Titanium nitride thin film forming method and semiconductor device

Abstract

The present invention relates to a titanium nitride thin film forming method and a semiconductor device and, more specifically, to a titanium nitride thin film forming method for forming a titanium nitride thin film on a substrate and a semiconductor device. A titanium nitride thin film forming method according to an embodiment of the present invention comprises the steps of: preparing a substrate in a process space; supplying a raw material gas containing titanium onto the substrate; and supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate, wherein the step of supplying a raw material gas and the step of supplying a reaction gas are sequentially performed, and plasma is formed in the process space when the reaction gas is supplied.

Description

Method for forming titanium nitride thin film and semiconductor device

[0001] The present invention relates to a method for forming a titanium nitride thin film and a semiconductor device, and more particularly, to a method for forming a titanium nitride thin film and a semiconductor device for forming a titanium nitride thin film on a substrate.

[0002] Titanium nitride thin films are used as barrier metal layers in the semiconductor device manufacturing process. A barrier metal layer is a diffusion-preventing metal layer formed before the wiring metal layer to prevent cross-diffusion between aluminum and silicon when the wiring metal, such as aluminum, comes into contact with the junction area formed on the silicon substrate.

[0003] Titanium nitride thin films are primarily formed using chemical vapor deposition to improve step coverage in response to the increasing integration of semiconductor devices. Specifically, titanium nitride thin films are formed using a chemical vapor deposition method that supplies a titanium-containing raw material gas and ammonia-containing reactant gas onto a substrate provided in a process space.

[0004] However, when forming a titanium nitride thin film using a chemical vapor deposition method that supplies a raw material gas containing titanium and a reaction gas containing ammonia, metal contamination occurs due to byproducts. That is, there was a problem in that byproducts generated during deposition reacted with metal materials within the chamber providing the process space or within the chamber, such as copper components contained in aluminum alloys, resulting in metal contamination of the titanium nitride thin film with copper components.

[0005] (Prior art literature)

[0006] Korean Patent Publication No. 10-2006-0107818

[0007] The present invention provides a method for forming a titanium nitride thin film and a semiconductor device capable of preventing metal contamination.

[0008] A method for forming a titanium nitride thin film according to an embodiment of the present invention comprises the steps of: providing a substrate in a process space; supplying a raw material gas containing titanium onto the substrate; and supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate; wherein the step of supplying the raw material gas and the step of supplying the reaction gas are performed sequentially, and when the reaction gas is supplied, plasma is formed in the process space.

[0009] The step of supplying the raw material gas and the step of supplying the reaction gas are performed sequentially, and plasma can be formed in the process space after supplying the raw material gas and before supplying the reaction gas.

[0010] The above process space can be maintained at a temperature of 100 to 400°C.

[0011] The step of supplying the above reaction gas can supply a larger amount of reaction gas than the raw material gas supplied in the step of supplying the raw material gas.

[0012] The method may further include a step of exposing a thin film formed by performing a process cycle including a step of supplying the raw material gas and a step of supplying the reaction gas to plasma.

[0013] The step of exposing to the plasma may include a step of supplying hydrogen, oxygen or argon gas to the process space.

[0014] The above raw material gas contains chlorine, and the step of exposing it to plasma may include a step of supplying hydrogen gas to the process space.

[0015] The step of supplying the raw material gas may further include a step of filling a buffer space capable of supplying the raw material gas to a raw material gas supply line or the process space with the raw material gas.

[0016] The step of supplying the reaction gas may further include a step of filling a reaction gas supply line or a buffer space capable of supplying the reaction gas to the process space with the reaction gas.

[0017] In addition, a method for forming a titanium nitride thin film according to an embodiment of the present invention includes the steps of (a) providing a substrate in a process space; (b) supplying a raw material gas containing titanium onto the substrate; (c) supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate and forming plasma of the reaction gas; (d) forming a titanium nitride thin film on the substrate; and (e) exposing the titanium nitride thin film to plasma of a gas containing hydrogen; and steps (b) to (e) may be repeated.

[0018] Meanwhile, a semiconductor device according to an embodiment of the present invention includes a substrate; and a titanium nitride thin film formed on the substrate by any one of the methods described above.

[0019] The above titanium nitride thin film may have a thickness of 50 to 200 Å.

[0020] According to an embodiment of the present invention, metal contamination of a titanium nitride thin film can be prevented.

[0021] In addition, when forming a titanium nitride thin film using a reaction gas containing ammonia, metal contamination can be prevented while maintaining properties such as resistivity, step coverage, and thin film thickness.

[0022] Figure 1 is a schematic drawing showing a substrate processing device according to an embodiment of the present invention.

[0023] FIG. 2 is a drawing for explaining a process cycle of a method for forming a titanium nitride thin film according to an embodiment of the present invention.

[0024] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms. These embodiments of the present invention are provided solely to ensure complete disclosure of the present invention and to fully inform those skilled in the art of the scope of the invention.

[0025] When a component, such as a layer, film, region or substrate, is referred to as being "on" another component throughout the specification, it can be interpreted that the component is either directly "on" the other component, or there may be other components intervening therebetween.

[0026] Additionally, relative terms such as "upper" or "lower" may be used herein to describe the relative relationship of certain elements to other elements as depicted in the drawings. It should be understood that relative terms are intended to encompass other orientations of the elements in addition to the orientation depicted in the drawings. To illustrate the invention in detail, the drawings may be exaggerated, and like reference numerals throughout the drawings designate like elements.

[0027]

[0028] FIG. 1 is a schematic drawing showing a substrate processing device according to an embodiment of the present invention.

[0029] Referring to FIG. 1, a substrate processing device according to an embodiment of the present invention is a device for depositing a thin film, for example, a titanium nitride thin film, on a substrate, and includes a chamber (10), a substrate support unit (20) provided within the chamber (10) to support a substrate provided within the chamber (10), a gas injection unit (30) provided within the chamber (10) so as to face the substrate support unit (20) to inject a process gas toward the substrate support unit (20), and a gas supply unit (40) for supplying the process gas to the substrate injection unit (30). In addition, the substrate processing device may include an RF power source (50) that supplies power to generate plasma within the chamber (10), and may further include a control unit (not shown) that controls the RF power source (50).

[0030] The chamber (10) provides a predetermined reaction space and maintains it airtight. The chamber (10) may include a body (12) having a predetermined reaction space, including a flat surface of approximately circular or rectangular shape and a side wall extending upward from the flat surface, and a cover (14) positioned on the body (12) in an approximately circular or rectangular shape to keep the chamber (10) airtight. However, the chamber (10) is not limited thereto and may be manufactured in various shapes corresponding to the shape of the substrate.

[0031] An exhaust port (not shown) may be formed in a predetermined area on the lower surface of the chamber (10), and an exhaust pipe (not shown) connected to the exhaust port may be provided on the outside of the chamber (10). In addition, the exhaust pipe may be connected to an exhaust device (not shown). A vacuum pump such as a turbo molecular pump may be used as the exhaust device. Therefore, the inside of the chamber (10) may be vacuum-sucked to a predetermined reduced pressure atmosphere, for example, a predetermined pressure of 0.1 mTorr or less, by the exhaust device. The exhaust pipe may be installed on the side of the chamber (10) below the substrate support member (20) described later in addition to the lower surface of the chamber (10). In addition, it goes without saying that a plurality of exhaust pipes and corresponding exhaust devices may be further installed in order to reduce the exhaust time.

[0032] Meanwhile, a substrate provided into the chamber (10) for a thin film formation process may be mounted on the substrate support member (20). Here, the substrate may include a silicon wafer or glass, and may include a substrate on which a separate thin film has already been formed on a silicon wafer or glass. The substrate support member (20) may be provided with, for example, an electrostatic chuck to hold the substrate by electrostatic force so that such a substrate may be mounted and supported, or the substrate may be supported by vacuum suction or mechanical force.

[0033] The substrate support (20) may be provided in a shape corresponding to the shape of the substrate, for example, a circle or a square. The substrate support (20) may include a substrate support (22) on which the substrate is mounted, and an elevator (24) disposed below the substrate support (22) to move the substrate support (22) up and down. Here, the substrate support (22) may be manufactured to be larger than the substrate, and the elevator (24) is provided to support at least a portion of the substrate support (22), for example, the center, and when the substrate is mounted on the substrate support (22), the substrate support (22) may be moved closer to the gas injection unit (20). In addition, a heater (not shown) may be installed inside the substrate support. The heater generates heat at a predetermined temperature to heat the substrate support (22) and the substrate mounted on the substrate support (22), thereby allowing a thin film to be uniformly deposited on the substrate.

[0034] The gas supply unit (40) may be installed at least partially outside the chamber (10) and supplies gas to the gas injection unit (30). The gas supply unit (40) may include a source gas supply unit (42) for supplying a source gas, and a reaction gas supply unit (44, 46) for supplying a reaction gas. Here, the source gas supply unit (42) may supply a gas containing titanium (Ti), for example, titanium tetrachloride (TiCl4) gas. In addition, the reaction gas supply unit (44, 46) may include a first reaction gas supply unit (44) for supplying a nitrogen-containing gas, for example, nitrogen (N2) gas, and a second reaction gas supply unit (46) for supplying a hydrogen-containing gas, for example, hydrogen (H2) gas, through a separate path from the first reaction gas supply unit (44). Additionally, the gas supply unit (40) may further include a purge gas supply unit (48) for supplying an inert gas such as argon (Ar) gas or a gas with low reactivity.

[0035] Meanwhile, the gas supply unit (40) does not necessarily supply one gas to the gas injection unit (30), but may be configured to supply multiple gases simultaneously or supply a gas selected from among multiple gases.

[0036] The gas injection unit (30) is provided at the upper side inside the chamber (10) and injects process gas toward the substrate. The gas injection unit (30) is connected to the gas supply unit (40) at the upper side, and an injection hole (not shown) for injecting the process gas to the substrate is formed at the lower side. Such a gas injection unit (30) may include a shower head in which a plurality of fine injection holes are formed. Alternatively, the gas injection unit (30) may include an injector in which an injection hole having a diameter relatively larger than the fine injection holes is formed at an end thereof. Hereinafter, the gas injection unit (30) includes a shower head as an example, but it is obvious that the following embodiment can be applied as is even when the gas injection unit (30) includes an injector.

[0037] The gas injection unit (30) can be manufactured in a shape corresponding to the shape of the substrate, and can be manufactured in an approximately circular or rectangular shape. Here, the gas injection unit (30) can be provided at a predetermined distance from the side wall and cover (14) of the chamber (10). In addition, when forming plasma in the reaction space within the chamber (10), the gas injection unit (30) can receive power from an RF power source (50) and act as an upper electrode.

[0038] The RF power source (50) supplies power to form plasma. That is, the RF power source (50) supplies power to generate plasma in the reaction space within the chamber (10). For example, the RF power source (50) supplies power to either the substrate support (20) or the gas injection unit (30), and the other of the substrate support (20) or the gas injection unit (30) is grounded, so that plasma can be formed in the space between the substrate support (20) and the gas injection unit (30).

[0039]

[0040] Hereinafter, the method for forming a titanium nitride thin film of the present invention will be described in detail with reference to FIG. 2. The method for forming a titanium nitride thin film according to an embodiment of the present invention can be performed by the substrate processing apparatus described above, and therefore, any description overlapping with the above-described content with respect to the substrate processing apparatus will be omitted.

[0041] FIG. 2 is a drawing for explaining a process cycle of a method for forming a titanium nitride thin film according to an embodiment of the present invention.

[0042] Referring to FIG. 2, a method for forming a titanium nitride thin film according to an embodiment of the present invention includes the steps of: providing a substrate in a process space; supplying a raw material gas containing titanium onto the substrate; and supplying a reaction gas containing a hydrogen-containing gas and a nitrogen-containing gas onto the substrate. Here, the step of supplying the raw material gas and the step of supplying the reaction gas are performed sequentially, and a process cycle including the step of supplying the raw material gas and the step of supplying the reaction gas can be performed multiple times.

[0043] The step of preparing a substrate is to prepare a substrate in the process space of the chamber (10). In the step of preparing a substrate, the substrate is brought into the process space of the chamber (10), and the brought-in substrate (S) can be seated on the substrate support member (20). The substrate may include a silicon wafer or glass, and as described above, may include a substrate on which a separate thin film is already formed on a silicon wafer or glass. Here, the substrate support member (20) may be provided with, for example, an electrostatic chuck or the like to adsorb and hold the substrate by electrostatic force so that the substrate can be seated and supported, or the substrate may be supported by vacuum adsorption or mechanical force.

[0044] The step of supplying the raw material gas supplies the raw material gas containing titanium onto the substrate provided in the process space. The step of supplying the raw material gas may supply a gas containing titanium (Ti), for example, titanium tetrachloride (TiCl4) gas, via the raw material gas supply unit (42) of the substrate processing device described above. In the step of supplying the raw material gas, the raw material gas containing titanium (Ti) is sprayed onto the substrate to be adsorbed. At this time, the step of supplying the raw material gas may be performed without applying RF power (50).

[0045] The step of supplying the raw material gas may further include a step of filling a raw material gas supply line or a buffer space capable of supplying the raw material gas to the process space with the raw material gas. In order for the deposition process to be performed efficiently, it is necessary to supply a uniform flow rate of gas per unit time. In other words, the raw material gas needs to be supplied uniformly from the start of the raw material gas supply section, where the raw material gas supply begins, to the end of the raw material gas supply section, where the raw material gas supply ends.

[0046] Therefore, the step of filling with raw material gas can be performed by filling the raw material gas supply line or the buffer space provided in the raw material gas supply line and capable of temporarily storing the raw material gas with the raw material gas before starting to supply the raw material gas. To this end, a valve (not shown) installed adjacent to the gas injection unit (30) is closed to block the raw material gas supply line or the buffer space provided in the raw material gas supply line and capable of temporarily storing the raw material gas from the process space. Thereafter, the raw material gas is supplied to the raw material gas supply line or the buffer space provided in the raw material gas supply line and capable of temporarily storing the raw material gas. At this time, the raw material gas supply line or the buffer space is filled with the raw material gas. Thereafter, by opening the valve to connect the raw material gas supply line or the buffer space with the process space, the raw material gas can be supplied evenly from the start to the end of the raw material gas supply section.

[0047] After the step of supplying the raw material gas, a step of purging the raw material gas may be performed. In the step of purging the raw material gas, the raw material gas remaining in the reaction space of the chamber (10) may be removed. This step of purging the raw material gas may be performed by supplying an inert gas, such as argon (Ar) gas, to the reaction space.

[0048] After the step of supplying the raw material gas, a step of forming plasma in the process space may be performed. In this case, plasma of argon (Ar) gas may be formed by applying RF power (50) in the step of purging the process space, and of course, plasma may be formed in the reaction space before or after the step of purging the process space. When forming plasma before or after the step of purging the process space, it may be performed by supplying argon (Ar) gas to the process space through the aforementioned purge gas supply unit (48) and applying RF power (50). In addition, of course, argon (Ar) gas may be supplied to the process space separately from the purge gas and RF power (50) may be applied. In this way, when the substrate is exposed to plasma after the step of supplying the raw material gas, stress of the thin film can be controlled and film quality can be improved.

[0049] After the step of purging the reaction space to which the raw material gas is supplied, a step of supplying a reaction gas is performed. The step of supplying a reaction gas supplies a reaction gas containing a nitrogen-containing gas and a hydrogen-containing gas onto the substrate. Here, the step of supplying a reaction gas supplies a reaction gas containing a nitrogen-containing gas and a hydrogen-containing gas through the first reaction gas supply unit (44) and the second reaction gas supply unit (44) of the substrate processing apparatus described above. At this time, the nitrogen-containing gas may include nitrogen (N2) gas, and the hydrogen-containing gas may include hydrogen (H2) gas.

[0050] The step of supplying the reaction gas may supply the nitrogen-containing gas and the hydrogen-containing gas simultaneously. That is, the step of supplying the reaction gas may supply the nitrogen-containing gas and the hydrogen-containing gas simultaneously along the first reaction gas supply path and the second reaction gas supply path, respectively. Alternatively, the step of supplying the reaction gas may supply the nitrogen-containing gas and the hydrogen-containing gas in a set order. That is, the step of supplying the reaction gas may supply the hydrogen-containing gas after supplying the nitrogen-containing gas, or may supply the nitrogen-containing gas after supplying the hydrogen-containing gas. Although FIG. 2 illustrates an embodiment in which the nitrogen-containing gas and the hydrogen-containing gas are supplied simultaneously, the timing of supplying the nitrogen-containing gas and the hydrogen-containing gas may be variously changed in the step of supplying the reaction gas.

[0051] The step of supplying a reaction gas may further include a step of filling a reaction gas supply line or a buffer space capable of supplying the reaction gas to the process space with the reaction gas. In order for the deposition process to be performed efficiently, it is necessary to supply a uniform flow rate of gas per unit time, and the reaction gas needs to be supplied uniformly from the start of the reaction gas supply section where the reaction gas supply begins to the end of the reaction gas supply section where the supply of the reaction gas ends, which is the same as in the case of the raw material gas.

[0052] Therefore, the step of filling with a reaction gas can be performed by filling the reaction gas supply line or the buffer space provided in the reaction gas supply line and capable of temporarily storing the reaction gas with the reaction gas before starting to supply the reaction gas. To this end, a valve (not shown) installed adjacent to the gas injection unit (30) is closed to block the reaction gas supply line or the buffer space provided in the reaction gas supply line and capable of temporarily storing the reaction gas from the process space. Thereafter, the reaction gas is supplied to the reaction gas supply line or the buffer space provided in the reaction gas supply line and capable of temporarily storing the reaction gas. At this time, the reaction gas supply line or the buffer space is filled with the raw material gas. Thereafter, by opening the valve to connect the reaction gas supply line or the buffer space with the process space, the reaction gas can be supplied evenly from the start to the end of the reaction gas supply section.

[0053] At this time, in the step of supplying the reaction gas, in order to effectively react the reaction gas with the titanium component, a larger amount of reaction gas may be supplied than the raw material gas supplied in the step of supplying the raw material gas. In addition, in order to effectively react the reaction gas with the titanium component, RF power (50) may be applied to the process space to activate the reaction gas and generate plasma. That is, when supplying the reaction gas, plasma may be formed in the process space of the chamber (10). To this end, the step of supplying the reaction gas may further include a step of applying power for forming plasma to the process space, and at least a part of the step of supplying the reaction gas may be performed while the power for forming plasma is applied to the process space. That is, at least a part of the section in which the step of supplying the reaction gas is performed may overlap with a section in which the power for forming plasma is applied to the process space. Although FIG. 2 illustrates that RF power (50) is applied to the reaction space only in the step of supplying the reaction gas, the step of applying RF power (50) to the reaction space includes all cases in which RF power (50) is applied to the reaction space while the step of supplying the reaction gas is performed. It goes without saying that RF power (50) may be applied before starting to supply the reaction gas to the process space, or after ending to supply the reaction gas to the process space, or RF power (50) may be applied intermittently, i.e., in a pulse form, while the reaction gas is supplied.

[0054] In this way, by activating and supplying the reaction gas in the step of supplying the reaction gas, a titanium nitride thin film can be formed at a lower process temperature. That is, when the reaction gas is activated and supplied onto the substrate, the titanium nitride thin film can be deposited by maintaining the process space of the chamber (10) at a low temperature of 100°C or higher and 400°C or lower.

[0055] After the step of supplying the reaction gas, a step of purging the reaction space to which the reaction gas has been supplied may be performed. In the step of purging the reaction space to which the reaction gas has been supplied, the reaction gas remaining in the reaction space of the chamber (10) can be removed. As described above, this step of purging the reaction gas can be performed by supplying an inert gas, for example, argon (Ar) gas, to the reaction space, similar to the step of purging the raw material gas.

[0056] Here, the method for forming a titanium nitride thin film according to an embodiment of the present invention can perform a process cycle including a step of supplying a raw material gas, a step of purging the raw material gas, a step of supplying a reaction gas, and a step of purging the reaction gas multiple times. That is, the method for forming a titanium nitride thin film comprises a step of supplying a raw material gas, a step of purging the raw material gas, a step of supplying a reaction gas, and a step of purging the reaction gas, which constitute one process cycle, and the process cycle can be repeatedly performed until a thin film having a desired thickness is formed on the substrate.

[0057] Meanwhile, the method for forming a titanium nitride thin film according to an embodiment of the present invention may further include a step of exposing the thin film formed by performing a process cycle including the step of supplying a raw material gas and the step of supplying a reaction gas as described above to plasma. Here, the step of exposing the thin film to plasma may expose the thin film formed by performing at least one process cycle to plasma. That is, the step of exposing the thin film to plasma may expose the thin film formed by performing one process cycle to plasma, or may expose the thin film formed by performing multiple process cycles to plasma. In addition, the step of exposing the thin film to plasma may be performed by supplying hydrogen (H2) gas, oxygen (O2) gas, or argon (Ar) gas to a process space and applying RF power (50). For example, the method for forming a titanium nitride thin film according to an embodiment of the present invention may include the steps of: (a) providing a substrate in a process space; (b) supplying a raw material gas containing titanium onto the substrate; (c) a step of supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate and forming plasma of the reaction gas; (d) a step of forming a titanium nitride thin film on the substrate; and (e) a step of exposing the titanium nitride thin film to plasma of a gas containing hydrogen; and steps (b) to (e) can be repeated.

[0058] As described above, the raw material gas may include titanium tetrachloride (TiCl4) gas containing chlorine (Cl). Accordingly, the step of exposing the thin film to plasma may be performed by supplying hydrogen (H2) gas to the process space and applying RF power (50) to expose the thin film to hydrogen plasma formed so as to remove residual chlorine (Cl) components. That is, when exposing the thin film to hydrogen plasma, not only can the residual chlorine (Cl) components be effectively removed, but also the stress of the thin film can be controlled, and it is also possible to effectively remove impurities remaining in the chamber (10) or impurities included in the thin film.

[0059] According to the method for forming a titanium nitride thin film according to an embodiment of the present invention, a semiconductor device including a barrier metal layer made of titanium nitride can be formed. That is, the semiconductor device can include a substrate and a titanium nitride thin film formed according to the method for forming a titanium nitride thin film according to the embodiment of the present invention described above. At this time, the titanium nitride thin film can be formed to a thickness of 50 Å or more and 200 Å or less. That is, according to the embodiment of the present invention, a titanium nitride thin film can be formed to a thickness of 50 Å to 200 Å by forming the titanium nitride thin film by an atomic layer deposition process that forms the thin film in atomic layer units and supplies energy.

[0060] In this way, according to an embodiment of the present invention, metal contamination of a titanium nitride thin film can be prevented.

[0061] In addition, when forming a titanium nitride thin film using a reaction gas containing ammonia, metal contamination can be prevented while maintaining properties such as resistivity, step coverage, and thin film thickness.

[0062]

[0063] While the preferred embodiments of the present invention have been described and illustrated using specific terms above, such terms are solely for the purpose of clearly describing the present invention, and it is to be understood that various modifications and variations may be made to the embodiments and terms described herein without departing from the spirit and scope of the appended claims. Such modified embodiments should not be construed individually from the spirit and scope of the present invention, but should be considered to fall within the scope of the claims.

Claims

1. Step of preparing a substrate in the process space; A step of supplying a raw material gas containing titanium onto the substrate; and A step of supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate; The step of supplying the raw material gas and the step of supplying the reaction gas are performed sequentially. A method for forming a titanium nitride thin film by forming plasma in the process space when supplying the above reaction gas.

2. In claim 1, The step of supplying the raw material gas and the step of supplying the reaction gas are performed sequentially. A method for forming a titanium nitride thin film, wherein plasma is formed in the process space after supplying the raw material gas and before supplying the reaction gas.

3. In claim 1, A method for forming a titanium nitride thin film, wherein the above process space is maintained at a temperature of 100 to 400°C.

4. In claim 1, The step of supplying the above reaction gas is: A method for forming a titanium nitride thin film, wherein a larger amount of reaction gas is supplied than the raw material gas supplied in the step of supplying the raw material gas.

5. In claim 1, A method for manufacturing a semiconductor device, further comprising: a step of exposing a thin film formed by performing a process cycle including a step of supplying the raw material gas and a step of supplying the reaction gas to plasma.

6. In claim 5, The step of exposing to the above plasma is: A method for manufacturing a semiconductor device, comprising: a step of supplying hydrogen, oxygen or argon gas to the above process space.

7. In claim 5, The above raw material gas contains chlorine, The step of exposing to the above plasma is: A method for manufacturing a semiconductor device, comprising: a step of supplying hydrogen gas to the above process space.

8. In claim 1, The step of supplying the above raw material gas is: A method for forming a titanium nitride thin film, further comprising: a step of filling a buffer space capable of supplying raw material gas to a raw material gas supply line or the process space with raw material gas.

9. In claim 1, The step of supplying the above reaction gas is: A method for forming a titanium nitride thin film, further comprising: a step of filling a buffer space capable of supplying a reaction gas to a reaction gas supply line or the process space with a reaction gas. 10.(a) Step of preparing a substrate in a process space; (b) a step of supplying a raw material gas containing titanium onto the substrate; (c) a step of supplying a reaction gas containing nitrogen gas and hydrogen gas onto the substrate and forming plasma of the reaction gas; (d) forming a titanium nitride thin film on the substrate; and (e) a step of exposing the titanium nitride thin film to a plasma of a gas containing hydrogen; A method for forming a titanium nitride thin film by repeating steps (b) to (e) above.

11. Substrate; and A semiconductor device comprising a titanium nitride thin film formed on the substrate by any one of the methods of claims 1 to 10.

12. In claim 11, The above titanium nitride thin film is a semiconductor device having a thickness of 50 to 200 Å.

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