attached to the shower head (4) and its surroundings x You can remove the membrane by focusing on it.

[0056] In addition, the gas supplied in the NH3 gas supply process is NH3 gas in this embodiment, but is not limited to this and may be any hydrogen nitride-based gas. Examples of hydrogen nitride-based gases other than NH3 gas include N2H4 (hydrazine) gas.

[0057] Next, a variation of the sequence of processes executed in the substrate processing device (1) will be explained with reference to FIGS. 6a to 6d. FIGS. 6a to 6d are flowcharts showing an example of a process executed in the substrate processing device shown in FIG. 1. In the variation shown in FIG. 6a, the process is executed in the order of wafer intake process, film formation process, ZrCl4 gas discharge process, discharge process, NH3 gas supply process, and N2 gas supply process, but the NH3 gas supply process and the N2 gas supply process are repeated. In addition, Ar gas may be used instead of N2 gas. Here, as described above, since it is desirable to make the product of the partial pressure of NH3 gas and the supply time of NH3 gas 25 Torr·sec or more, when repeating the NH3 gas supply process, it is also desirable to make the cumulative value between the partial pressure of NH3 gas and the total supply time of NH3 gas supply 25 Torr·sec or more.

[0058] In the modified example shown in FIG. 6b, the wafer receiving process, film formation process, ZrCl4 gas discharge process, outgoing process, and NH3 gas supply process are executed in that order, but the N2 gas supply process (Ar gas supply process) is omitted. By omitting the N2 gas supply process, throughput can be further improved.

[0059] The modified example shown in FIG. 6c corresponds to a case where multiple film deposition processes are repeated, but in this case, the NH3 gas supply process or the N2 gas supply process is not performed every time the outgoing process is executed. That is, the wafer receiving process, film deposition process, ZrCl4 gas discharge process, and outgoing process are repeated, but after forming a Zr film on a predetermined number of wafers (W), the NH3 gas supply process and the N2 gas supply process are repeated for the first time. By doing so, the number of times the NH3 gas supply process or the N2 gas supply process is executed in total can be reduced, and throughput can be further improved.

[0060] The modified example shown in FIG. 6d corresponds to a case where the NH3 gas supply process and the N2 gas supply process are not repeated compared to the modified example shown in FIG. 6c, and the N2 gas supply process is omitted. By doing so, the number of times the NH3 gas supply process and the N2 gas supply process are executed in the whole can be reduced, and the throughput can be significantly improved.

[0061] Although preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the embodiments described above, and various modifications and changes are possible within the scope of the gist thereof.

[0062] The present application claims priority based on Japanese patent application No. 2024-006671 filed on January 19, 2024, and incorporates all of the contents of the application herein. Explanation of the symbols

[0063] 1: Substrate processing device 2: Zr Tabernacle Room 7: Exhaust system 8: NH3 Gas Supply Unit 23: Aluminum components U: Processing space W: Wafer

Claims

Claim 1 A post-film deposition method comprising a processing space in which a processing gas containing zirconium chloride is supplied while a substrate is housed to perform a film deposition process in which a film composed of zirconium is formed on the substrate, and a chamber in which at least a portion exposed to the processing space is made of a material containing aluminum, wherein the processing gas discharge process of stopping the supply of the processing gas and discharging the processing gas from the processing space after the film deposition process, and a hydrogen nitride-based gas supply process of supplying a hydrogen nitride-based gas into the processing space after the processing gas discharge process. Claim 2 A post-treatment method for film formation according to claim 1, wherein in the hydrogen nitride-based gas supply process, the partial pressure of the hydrogen nitride-based gas and the supply time for supplying the hydrogen nitride-based gas are adjusted. Claim 3 A post-treatment method for film formation according to paragraph 2, wherein the product of the partial pressure of the hydrogen nitride-based gas and the supply time of supplying the hydrogen nitride-based gas is 25 Torr·sec or more. Claim 4 A post-treatment method for film formation according to claim 1, wherein in the hydrogen nitride-based gas supply process, the flow rate of the hydrogen nitride-based gas is 800 sccm or more and 10,000 sccm or less. Claim 5 A post-treatment method for film formation according to claim 1, wherein in the hydrogen nitride-based gas supply process, a film composed of zirconium is formed covering a portion of the chamber composed of a material including aluminum. Claim 6 A post-processing method for film deposition according to claim 1, wherein a loading platform including a loading surface on which the substrate is loaded is provided within the processing space, and the surface temperature of the loading surface during the film deposition process is 400 degrees or more and 450 degrees or less. Claim 7 A post-treatment method for film formation according to claim 1, wherein the temperature of the part of the chamber composed of the aluminum-containing material during the film formation treatment is 200 degrees or less. Claim 8 A post-treatment method for film formation according to claim 1, wherein the hydrogen nitride-based gas is ammonia gas or hydrazine gas. Claim 9 A post-treatment method for film formation according to claim 1, comprising a nitrogen gas supply process for supplying nitrogen gas into the treatment space after the hydrogen nitride-based gas supply process. Claim 10 A post-treatment method for film formation according to claim 9, wherein the above hydrogen nitride-based gas supply process and the above nitrogen gas supply process are repeated. Claim 11 A post-treatment method for film formation according to claim 10, wherein in the hydrogen nitride-based gas supply process, the partial pressure of the hydrogen nitride-based gas and the supply time for supplying the hydrogen nitride-based gas are adjusted, and when the hydrogen nitride-based gas supply process is repeated, the cumulative sum of the partial pressure of the hydrogen nitride-based gas and the total supply time for supplying the hydrogen nitride-based gas is 25 Torr·sec or more. Claim 12 A post-treatment method for film formation according to claim 1, comprising a removal process for removing the substrate from the treatment space after the treatment gas discharge process. Claim 13 A post-treatment method for film formation according to claim 1, wherein the film formation treatment is performed by generating plasma from the treatment gas within the treatment space, and the generation of the plasma is stopped in the treatment gas discharge process and the hydrogen nitride-based gas supply process. Claim 14 In claim 1, the chamber is a post-treatment method for film formation in which the volume of the processing space is 15L or more and 30L or less. Claim 15 A substrate processing apparatus comprising a processing space in which a processing gas containing zirconium chloride is supplied while a substrate is housed to perform a film formation process in which a film composed of zirconium is formed on the substrate, and a chamber in which at least a portion exposed to the processing space is made of a material containing aluminum, wherein the processing gas discharge means for stopping the supply of the processing gas and discharging the processing gas from the processing space after the film formation process, and a hydrogen nitride gas supply means for supplying a hydrogen nitride gas into the processing space after the processing gas is discharged from the processing space by the processing gas discharge means.

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