Substrate processing method

Abstract

A substrate processing method according to one aspect of the present invention is a substrate processing method using a substrate processing apparatus comprising a process chamber having a reaction space formed therein, a gas injection unit installed in the process chamber to supply process gas to the reaction space, and a substrate support unit installed in the process chamber to face the gas injection unit so as to support a substrate. The substrate processing method comprises the steps of: forming a seasoning layer in the process chamber; seating a substrate on the substrate support unit in the process chamber in which the seasoning layer has been formed; and forming a thin film on the substrate seated on the substrate support unit, wherein the seasoning layer comprises at least a molybdenum compound, and the thin film comprises at least molybdenum.

Description

Substrate processing method

[0001] The present invention relates to semiconductor manufacturing, and more specifically, to a substrate processing method.

[0002] To manufacture semiconductor devices, various substrate processing steps are performed in a vacuum-based substrate processing apparatus. For example, processes such as loading a substrate into a process chamber and depositing a thin film on the substrate may be carried out. The substrate is supported by a substrate support installed within the process chamber, and the substrate can be processed by injecting process gas onto the substrate through a gas injection unit installed on the upper part of the substrate support.

[0003] For example, a metal thin film, such as a molybdenum thin film, can be formed on a substrate using a substrate processing device. During the metal thin film formation process using the substrate processing device, reaction products generated during thin film formation are deposited not only on the surface of the thin film but also inside the process chamber. Consequently, when depositing a metal thin film on a substrate using the substrate processing device, there is a problem of poor thickness uniformity and reduced reproducibility during repeated processes.

[0004] The present invention aims to solve various problems, including those mentioned above, by providing a substrate processing method that can improve thickness uniformity and reproducibility during repeated processes when depositing a thin film containing molybdenum on a substrate. However, these problems are exemplary and do not limit the scope of the present invention.

[0005] A substrate processing method according to one aspect of the present invention for solving the above problem is a substrate processing method using a substrate processing apparatus comprising: a process chamber having a reaction space formed therein; a gas injection unit installed in the process chamber to supply process gas to the reaction space; and a substrate support unit installed in the process chamber opposite to the gas injection unit to support the substrate, the method comprising the steps of: forming a seasoning layer inside the process chamber; placing a substrate on the substrate support unit inside the process chamber where the seasoning layer is formed; and forming a thin film on the substrate placed on the substrate support unit, wherein the seasoning layer comprises at least a molybdenum compound and the thin film comprises at least molybdenum.

[0006] In the above-described substrate processing method, the step of forming the seasoning layer includes the step of forming a first seasoning layer containing a molybdenum compound, and the step of forming the first seasoning layer can be performed by supplying a gas containing molybdenum and a gas containing an auxiliary component for forming the compound to the reaction space through the gas injection unit.

[0007] In the above substrate processing method, the auxiliary component-containing gas is a gas containing at least one of nitrogen (N), silicon (Si), boron (B), and oxygen (O), and the first seasoning layer is MoN a , MoSi a H b, Mo a B b H c and MoO x It may include any one of the following.

[0008] In the above-described substrate processing method, the step of forming the seasoning layer includes the step of forming a second seasoning layer containing molybdenum on the first seasoning layer, and the step of forming the second seasoning layer can be performed by supplying a molybdenum-containing gas and a hydrogen-containing gas into the reaction space through the gas injection unit.

[0009] In the above substrate processing method, the second seasoning layer may be formed thinner than the first seasoning layer.

[0010] In the above substrate processing method, the step of forming the seasoning layer comprises MoO on the first seasoning layer. x The method includes the step of forming a second seasoning layer comprising, wherein the step of forming the second seasoning layer can be performed by supplying a molybdenum-containing gas and a hydrogen-containing gas or an oxygen-containing gas into the reaction space through the gas injection unit.

[0011] In the above substrate processing method, the step of forming the first seasoning layer can be performed by repeating a cycle of sequentially supplying the molybdenum-containing gas and the auxiliary component-containing gas into the reaction space multiple times.

[0012] In the above substrate processing method, the first seasoning layer is MoN a The step of forming the first seasoning layer, including the above, can be performed by repeating the cycle 1,000 times or more.

[0013] In the above-described substrate processing method, the step of forming the thin film comprises the step of forming a nucleation layer containing a molybdenum compound on the substrate and the step of forming a main layer containing molybdenum on the nucleation layer, and the molybdenum compound of the seasoning layer and the molybdenum compound of the nucleation layer may be of the same material.

[0014] In the above substrate processing method, the molybdenum compound of the seasoning layer and the molybdenum compound of the nucleation layer are MoN a It may include.

[0015] The above-described substrate processing method includes, before the step of forming the seasoning layer, a step of placing a cover substrate on the substrate support, and after the step of forming the seasoning layer, a step of removing the cover substrate from the process chamber, and the step of forming the seasoning layer can be performed while the cover substrate is placed on the substrate support.

[0016] In the above substrate processing method, the step of forming the seasoning layer and the step of forming the thin film may utilize a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.

[0017] According to some embodiments of the present invention as described above, thickness uniformity can be increased and reproducibility improved during repeated processes when depositing a thin film containing molybdenum on a substrate. Of course, the scope of the present invention is not limited by these effects.

[0018] FIG. 1 is a schematic cross-sectional view showing a substrate processing apparatus according to one embodiment of the present invention.

[0019] FIG. 2 is a schematic flowchart showing a substrate processing method according to one embodiment of the present invention.

[0020] FIG. 3 is a schematic flowchart showing a substrate processing method according to another embodiment of the present invention.

[0021] FIG. 4 is a schematic flowchart showing the step of forming a seasoning layer in substrate processing methods according to embodiments of the present invention.

[0022] FIG. 5 is a schematic flowchart showing the step of forming a first seasoning layer in substrate processing methods according to embodiments of the present invention.

[0023] FIG. 6 is a schematic flowchart showing the step of forming a thin film in substrate processing methods according to embodiments of the present invention.

[0024] FIG. 7 is a schematic diagram showing the characteristics of thin films formed according to substrate processing methods according to comparative examples.

[0025] FIGS. 8 and 9 are schematic diagrams showing the characteristics of thin films formed according to the substrate processing method according to the embodiments.

[0026] Hereinafter, several preferred embodiments of the present invention will be described in detail with reference to the attached drawings.

[0027] The embodiments of the present invention are provided to more fully explain the invention to those skilled in the art, and the following embodiments may be modified in various different forms, and the scope of the invention is not limited to the following embodiments. Rather, these embodiments are provided to make the disclosure more faithful and complete and to fully convey the spirit of the invention to those skilled in the art. In addition, the thickness or size of each layer in the drawings is exaggerated for convenience and clarity of explanation.

[0028] FIG. 1 is a cross-sectional view schematically showing a substrate processing device (100) according to one embodiment of the present invention.

[0029] Referring to FIG. 1, the substrate processing device (100) may include a process chamber (110), a gas injection unit (120), and a substrate support unit (130).

[0030] More specifically, a reaction space (112) in which a substrate (S) can be processed may be formed in the process chamber (110). The process chamber (110) may be connected to a vacuum pump (not shown) through an exhaust pipe (114) to form a vacuum atmosphere and pumped.

[0031] The process chamber (110) may be equipped with an entrance / exit for loading a substrate (S) into or from the reaction space (112) and a gate structure (not shown) for opening and closing the same. The process chamber (110) may be provided in various shapes and, for example, may include a body portion (115) and a cover portion (117). The body portion (115) may define the reaction space (112) but may be open at the top. The cover portion (117) may be coupled to the body portion (115) to cover the body portion (115), and, for example, the cover portion (117) may include a top lead.

[0032] A gas injection unit (120) may be coupled to a process chamber (110) to supply process gas to a reaction space (112). More specifically, the gas injection unit (120) may be installed in the process chamber (110) so as to face a substrate support (130). For example, the gas injection unit (120) may be installed at the top of the process chamber (110) to inject process gas onto a substrate (S) placed on the substrate support (130).

[0033] In some embodiments, the gas injection unit (120) may include an inlet (122) into which process gas is introduced through a gas pipe (126), and a distribution plate (124) for injecting the process gas introduced through the inlet (122) and dispersed internally into a reaction space (112). Furthermore, the gas injection unit (120) may further include a blocker plate internally for dispersing the process gas that has passed through the inlet (122).

[0034] In some embodiments, the gas injection unit (120) may have various forms, such as a shower head or a nozzle. If the gas injection unit (120) is in the form of a shower head, the gas injection unit (120) may be coupled to the process chamber (110) in a manner that partially covers the upper part of the process chamber (110). For example, the gas injection unit (120) may be coupled to the cover portion (117) of the process chamber (110).

[0035] A substrate support member (130) may be coupled to a process chamber (110) to support a substrate (S). For example, the substrate support member (130) may be installed in the process chamber (110) opposite to a gas injection member (120). The substrate support member (130) may include a top plate (132) on which the substrate (S) is placed and a shaft (135) for supporting it.

[0036] In some embodiments, the substrate support (130) may include a heater (182) for heating the substrate (S) inside its top plate (132). For example, a heater power supply (180) for applying power may be connected to the heater (182). Furthermore, an AC filter (185) may be connected between the heater power supply (180) and the heater (182).

[0037] The shape of the top plate (132) generally corresponds to the shape of the substrate (S), but is not limited thereto and can be provided in various shapes larger than the substrate (S) so as to stably seat the substrate (S). The shaft (135) may be connected to an external motor (not shown) to enable vertical movement, and optionally, a bellows tube (not shown) may be connected to maintain airtightness. Since the substrate support part (130) is configured to seat the substrate (S) thereon, it may be called a substrate seating part, a substrate holder, a susceptor, etc.

[0038] In some embodiments, the substrate support (130) may include an electrostatic electrode (not shown) inside it. The electrostatic electrode may serve as an electrostatic electrode for fixing the substrate (S) by electrostatic force. When the substrate (S) is chucked by electrostatic force, the substrate support (130) may be called an electrostatic chuck. The electrostatic electrode may apply electrostatic force to the substrate (S) by receiving DC power.

[0039] In some embodiments, the substrate processing device (100) may include a plasma power supply (140) to form a plasma atmosphere within a process chamber (110). The plasma power supply (140) may be connected to the process chamber (110) to supply radio frequency (RF) power to form a plasma atmosphere within a reaction space (112) inside the process chamber (110). For example, the plasma power supply (140) may be connected to a gas injection unit (120), and the gas injection unit (120) may be referred to as a power supply electrode or an upper electrode. For example, the plasma power supply (140) may supply high frequency (HF) power and / or low frequency (LF) power.

[0040] Additionally, an impedance matching unit (146) may be placed between the plasma power supply unit (140) and the gas injection unit (120) for impedance matching. RF power supplied from the plasma power supply unit (140) must be properly impedance matched through the impedance matching unit (146) between the plasma power supply unit (140) and the process chamber (110) so that it can be effectively transmitted to the process chamber (110) without being reflected back from the process chamber (110).

[0041] The impedance matching unit (146) may be composed of two or more series or parallel combinations selected from the group of resistors, inductors, and capacitors. Furthermore, the impedance matching unit (146) may adopt at least one variable capacitor or capacitor array switching structure so that its impedance value can be varied according to the frequency of RF power and process conditions.

[0042] In some embodiments, the aforementioned substrate processing apparatus (100) may be used for thin film deposition using chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), or atomic layer deposition (ALD).

[0043] In some embodiments, the plasma power supply unit (140) in the aforementioned substrate processing device (100) is omitted, and the substrate processing device (100) can be used for thin film deposition using a thermal chemical vapor deposition (thermal CVD) method that does not use plasma.

[0044] Hereinafter, a substrate processing method according to embodiments of the present invention will be explained using the aforementioned substrate processing device (100).

[0045] FIG. 2 is a schematic flowchart showing a substrate processing method according to one embodiment of the present invention.

[0046] Referring to FIGS. 1 and 2, the substrate processing method may include the step (S20) of forming a seasoning layer inside a process chamber (110), the step (S40) of placing a substrate (S) on a substrate support (130) inside the process chamber (110) where the seasoning layer is formed, and the step (S50) of forming a thin film on the substrate (S) placed on the substrate support (130).

[0047] In some embodiments, the thin film comprises at least molybdenum (Mo), and the seasoning layer may comprise a material associated with the thin film. For example, the seasoning layer may comprise at least a molybdenum compound (Mo compound), and the seasoning layer may be formed inside the process chamber (110). For example, the seasoning layer may be formed on at least the inner wall of the process chamber (110). Furthermore, the seasoning layer may be formed on a structure inside the process chamber (110), such as the surface of the gas injection part (120) and / or the surface of the substrate support part (130).

[0048] More specifically, the step (S20) of forming the seasoning layer can be performed by supplying a gas containing molybdenum and a gas containing an auxiliary component for forming a compound into the reaction space (112) through the gas injection unit (120). The molybdenum-containing gas and the gas containing the auxiliary component react within the reaction space (112) to form a molybdenum compound on the substrate (S).

[0049] In some embodiments, the step (S20) of forming the seasoning layer may be performed using a CVD method or an ALD method. For example, a molybdenum-containing gas and an auxiliary component-containing gas may be supplied together into a reaction space (112) so that these gases react within the reaction space (112) by the CVD method to form a molybdenum compound on the substrate (S). As another example, a molybdenum compound may be formed on the substrate (S) by the ALD method by repeating the sequential supply of a molybdenum-containing gas and an auxiliary component-containing gas into the reaction space (112).

[0050] In some embodiments, as illustrated in FIG. 4, the step of forming a seasoning layer (S20) may include the step of forming a first seasoning layer (S22) containing a molybdenum compound. For example, the step of forming the first seasoning layer (S22) may be performed by supplying a gas containing molybdenum and a gas containing an auxiliary component for forming a compound into a reaction space (112) through a gas injection unit (120).

[0051] In some embodiments, as illustrated in FIG. 5, the step of forming a first seasoning layer (S22) may be performed by repeating the cycle multiple times, and the cycle may sequentially include the step of supplying a molybdenum-containing gas into the reaction space (112) (S221) and the step of supplying an auxiliary component-containing gas into the reaction space (112) (S223). Optionally, steps of supplying a purge gas may be added after each of the steps (S221, S223). This purge gas may be used to remove residual gases within the reaction space (112).

[0052] More specifically, in step (S221), a molybdenum-containing gas can be adsorbed onto the substrate (S) at the atomic layer level. In step (S223), an auxiliary component-containing gas reacts with the molybdenum-containing gas adsorbed onto the substrate (S), so that a molybdenum compound can be formed on the substrate (S) at the atomic layer level. By repeating this cycle, a first seasoning layer composed of a molybdenum compound can be formed on the substrate (S) with a predetermined thickness.

[0053] For example, the first seasoning layer may include a molybdenum compound, e.g., MoN a , MoSi a H b, Mo a B b H c and MoO xIt may include any one of the following. As a molybdenum-containing gas, molybdenum or various molybdenum compounds may be provided in gaseous form, and may include, for example, a MoO2Cl2 or MoCl5 precursor. For example, the auxiliary component-containing gas may be a gas containing at least one of nitrogen (N), silicon (Si), boron (B), and oxygen (O). As a nitrogen-containing gas, N2, NH3, N2O gas, etc. may be used; as a silicon-containing gas, silene (SiH4), dichlorosilane gas, etc. may be used; as a boron-containing gas, B2H6 gas, etc. may be used; and as an oxygen-containing gas, O2, H2O2, O3 gas, etc. may be used.

[0054] In some embodiments, as illustrated in FIG. 4, the step of forming a seasoning layer (S20) may include the step of forming a second seasoning layer containing molybdenum on the first seasoning layer in the process chamber (110) after the step of forming a first seasoning layer (S22). For example, the step of forming the second seasoning layer (S24) may be performed by supplying a molybdenum-containing gas and a hydrogen-containing gas into the reaction space (112) through a gas injection unit (120).

[0055] The step (S24) of forming the second seasoning layer can be performed using the CVD method or the ALD method. For example, a molybdenum-containing gas and a hydrogen-containing gas can be supplied together into the reaction space (112) so that these gases react within the reaction space (112) by the CVD method to form a molybdenum layer on the substrate (S). As another example, a molybdenum layer can be formed on the substrate (S) by the ALD method by repeating a cycle of sequentially supplying a molybdenum-containing gas and a hydrogen-containing gas into the reaction space (112) multiple times. For example, a molybdenum-containing gas can be supplied into the reaction space (112), followed by a purge gas into the reaction space (112), followed by a hydrogen-containing gas into the reaction space (112), and then a purge gas into the reaction space (112) in sequence.

[0056] For example, as a molybdenum-containing gas, molybdenum or various molybdenum compounds may be provided in gaseous form, and may include, for instance, MoO2Cl2 or MoCl5 precursors. As a hydrogen-containing gas, H2 or H2O gas, etc., may be used.

[0057] In some embodiments, in the step (S24) of forming the second seasoning layer, the second seasoning layer is MoO x It may include. For example, MoO as a second seasoning layer. x The layer can be formed by supplying a molybdenum-containing gas and a hydrogen-containing gas into the reaction space (112), by supplying a molybdenum-containing gas and an oxygen-containing gas, or by supplying a molybdenum-containing gas, a hydrogen-containing gas, and an oxygen-containing gas. More specifically, as a second seasoning layer, MoO x The layer is a molybdenum-containing gas (MoO₂) x N) and hydrogen-containing gas (NH3 or H2) react to form molybdenum-containing gas without sufficient reduction, or molybdenum-containing gas (MoOx It may also be formed by the reaction of N) and an oxygen-containing gas (O2, H2O2, or O3).

[0058] In some embodiments, the second seasoning layer may be formed thinner than the first seasoning layer. For example, the first seasoning layer needs to be formed with a thickness sufficient to cover the inside of the process chamber (110) and may be formed with a thickness of at least 100 nm. The second seasoning layer may be formed as an optional additional layer with a thickness of at least 20 nm. For example, the second seasoning layer may be formed with a thickness of 1 / 2 or less, more strictly 2 / 5 or less of the first seasoning layer.

[0059] After the step (S20) of forming a seasoning layer in the process chamber (110), a process of depositing a thin film on the substrate (S) may be performed. As shown in FIG. 2, the substrate (S) may be placed on the substrate support (130) inside the process chamber (110) where the seasoning layer is formed (S40). Subsequently, a thin film containing at least molybdenum may be formed on the substrate (S) placed on the substrate support (130) (S50).

[0060] In some embodiments, as illustrated in FIG. 6, the step of forming a thin film (S50) may include the step of forming a nucleation layer on a substrate (S) (S52) and the step of forming a main layer on the nucleation layer (S54). For example, the step of forming the nucleation layer (S52) may include a molybdenum compound, and the main layer may include molybdenum. The nucleation layer may serve as an underlayer on which the main layer is grown when it is difficult to grow the main layer directly on the substrate (S).

[0061] For example, the molybdenum compound of the nucleation layer may be of the same material as the molybdenum compound of the seasoning layer. That is, the nucleation layer may be of the same material as the first seasoning layer. For example, the nucleation layer and the first seasoning layer are MoN a , MoSia H b, Mo a B b H c or MoO x It may include. In some embodiments, the nucleation layer and the first seasoning layer are MoN a It can include.

[0062] In some embodiments, a cleaning process may be performed on the inside of the process chamber (110) before forming a seasoning layer on the inside of the process chamber (110). For example, if a thin film formation process is performed multiple times in the process chamber (110), thin films may be formed on the inside of the process chamber (110) and particles may be formed. To this end, a cleaning process may be performed on the process chamber (110). After the cleaning process on the process chamber (110), a seasoning layer may be formed on the inside of the process chamber (110).

[0063] In some embodiments, after the step of forming a seasoning layer (S20), the step of mounting a substrate (S) and the step of forming a thin film on the substrate (S50) may be repeated multiple times. Accordingly, after forming a seasoning layer once inside the process chamber (110), a thin film can be formed on multiple substrates (S). Furthermore, after a certain number of substrates (S) are processed inside the process chamber (110), a cleaning process for the process chamber (110) is performed, and the step of forming a seasoning layer (S20) may follow again.

[0064] FIG. 3 is a schematic flowchart showing a substrate processing method according to another embodiment of the present invention. The substrate processing method according to this embodiment adds some components to the substrate processing method of FIG. 2, and since the embodiments can be referenced to one another, redundant descriptions are omitted.

[0065] Referring to FIG. 3, the substrate processing method may include the step of placing a cover substrate on a substrate support (130) (S10), the step of forming a seasoning layer inside a process chamber (110) (S20), the step of removing the cover substrate from the process chamber (110) (S30), the step of placing a substrate (S) on a substrate support (130) inside the process chamber (110) (S40), and the step of forming a thin film on the substrate (S) placed on the substrate support (130) (S50).

[0066] For example, the cover substrate may be in the form of a substrate capable of covering the substrate support (130), such as a dummy substrate. The cover substrate may be supplied from outside the substrate processing device or stored in a stocker within the substrate processing device. In the step (S10) of placing the cover substrate, the cover substrate may be loaded into the process chamber (110) from an external or internal stocker. For example, if the substrate support (130) is used as an electrostatic chuck, the cover substrate may be placed on the substrate support (130) before forming the seasoning layer in order to prevent the formation of a conductive seasoning layer on the substrate support (130).

[0067] In step (S20), with the cover substrate seated on the substrate support (130), a seasoning layer may be formed inside the process chamber (110). Accordingly, the seasoning layer may be formed on the inner wall of the process chamber (110) and on the gas injection part (120), and may not be formed on the upper surface of the substrate support (130).

[0068] In step (S30), the cover substrate with the seasoning layer formed thereon can be removed from the process chamber (110). For example, the cover substrate can be removed from the process chamber (110) to outside the substrate processing device (100) or moved into a stoker inside the substrate processing device (100).

[0069] Next, the substrate (S) is placed on the substrate support (130) inside the process chamber (110) where the seasoning layer is formed (S40), and a thin film can be formed on the substrate (S) (S50).

[0070] Meanwhile, in some embodiments, when the substrate support (130) does not function as an electrostatic chuck, the cover substrate is not seated on the substrate support (130) when the seasoning layer is formed, and the seasoning layer may also be formed on the substrate support (130).

[0071] According to the aforementioned substrate processing methods, a seasoning layer is uniformly formed inside the process chamber (110) before forming a thin film on the substrate (S), thereby increasing thickness uniformity and reducing particle generation when forming a thin film on the substrate (S). Furthermore, when repeatedly forming thin films on the substrates (S) inside the process chamber (110), thin film reproducibility can be increased.

[0072] Below, the characteristics of thin films formed according to substrate processing methods according to comparative examples and embodiments are explained by comparison.

[0073] FIG. 7 is a schematic diagram showing the characteristics of thin films formed according to the substrate processing method according to comparative examples. Comparative Examples 1 to 7 show that a seasoning layer is formed with molybdenum (Mo) in a process chamber (110), and then a MoN nucleation layer / Mo main layer is formed as a thin film on a substrate (S). From Comparative Example 1 to Comparative Example 7, the number of cycles for forming the Mo seasoning layer increased from 295 to 2655.

[0074] Referring to FIG. 7, it can be seen that in all Comparative Examples 1 to 7, the target values ​​for sheet resistance uniformity (Rs unif.) and thickness uniformity (THK unif.) are not satisfied. Therefore, it can be seen that when depositing a Mo thin film, the Mo deposition as a seasoning layer for the process chamber (110) is unsatisfactory. It is presumed that one of the causes of this result is that the Mo seasoning layer was not grown uniformly on the inner wall of the process chamber (110). For example, when the inner wall of the process chamber is formed by coating with tungsten oxide (WOx), it is understood that the difference in surface energy between molybdenum and tungsten oxide is large, making it difficult for molybdenum to grow uniformly on the tungsten oxide.

[0075] FIGS. 8 and 9 are schematic diagrams showing the characteristics of thin films formed according to the substrate processing method according to the embodiments.

[0076] Examples 1 to 5 show that a MoN layer is formed as a seasoning layer, and subsequently, a MoN nucleation layer / Mo main layer is formed as a thin film on a substrate (S). From Example 1 to Example 5, the number of cycles for forming the MoN seasoning layer increased from 400 to 1500.

[0077] Referring to FIG. 8, it can be seen that as the number of cycles of the MoN seasoning layer increases, the surface resistance uniformity (Rs unif.) and thickness uniformity (THK unif.) tend to decrease. More specifically, in Examples 1 to 3, where the number of cycles of the MoN seasoning layer is up to 800, the target values ​​for surface resistance uniformity (Rs unif.) and thickness uniformity (THK unif.) are not satisfied, but in cycles beyond that, the target values ​​are satisfied.

[0078] Therefore, it can be seen that in order to satisfy the characteristic specifications of the Mo main layer formed on the substrate (S), the number of cycles of the MoN seasoning layer must exceed at least 800, and more strictly, as in Examples 4 and 5, the number of cycles of the MoN seasoning layer must exceed 1000. Considering the deposition rate per cycle, in order to satisfy the characteristic specifications of the Mo main layer formed on the substrate (S), the thickness of the MoN seasoning layer may be about 120 nm or more, and more strictly, 150 nm or more. When the thickness of the Mo main layer is 20 nm, the thickness of the MoN seasoning layer may be about 6 times or more, and more strictly, 7.5 times or more compared to the thickness of the Mo main layer.

[0079] Examples 6 to 8 show that a MoN layer was formed as a seasoning layer for 2000 cycles, and subsequently, a MoN nucleation layer / Mo main layer was formed as a thin film on a substrate (S). From Example 6 to Example 8, the number of times a thin film was formed on the substrate (S) increased from 1 to 3.

[0080] As described above, it was understood that the reason the MoN seasoning layer is effective is that the difference in surface energy between the tungsten oxide, which is the inner wall coating material of the process chamber (110), and the MoN layer is small, so the MoN seasoning layer can grow uniformly on the inner wall of the process chamber (110). Furthermore, it was determined that in order not to have a negative effect on the thin film formation process on the substrate (S), the MoN seasoning layer needs to be formed on the inner wall of the process chamber (110) with a thickness greater than a certain amount.

[0081] Referring to FIG. 9, it can be seen that Examples 6 to 8 all satisfy the specification values ​​for sheet resistance uniformity (Rs unif.) and thickness uniformity (THK unif.). However, it can be seen that the thin film characteristics change depending on the number of times the thin film is formed. For example, the thin films according to Examples 7 and 8, which have two or more thin film formations, show reproducible values, but the thin film according to Example 6, which has the first formation, shows somewhat different values.

[0082] Therefore, it can be seen that even after forming a seasoning layer in the process chamber (110) for 2000 cycles, a Mo thin film needs to be formed to a certain extent to ensure stable reproducibility when forming a thin film on the substrate (S). In this regard, it can be seen that when forming a seasoning layer, if a MoN layer is formed to a sufficient thickness and then a Mo layer is formed to a predetermined thickness, the reproducibility during thin film formation can be increased. For example, the thickness of the Mo layer formed as the seasoning layer may be at least 20 nm, which is the thickness of one thin film, and more stably, it may be at least 60 nm. In addition, from the results of Examples 6 to 8 above, it can be seen that after forming the MoN seasoning layer, a MoN layer / Mo layer may be additionally formed at least once on the MoN layer.

[0083] According to the aforementioned comparative examples and embodiments, it can be seen that compared to the case where a Mo seasoning layer is formed inside the process chamber (110) before forming a thin film on the substrate (S), the case where a MoN seasoning layer is formed with a thickness greater than a certain thickness can satisfy the physical properties of the thin film. Furthermore, in order to increase the reproducibility of the thin film properties, a Mo layer may be further formed on the MoN seasoning layer after forming the MoN seasoning layer, taking into account the thin film process.

[0084] The present invention has been described with reference to the embodiments illustrated in the drawings, but this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent alternative embodiments are possible therefrom. Accordingly, the true technical scope of protection of the present invention should be determined by the technical spirit of the appended claims.

Claims

1. A method for processing a substrate using a substrate processing apparatus comprising a process chamber having a reaction space formed therein, a gas injection unit installed in the process chamber to supply process gas to the reaction space, and a substrate support unit installed in the process chamber opposite to the gas injection unit to support the substrate, wherein A step of forming a seasoning layer inside the above process chamber; A step of placing a substrate on a substrate support within a process chamber in which the seasoning layer is formed; and The method includes the step of forming a thin film on a substrate seated on the substrate support, The above seasoning layer comprises at least a molybdenum compound, and The above thin film comprises at least molybdenum, Substrate processing method.

2. In Paragraph 1, The step of forming the seasoning layer includes the step of forming a first seasoning layer containing a molybdenum compound, and The step of forming the first seasoning layer is performed by supplying a molybdenum-containing gas and a gas containing an auxiliary component for forming a compound into the reaction space through the gas injection unit. Substrate processing method.

3. In Paragraph 2, The above auxiliary component-containing gas is a gas containing at least one of nitrogen (N), silicon (Si), boron (B), and oxygen (O), and The above first seasoning layer is MoN a , MoSi a H b , Mo a B b H c and MoO x including any one of Substrate processing method.

4. In Paragraph 2, The step of forming the seasoning layer includes the step of forming a second seasoning layer containing molybdenum on the first seasoning layer, and The step of forming the second seasoning layer is performed by supplying a molybdenum-containing gas and a hydrogen-containing gas into the reaction space through the gas injection unit. Substrate processing method.

5. In Paragraph 4, A substrate processing method in which the second seasoning layer is formed thinner than the first seasoning layer.

6. In Paragraph 2, The step of forming the seasoning layer above involves MoO on the first seasoning layer. x The method includes the step of forming a second seasoning layer comprising, The step of forming the second seasoning layer is performed by supplying a molybdenum-containing gas and a hydrogen-containing gas or an oxygen-containing gas into the reaction space through the gas injection unit. Substrate processing method.

7. In Paragraph 2, A substrate processing method in which the step of forming the first seasoning layer is performed by repeating a cycle of sequentially supplying the molybdenum-containing gas and the auxiliary component-containing gas into the reaction space multiple times.

8. In Paragraph 7, The above first seasoning layer is MoN a Includes, A substrate processing method wherein the step of forming the first seasoning layer is performed by repeating the cycle 1,000 times or more.

9. In Paragraph 1, The step of forming the above thin film is, A step of forming a nucleation layer containing a molybdenum compound on the substrate; and The method includes the step of forming a main layer containing molybdenum on the nucleation layer. The molybdenum compound of the seasoning layer and the molybdenum compound of the nucleation layer are of the same material. Substrate processing method.

10. In Paragraph 9, The molybdenum compound of the seasoning layer and the molybdenum compound of the nucleation layer are MoN a A substrate processing method comprising 11. In Paragraph 1, Before the step of forming the seasoning layer, the step of seating a cover substrate on the substrate support; and The method includes the step of removing the cover substrate from the process chamber after the step of forming the seasoning layer, and The step of forming the seasoning layer is performed while the cover substrate is seated on the substrate support. Substrate processing method.

12. In Paragraph 1, A substrate processing method in which the step of forming the seasoning layer and the step of forming the thin film utilize a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.

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