Substrate processing method

Abstract

According to a substrate processing method of the present invention, a substrate processing apparatus is used, the substrate processing apparatus comprising: a process chamber having a reaction space formed therein; a gas injection unit disposed in the process chamber for supplying process gas to the reaction space; and a substrate support unit disposed in the process chamber opposite to the gas injection unit for supporting a substrate. The substrate processing method includes the following steps: forming a processing layer inside the process chamber; placing a substrate on the substrate support unit inside the process chamber where the processing layer is formed; forming a thin film on the substrate placed on the substrate support unit; wherein the processing layer contains at least a molybdenum compound, and the thin film contains at least molybdenum.

Description

Technical Field

[0001] This invention relates to a semiconductor manufacturing process, and more specifically, to a substrate processing method. Prior Technology

[0002] To manufacture semiconductor devices, various substrate processing procedures are performed in a substrate processing apparatus in a vacuum environment. For example, a substrate is loaded into a process chamber, and processes such as depositing thin films on the substrate can be performed. The substrate is supported by a substrate support provided in the process chamber, and the substrate can be processed by spraying process gas onto the substrate through a gas jet provided above 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 apparatus. During the metal thin film formation process using the substrate processing apparatus, reaction products generated during film formation are deposited not only on the film surface but also inside the process chamber. Therefore, the following problems exist: depositing metal thin films on substrates using a substrate processing apparatus results in poor thickness uniformity and reduced reproducibility when repeated. Summary of the Invention

[0004] The technical problems to be solved

[0005] The present invention aims to solve various problems, including those described above, and to provide a substrate processing method that improves thickness uniformity and reproducibility during repeated processing when depositing a molybdenum-containing thin film on a substrate. However, this problem is exemplary and should not be construed as limiting the scope of the invention. Problem-solving methods

[0006] According to one aspect of the present invention, a substrate processing method for solving the above-mentioned problems utilizes a substrate processing apparatus, the substrate processing apparatus comprising: a process chamber having a reaction space formed therein; a gas injection unit disposed in the process chamber for supplying process gas to the reaction space; and a substrate support unit disposed in the process chamber opposite to the gas injection unit for supporting the substrate; the substrate processing method comprising the following steps: forming a processing layer inside the process chamber; placing a substrate on the substrate support unit inside the process chamber where the processing layer is formed; and forming a thin film on the substrate placed on the substrate support unit; wherein the processing layer contains at least a molybdenum compound, and the thin film contains at least molybdenum.

[0007] In the substrate processing method, the processing layer forming step includes a first processing layer forming step containing a molybdenum compound; the first processing layer forming step can be performed by supplying molybdenum-containing gas and a gas containing auxiliary components for forming the compound to the reaction space through the gas injection section.

[0008] In the substrate processing method, the gas containing auxiliary components is a gas containing at least one of nitrogen (N), silicon (Si), boron (B) and oxygen (O); the first processing layer may contain any one of MoNa, MoSiaHb, MoaBbHc and MoOx.

[0009] In the substrate processing method, the processing layer forming step includes forming a molybdenum-containing second processing layer on the first processing layer; the second processing layer forming step can be performed by supplying molybdenum-containing gas and hydrogen-containing gas into the reaction space through the gas injection section.

[0010] In the substrate processing method, the second processing layer may be formed to be thinner than the first processing layer.

[0011] In the substrate processing method, the processing layer forming step includes forming a second processing layer containing MoO x on the first processing layer; the second processing layer forming step can be performed by supplying molybdenum-containing gas and hydrogen-containing gas or oxygen-containing gas into the reaction space through the gas injection section.

[0012] In the substrate processing method, the first processing layer forming step can be performed by repeatedly cycling the molybdenum-containing gas and the gas containing auxiliary components into the reaction space.

[0013] In the substrate processing method, the first processing layer comprises MoNa, and the first processing layer formation step can be performed by repeating the cycle more than 1000 times.

[0014] In the substrate processing method, the thin film forming step includes: forming a nucleation layer containing a molybdenum compound on the substrate; and forming a molybdenum-containing main layer on the nucleation layer; the molybdenum compound of the processing layer and the molybdenum compound of the nucleation layer may be the same material.

[0015] In the substrate processing method, the molybdenum compound of the processing layer and the molybdenum compound of the nucleation layer may contain MoNa.

[0016] In the substrate processing method, before the processing layer forming step, a step of placing a cover substrate on the substrate support is included; after the processing layer forming step, a step of removing the cover substrate from the process chamber is included; the processing layer forming step can be performed while the cover substrate is placed on the substrate support.

[0017] In the substrate processing method, the processing layer formation step and the thin film formation step can be performed using chemical vapor deposition (CVD) or atomic layer deposition (ALD). Effects of the Invention

[0018] According to a portion of the embodiments of the present invention configured as described above, when depositing a molybdenum-containing thin film on a substrate, the uniformity of thickness is improved, and reproducibility is enhanced during repeated operations. Of course, this effect should not be used to limit the scope of the invention. Simple Explanation of the Diagram

[0019] Figure 1 is a schematic cross-sectional view showing a substrate processing apparatus according to an embodiment of the present invention; Figure 2 is a schematic flowchart illustrating a substrate processing method according to an embodiment of the present invention; Figure 3 is a schematic flowchart showing a substrate processing method according to another embodiment of the present invention; Figure 4 is a schematic flowchart showing the processing layer formation steps in the substrate processing method according to an embodiment of the present invention; Figure 5 is a schematic flowchart showing the first processing layer formation step in the substrate processing method according to an embodiment of the present invention; Figure 6 is a schematic flowchart showing the thin film formation steps in a substrate processing method according to an embodiment of the present invention; Figure 7 is a schematic diagram showing the relevant properties of the thin film formed according to the substrate processing method of the comparative example; and Figures 8 and 9 are schematic diagrams showing the relevant characteristics of the thin film formed by the substrate processing method according to the embodiment. Implementation

[0020] Hereinafter, various preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0021] The embodiments of the present invention are provided to provide a more complete explanation of the invention to those skilled in the art. The embodiments described below can be modified in various ways, and the scope of the invention is not limited to these embodiments. Rather, these embodiments are provided to make the invention more comprehensive and complete, and to fully convey the spirit of the invention to those skilled in the art. Furthermore, for ease of explanation and clarity, the thickness or size of each layer is exaggerated in the accompanying drawings.

[0022] Figure 1 is a schematic cross-sectional view showing a substrate processing apparatus 100 according to an embodiment of the present invention.

[0023] Referring to FIG1, the substrate processing apparatus 100 may include: a process chamber 110, a gas injection section 120, and a substrate support section 130.

[0024] More specifically, a reaction space 112 for processing the substrate S can be formed inside the process chamber 110. The process chamber 110 can be connected to a vacuum pump (not shown) via an exhaust pipe 114 to create a vacuum environment.

[0025] An inlet / outlet and a gate structure (not shown) may be provided in the process chamber 110. The inlet / outlet is used to load the substrate S into or unload the substrate S from the reaction space 112, and the gate structure is used to open and close the inlet / outlet. The process chamber 110 may be provided in various shapes, for example, it may include a main body 115 and a cover 117. For example, the main body 115 defines the reaction space 112 and may be open at the top. The cover 117 may be attached to the main body 115 to cover the main body 115, for example, the cover 117 may include a top cover.

[0026] The gas injection unit 120 can be integrated into the process chamber 110 to supply process gas to the reaction space 112. More specifically, the gas injection unit 120 can be disposed in the process chamber 110 facing the substrate support 130. For example, the gas injection unit 120 can be disposed at the upper part of the process chamber 110 to inject process gas onto the substrate S placed on the substrate support 130.

[0027] In some embodiments, the gas injection unit 120 may include: an inlet 122 through which process gas enters via a gas pipe 126; and an injection plate 124 for injecting the process gas dispersed inside through the inlet 122 into the reaction space 112. Further, the gas injection unit 120 may also include a baffle inside for dispersing the process gas passing through the inlet 122.

[0028] In some embodiments, the gas injection unit 120 may have various forms such as a nozzle or a spray nozzle. When the gas injection unit 120 is in the form of a nozzle, it may also be attached 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 attached to the cover 117 of the process chamber 110.

[0029] The substrate support portion 130 may be integrated into the process chamber 110 to support the substrate S. For example, the substrate support portion 130 may be disposed in the process chamber 110 facing the gas injection portion 120. The substrate support portion 130 may include an upper plate 132 and a shaft 135, wherein the upper plate 132 holds the substrate S and the shaft 135 supports the upper plate 132.

[0030] In some embodiments, the substrate support 130 may include a heater 182 for heating the substrate S within the upper plate 132. For example, a heater power supply 180 for supplying power may be connected to the heater 182. Further, an AC filter 185 may be connected between the heater power supply 180 and the heater 182.

[0031] The shape of the upper plate 132 roughly corresponds to the shape of the substrate S, but is not limited to this; various shapes are available, larger than the substrate S, to stably place the substrate S. The shaft 135 can be connected to an external motor (not shown) to achieve lifting; alternatively, a bellows (not shown) can be connected to maintain airtightness. The substrate support 130 is configured to place the substrate S on it, and therefore can also be called a substrate placement part, substrate holder, base, etc.

[0032] In some embodiments, the substrate support portion 130 may include an electrostatic electrode (not shown). The electrostatic electrode serves as an electrostatic electrode for fixing the substrate S by electrostatic force. When the substrate S is attracted by electrostatic force, the substrate support portion 130 may also be referred to as an electrostatic chuck. The electrostatic electrode may receive DC power to apply electrostatic force to the substrate S.

[0033] In some embodiments, the substrate processing apparatus 100 may include a plasma power supply unit 140 to form a plasma environment within the process chamber 110. The plasma power supply unit 140 may be connected to the process chamber 110 to supply RF (radio frequency) power for forming the plasma environment within the reaction space 112 inside the process chamber 110. For example, the plasma power supply unit 140 may be connected to a gas jet unit 120, which may also be referred to as a power supply electrode or upper electrode. For example, the plasma power supply unit 140 may supply high-frequency (HF) power and / or low-frequency (LF) power.

[0034] Additionally, the impedance matching section 146 can be configured between the plasma power supply section 140 and the gas injection section 120 to achieve impedance matching. The RF power supplied from the plasma power supply section 140 needs to be properly impedance matched between the plasma power supply section 140 and the process chamber 110 through the impedance matching section 146 so that it will not be reflected back from the process chamber 110, but can be effectively transmitted to the process chamber 110.

[0035] The impedance matching section 146 may be composed of two or more resistors, inductors, and capacitors connected in series or in parallel. Furthermore, the impedance matching section 146 may employ at least one variable capacitor or capacitor array switching structure to change the impedance value according to the frequency and process conditions of the RF power.

[0036] In some embodiments, the substrate processing apparatus 100 described above can be used for thin film deposition using chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), or atomic layer deposition (ALD).

[0037] In some embodiments, the plasma power supply unit 140 in the substrate processing apparatus 100 described above is omitted, and the substrate processing apparatus 100 can be used for thin film deposition using the thermochemical vapor deposition (thermal CVD) method without plasma.

[0038] Hereinafter, a substrate processing method according to an embodiment of the present invention will be described using the substrate processing apparatus 100 described above.

[0039] Figure 2 is a schematic flowchart illustrating a substrate processing method according to an embodiment of the present invention.

[0040] Referring to Figures 1 and 2, the substrate processing method may include: step S20 of forming a processing layer inside the process chamber 110; step S40 of placing a substrate S on a substrate support 130 inside the process chamber 110 where the processing layer is formed; and step S50 of forming a thin film on the substrate S placed on the substrate support 130.

[0041] In some embodiments, the thin film contains at least molybdenum (Mo), and the processing layer may contain materials associated with the thin film. For example, the processing layer may contain at least a molybdenum compound, and the processing layer may be formed inside the process chamber 110. For example, the processing layer may be formed at least on the inner wall of the process chamber 110. Further, the processing layer may be formed on structures inside the process chamber 110, such as the surface of the gas jet section 120 and / or the surface of the substrate support section 130.

[0042] More specifically, the processing layer formation step S20 can be performed by supplying molybdenum-containing gas and a gas containing auxiliary components for compound formation to the reaction space 112 through the gas injection section 120. Within the reaction space 112, the molybdenum-containing gas reacts with the gas containing auxiliary components, thereby forming a molybdenum compound on the substrate S.

[0043] In some embodiments, the processing layer formation step S20 can be performed using CVD or ALD methods. For example, a molybdenum-containing gas and a gas containing auxiliary components are supplied together in the reaction space 112, and these gases react within the reaction space 112 using CVD, thereby forming a molybdenum compound on the substrate S. As another example, a molybdenum-containing gas and a gas containing auxiliary components are repeatedly supplied sequentially to the reaction space 112, and a molybdenum compound can be formed on the substrate S using ALD.

[0044] In some embodiments, as shown in FIG4, the processing layer forming step S20 may include a first processing layer forming step S22 containing a molybdenum compound. For example, the first processing layer forming step S22 may be performed by supplying a molybdenum-containing gas and a gas containing auxiliary components for forming the compound to the reaction space 112 through the gas injection unit 120.

[0045] In some embodiments, as shown in FIG5, the first processing layer forming step S22 can be performed repeatedly in a cycle, which may sequentially include: step S221 of supplying molybdenum-containing gas into the reaction space 112 and step S223 of supplying gas containing auxiliary components into the reaction space 112. Optionally, the step of supplying purge gas may be added after steps S221 and S223, respectively. This purge gas can be used to remove gas remaining in the reaction space 112.

[0046] More specifically, in step S221, an atomic-level molybdenum-containing gas is adsorbed onto the substrate S. In step S223, a gas containing auxiliary components reacts with the molybdenum-containing gas adsorbed on the substrate S, forming an atomic-level molybdenum compound on the substrate S. Through repeated cycles, a first processing layer of molybdenum compound of predetermined thickness can be formed on the substrate S.

[0047] For example, the first processing layer may contain a molybdenum compound, such as any one of MoNa, MoSiaHb, MoaBbHc, and MoOx. As the molybdenum-containing gas, molybdenum or various molybdenum compounds can be provided in gaseous form, such as a precursor of MoO₂Cl₂ or MoCl₅. For example, the gas containing auxiliary components may be a gas containing at least one of nitrogen (N), silicon (Si), boron (B), and oxygen (O). As the nitrogen-containing gas, N₂, NH₃, N₂O, etc., can be used; as the silicon-containing gas, silane (SiH₄), dichlorosilane, etc., can be used; as the boron-containing gas, B₂H₆, etc., can be used; and as the oxygen-containing gas, O₂, H₂O₂, O₃, etc., can be used.

[0048] In some embodiments, as shown in FIG4, the processing layer forming step S20 may include a step S24, after the first processing layer forming step S22, of forming a molybdenum-containing second processing layer on the first processing layer within the process chamber 110. For example, the second processing layer forming step S24 may be performed by supplying molybdenum-containing gas and hydrogen-containing gas into the reaction space 112 through the gas injection unit 120.

[0049] The second processing layer formation step S24 can be performed using either CVD or ALD methods. For example, molybdenum-containing gas and hydrogen-containing gas are supplied together in the reaction space 112, and these gases react within the reaction space 112 using CVD to form a molybdenum layer on the substrate S. As another example, the molybdenum-containing gas and hydrogen-containing gas are sequentially supplied to the reaction space 112 in a cycle repeated multiple times, and a molybdenum layer can be formed on the substrate S using ALD. For example, the reaction space 112 can be sequentially supplied with molybdenum-containing gas, followed by purge gas, then hydrogen-containing gas, and finally purge gas.

[0050] For example, as a molybdenum-containing gas, molybdenum or various molybdenum compounds can be supplied in gaseous form, such as containing precursors like MoO₂Cl₂ or MoCl₅. As a hydrogen-containing gas, H₂ or H₂O gases can be utilized.

[0051] In some embodiments, in the second processing layer formation step S24, the second processing layer may include MoOx. For example, as the second processing layer, the MoOx layer may be formed by supplying molybdenum-containing gas and hydrogen-containing gas into the reaction space 112, or by supplying molybdenum-containing gas and oxygen-containing gas, or by supplying molybdenum-containing gas, hydrogen-containing gas, and oxygen-containing gas. More specifically, as the second processing layer, the MoOx layer may be formed by reacting molybdenum-containing gas (MoOxN) and hydrogen-containing gas (NH3 or H2) in a state where the molybdenum-containing gas is not fully reduced, or it may be formed by reacting molybdenum-containing gas (MoOxN) with oxygen-containing gas (O2, H2O2 or O3).

[0052] In some embodiments, the second processing layer may be thinner than the first processing layer. For example, the first processing layer needs to be formed to a thickness sufficient to cover the interior of the process chamber 110, and may be formed to a thickness of 100 nm or more. The second processing layer, as an optional additional layer, may be formed to a thickness of 20 nm or more. For example, the second processing layer may be formed to a thickness of less than half that of the first processing layer, or more precisely, to a thickness of less than two-fifths that of the first processing layer.

[0053] After the processing layer is formed in the process chamber 110 in step S20, a process for depositing a thin film on the substrate S can be performed. As shown in FIG2, the substrate S can be placed on the substrate support 130 in the process chamber 110 where the processing layer is formed (S40). Next, a thin film containing at least molybdenum can be formed on the substrate S placed on the substrate support 130 (S50).

[0054] In some embodiments, as shown in FIG6, the thin film formation step S50 may include: step S52 of forming a nucleation layer on the substrate S and step S54 of forming a main layer on the nucleation layer. For example, the nucleation layer formation step S52 may include a molybdenum compound, and the main layer may contain molybdenum. The nucleation layer serves as a base layer for the growth of the main layer when it is difficult to directly grow the main layer on the substrate S.

[0055] For example, the molybdenum compound in the nucleation layer and the molybdenum compound in the treatment layer can be the same material. That is, the nucleation layer and the first treatment layer can be the same material. For example, the nucleation layer and the first treatment layer can contain MoNa, MoSiaHb, MoaBbHc, or MoOx. In some embodiments, the nucleation layer and the first treatment layer can contain MoNa.

[0056] In some embodiments, a cleaning process can be performed inside the process chamber 110 before the processing layer is formed inside the process chamber 110. For example, if multiple thin film formation processes are performed in the process chamber 110, a thin film may also be formed inside the process chamber 110, which may then form particles. For this purpose, a cleaning process can be performed on the process chamber 110. After the cleaning process is performed on the process chamber 110, a processing layer can be formed inside the process chamber 110.

[0057] In some embodiments, after the processing layer formation step S20, the steps of placing the substrate S and forming a thin film on the substrate S can be repeated multiple times. Accordingly, after forming a processing layer once inside the process chamber 110, a thin film can be formed on multiple substrates S. Further, after performing a predetermined number of substrate S processing steps inside the process chamber 110, and then performing a cleaning process on the process chamber 110, the processing layer formation step S20 can be continued again.

[0058] Figure 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 steps to the substrate processing method of Figure 2. The embodiments can be referred to each other, so repeated descriptions are omitted.

[0059] Referring to FIG3, the substrate processing method may include: step S10 of placing a cover substrate on the substrate support 130, step S20 of forming a processing layer inside the process chamber 110, step S30 of removing the cover substrate from the process chamber 110, step S40 of placing a substrate S on the substrate support 130 inside the process chamber 110, and step S50 of forming a thin film on the substrate S placed on the substrate support 130.

[0060] For example, the cover substrate can utilize the substrate shape that covers the substrate support portion 130, such as a dummy substrate. The cover substrate can be supplied from outside the substrate processing apparatus or stored in a storage container within the substrate processing apparatus. In the cover substrate placement step S10, the cover substrate can be loaded into the process chamber 110 from an external or internal storage container. For example, if the substrate support portion 130 is used as an electrostatic chuck, in order to suppress the formation of a conductive processing layer on the substrate support portion 130, the cover substrate can be placed on the substrate support portion 130 before the processing layer is formed.

[0061] In step S20, with the cover substrate placed on the substrate support 130, a processing layer can be formed inside the process chamber 110. Accordingly, the processing layer is formed on the inner wall of the process chamber 110 and the gas injection section 120, and may not be formed on the top surface of the substrate support 130.

[0062] In step S30, the cover substrate with the processing layer formed can be transported out of the process chamber 110. For example, the cover substrate can be transported out of the process chamber 110 to the outside of the substrate processing apparatus 100 or can be moved into the storage container in the substrate processing apparatus 100.

[0063] Next, a substrate S is placed on a substrate support 130 within a process chamber 110 where a processing layer is formed (S40), and a thin film can be formed on the substrate S (S50).

[0064] On the other hand, in some embodiments, when the substrate support portion 130 does not have the function of an electrostatic chuck, the processing layer can be formed on the substrate support portion 130 without placing a cover substrate on the substrate support portion 130 when forming the processing layer.

[0065] According to the substrate processing method described above, a uniform processing layer is formed inside the process chamber 110 before forming a thin film on the substrate S, thereby improving the thickness uniformity and reducing particle generation when forming the thin film on the substrate S. Furthermore, when the thin film is repeatedly formed on the substrate S inside the process chamber 110, the reproducibility of the thin film can be improved.

[0066] The characteristics of the thin films formed according to the substrate processing methods of the comparative examples and embodiments are described below.

[0067] Figure 7 is a schematic diagram showing the relevant characteristics of the thin film formed according to the substrate processing method of the comparative examples. In Comparative Examples 1 to 7, a processing layer was formed with molybdenum (Mo) in the process chamber 110, and then a MoN nucleation layer and a Mo main layer were formed on the substrate S as thin films. From Comparative Examples 1 to 7, the number of cycles used to form the Mo processing layer was gradually increased from 295 to 2655.

[0068] Referring to Figure 7, it can be seen that Comparative Examples 1 to 7 all failed to meet the target values ​​for surface resistivity uniformity (Rs uniformity) and thickness uniformity (THK uniformity). Therefore, when depositing Mo thin films, the Mo deposition as the processing layer in the process chamber 110 was unsatisfactory. This result is presumably caused by the inability of the Mo processing layer to grow uniformly on the inner wall of the process chamber 110. For example, when the inner wall of the process chamber is coated with tungsten oxide (WOx), the surface energy difference between molybdenum and tungsten oxide is large, making it difficult for molybdenum to grow uniformly on the tungsten oxide.

[0069] Figures 8 and 9 are schematic diagrams showing the relevant characteristics of the thin film formed by the substrate processing method according to the embodiment.

[0070] Examples 1 to 5 illustrate the formation of a MoN nucleation layer and a Mo main layer as a thin film on a substrate S after forming a MoN layer as a processing layer. In Examples 1 to 5, the number of cycles for forming the MoN processing layer gradually increased from 400 to 1500.

[0071] Referring to Figure 8, it can be seen that as the number of cycles of the MoN processing layer increases, the surface resistance uniformity (Rs uniformity) and thickness uniformity (THK uniformity) show a decreasing trend. More specifically, it can be seen that in Examples 1 to 3, where the number of cycles of the MoN processing layer is 800, the target values ​​for surface resistance uniformity (Rs uniformity) and thickness uniformity (THK uniformity) cannot be met, but the target values ​​are met for more than this number of cycles.

[0072] Therefore, it can be understood that in order to meet the characteristic specifications of the Mo main layer formed on substrate S, the number of cycles of the MoN treatment layer should exceed 800. More precisely, as in Examples 4 and 5, the number of cycles of the MoN treatment layer should be 1000 or more. Considering the deposition rate per cycle, in order to meet the characteristic specifications of the Mo main layer formed on substrate S, the thickness of the MoN treatment layer can be approximately 120 nm or more, and more precisely, 150 nm or more. When the thickness of the Mo main layer is 20 nm, the thickness of the MoN treatment layer can be approximately 6 times or more than the thickness of the Mo main layer, and more precisely, 7.5 times or more.

[0073] Examples 6 to 8 involve forming a MoN layer 2000 times as a processing layer, followed by forming a MoN nucleation layer and a Mo main layer as a thin film on the substrate S. From Examples 6 to 8, the number of times the thin film is formed on the substrate S is increased from 1 to 3.

[0074] As described above, the reason for the effectiveness of the MoN treatment layer can be understood as the small surface energy difference between the tungsten oxide coating material on the inner wall of the process chamber 110 and the MoN layer. Therefore, the MoN treatment layer can grow uniformly on the inner wall of the process chamber 110. Furthermore, in order to avoid adverse effects on the thin film formation process on the substrate S, it is determined that it is necessary to form a MoN treatment layer with a predetermined thickness or more on the inner wall of the process chamber 110.

[0075] Referring to Figure 9, it can be seen that Examples 6 to 8 all meet the specifications for surface resistivity uniformity (Rs uniformity) and thickness uniformity (THK uniformity). However, it can be seen that the film properties change with the number of film formations. For example, it can be seen that the films of Examples 7 and 8, which have been formed more than twice, exhibit reproducible values, but the values ​​of the film of Example 6, which has only been formed once, are slightly different.

[0076] Therefore, it can be seen that after forming the processing layer 2000 times in the process chamber 110, it is necessary to form a Mo thin film of a predetermined thickness in order to ensure reproducibility when forming a thin film on the substrate S. From this point of view, it can be seen that when forming a Mo layer of predetermined thickness after forming a MoN layer of sufficient thickness during the formation of the processing layer, the reproducibility during the formation of the thin film can be improved. For example, the thickness of the Mo layer formed as the processing layer can be at least 20 nm, which is the thickness of one thin film, and more reliably, it can be 60 nm or more. In addition, from the results of Examples 6 to 8 above, it can be seen that after forming the MoN processing layer, at least one MoN layer and a Mo layer can be formed on the MoN layer.

[0077] Based on the comparative examples and embodiments described above, it can be seen that, compared to the case where a Mo treatment layer is formed inside the process chamber 110 before forming a thin film on the substrate S, forming a MoN treatment layer of a predetermined thickness or greater satisfies the physical properties of the thin film. Furthermore, in order to improve the reproducibility of the physical properties of the thin film, after forming the MoN treatment layer, considering the thin film process, a Mo layer may also be formed on the MoN treatment layer.

[0078] The invention has been described with reference to the embodiments shown in the accompanying drawings; however, these are merely exemplary, and it will be understood by one of ordinary skill in the art that various modifications and equivalent embodiments can be implemented. Therefore, the true scope of protection of this invention should be defined by the technical concept of the claims.

[0079] 100: Substrate processing apparatus 110: Process Chamber 112: Reaction space 114: Exhaust pipe 115: Main body 117:Gaibu 120: Gas injection section 122: Entrance 124: Spray Plate 126: Gas pipeline 130: Substrate support portion 132:On the board 135: Axis 140: Plasma Power Supply Department 146: Impedance Matching Section 180: Heater power supply section 182: Heater 185: AC filter S:Substrate S10: Steps S20: Steps S22: Steps S24: Steps S30: Steps S40: Steps S50: Steps S52: Steps S54: Steps S221: Steps S223: Steps

Claims

1. A substrate processing method, utilizing a substrate processing apparatus, the substrate processing apparatus comprising: A process chamber having a reaction space formed inside; a gas injection unit disposed in the process chamber for supplying a process gas to the reaction space; The method includes a substrate support portion disposed in the process chamber opposite to the gas jet portion for supporting a substrate; the substrate processing method includes the following steps: forming a processing layer inside the process chamber; The substrate is placed on the substrate support within the process chamber where the processing layer is formed; and a thin film is formed on the substrate placed on the substrate support; wherein the processing layer comprises at least a molybdenum compound, and wherein the thin film comprises at least molybdenum, the processing layer forming step includes a first processing layer forming step containing the molybdenum compound, and in the first processing layer forming step, a molybdenum-containing gas and a gas containing auxiliary components for forming the compound are supplied to the reaction space through the gas injection section, the first processing layer comprises MoNa, and in the first processing layer forming step, the molybdenum-containing gas and the gas containing auxiliary components are sequentially supplied to the reaction space in a cycle repeated more than 1000 times.

2. The substrate processing method as described in claim 1, wherein, The gas containing the auxiliary components is a gas containing at least one of nitrogen (N), silicon (Si), boron (B) and oxygen (O), and the first processing layer contains any one of MoNa, MoSiaHb, MoaBbHc and MoOx.

3. The substrate processing method as described in claim 1, wherein, The processing layer forming step includes forming a second processing layer containing molybdenum on the first processing layer, and in the second processing layer forming step, supplying the molybdenum-containing gas and the hydrogen-containing gas into the reaction space through the gas injection section.

4. The substrate processing method as described in claim 3, wherein, The second processing layer is formed to be thinner than the first processing layer.

5. The substrate processing method as described in claim 1, wherein, The processing layer forming step includes forming a second processing layer containing MoOx on the first processing layer, and in the second processing layer forming step, supplying the molybdenum-containing gas and hydrogen-containing gas or oxygen-containing gas into the reaction space through the gas injection section.

6. The substrate processing method as described in claim 1, wherein, The thin film forming step includes: forming a nucleation layer containing the molybdenum compound on the substrate; and forming a molybdenum-containing main layer on the nucleation layer, wherein the molybdenum compound in the processing layer and the molybdenum compound in the nucleation layer are the same material.

7. The substrate processing method as described in claim 6, wherein, The molybdenum compound in the treatment layer and the molybdenum compound in the nucleation layer comprise MoNa.

8. The substrate processing method as described in claim 1, wherein, The process includes a step of placing a cover substrate on the substrate support before the processing layer formation step, a step of removing the cover substrate from the process chamber after the processing layer formation step, and the processing layer formation step is performed while the cover substrate is placed on the substrate support.

9. The substrate processing method as described in claim 1, wherein, The processing layer formation step and the thin film formation step utilize chemical vapor deposition or atomic layer deposition.

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