Method for forming electrodes of semiconductor element and electrodes of semiconductor element

Abstract

A method for forming an electrode of a semiconductor device according to an embodiment of the present invention may include the steps of preparing a substrate, spraying a precursor containing a low-resistance metal element onto the substrate, and spraying a gas containing hydrogen (H) or oxygen (O) onto the substrate to form a low-resistance metal thin film layer. Therefore, according to the embodiment of the present invention, an electrode can be provided in which ligand impurities resulting from precursors containing low-resistance metal elements are removed, and therefore an electrode with low resistance can be provided.

Description

[Technical field]

[0001] The present invention relates to a method for forming an electrode of a semiconductor device, and more particularly to a method for forming an electrode of a semiconductor device and an electrode of a semiconductor device that can improve characteristics. [Background technology]

[0002] In order to improve the electrical characteristics of semiconductor devices such as NAND flash, it is necessary to reduce the resistance of the electrodes.

[0003] When forming an electrode of a semiconductor device, a precursor containing a metal is sprayed and then evaporated onto a substrate.

[0004] Meanwhile, the precursor used for forming the electrode contains at least one ligand selected from carbon (C), oxygen (O) and hydrogen (H). However, these ligands act as impurities that increase the resistance of the electrode, which may result in a deterioration in the electrical characteristics of the semiconductor device.

[0005] In addition, recent semiconductor technology has been developing remarkably, and the speed and integration of semiconductor devices are rapidly increasing, which has led to an increasing need for finer patterns and higher pattern dimensions. However, the film quality of the electrodes of semiconductor devices may deteriorate depending on the lower and upper films, which may affect the operation of the semiconductor devices. For this reason, research and development efforts have been made recently to improve the operation of semiconductor devices by manufacturing semiconductor devices in a three-dimensional structure.

[0006] In such a manufacturing process, the silicon or silicon-containing film and electrodes constituting the semiconductor device are exposed to an etching gas during the patterning or planarization process. The etching gas may be a gas containing a halogen element. Elements such as fluorine (F) and chlorine (Cl), which are representative examples of halogen elements, can react with the surface of the silicon or silicon-containing film. The silicon or silicon-containing film may be etched when exposed to a deposition gas. When an insulating film, a dielectric film, or a metal film is formed on the silicon or silicon-containing film, if the gas for depositing these thin films contains a halogen element such as fluorine or chlorine, the silicon or silicon-containing film, which is the lower film, may be unintentionally etched by the halogen element such as fluorine or chlorine during the thin film formation process. If the silicon or silicon-containing film is etched by the halogen element contained in the deposition gas during the deposition process, the surface of the etched silicon or silicon-containing film is damaged, resulting in an uneven and irregular surface. An upper film formed on a lower film having an uneven and irregular surface may cause defects at the interface with the lower film, and may also adversely affect the formation of the upper film.

[0007] In order to prevent damage to the underlying film during the deposition process, a barrier film may be formed on the silicon or silicon-containing film instead of forming a deposition film directly on the silicon or silicon-containing film to prevent damage to the underlying film. If the deposition film is to be used as an electrode for a semiconductor device, a titanium nitride film (TiN) may be formed on the silicon or silicon-containing film as a barrier film.

[0008] The titanium nitride film as a barrier film also plays a role in preventing halogen elements generated during the subsequent formation of a metal film, an electrode, from damaging the underlying silicon or silicon-containing film. The reaction gas for forming the titanium nitride film may also contain halogen elements. For example, titanium tetrachloride (TiCl 4) is used to form the titanium nitride film. Therefore, the titanium nitride film, which is a barrier film formed between the silicon or silicon-containing film and the electrode, may also damage the silicon or silicon-containing film, which is the underlying film, during the formation process, and the surface of the silicon or silicon-containing film may become uneven and irregular. When an electrode is formed on the titanium nitride film, which is a barrier film, the titanium nitride film may be damaged by halogen elements contained in the deposition gas forming the electrode. Even if damage to the silicon or silicon-containing film, which is the underlying film, is reduced, the titanium nitride film, which is a barrier film, may itself be damaged, causing cracks in the titanium nitride film or the titanium nitride film itself to be damaged. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent No. 10-0942958 [Patent Document 2] Korean Patent Publication No. 10-2011-0001487 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention provides a method for forming electrodes of a semiconductor device, which can reduce the resistance of the electrodes.

[0011] The present invention provides a method for forming an electrode of a semiconductor device that can remove impurities.

[0012] The present invention provides a method for forming an electrode of a semiconductor device, and an electrode of a semiconductor device, which reduces damage to an underlying layer that occurs during the process of forming the electrode. [Means for solving the problem]

[0013] A method for forming an electrode of a semiconductor device according to an embodiment of the present invention may include the steps of preparing a substrate, spraying a precursor containing a low-resistance metal element onto the substrate, and spraying a gas containing hydrogen (H) or oxygen (O) onto the substrate to form a low-resistance metal thin film layer.

[0014] The step of spraying the precursor and the step of forming the low resistance metal thin film layer may be performed multiple times in this order.

[0015] The method for forming an electrode of a semiconductor element includes a step of exposing the substrate to a first plasma after the step of spraying the precursor to remove impurities adsorbed on the substrate, and a step of exposing the low-resistance metal thin film layer to a second plasma after the step of forming the low-resistance metal thin film layer to remove impurities, and the steps of spraying the precursor, exposing to the first plasma, and exposing to the second plasma may be performed multiple times in this order.

[0016] The low-resistance metal element may include at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

[0017] The first plasma may be formed by a plasma containing hydrogen (H) or a plasma containing oxygen (O).

[0018] The second plasma may be formed by a plasma containing hydrogen (H) or a plasma containing oxygen (O).

[0019] The method for forming an electrode of a semiconductor element further includes a step of forming a TiN thin film layer on the substrate, and the step of forming the TiN thin film layer includes a step of spraying a source containing titanium (Ti) onto the substrate, and a step of spraying a gas containing nitrogen (N) onto the substrate, and the step of spraying a precursor containing the low-resistance metal element, the step of forming a low-resistance metal thin film layer, and the step of forming the TiN thin film layer may be performed multiple times in this order.

[0020] The step of preparing a substrate may include preparing a substrate having a TiN thin film layer formed on an upper surface thereof.

[0021] A method for forming an electrode of a semiconductor element according to an embodiment of the present invention includes the steps of preparing a substrate, injecting a source containing a first low-resistance metal element and injecting a gas containing hydrogen (H) or oxygen (O) to form a first low-resistance metal thin film layer, and injecting a source containing a second low-resistance metal element and injecting a gas containing hydrogen (H) or oxygen (O) to form a second low-resistance metal thin film layer, and the steps of forming the first low-resistance metal thin film layer and forming the second low-resistance metal thin film layer may be performed multiple times in this order.

[0022] The first low-resistance metal element and the second low-resistance metal element may include at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

[0023] The first low-resistance metal element and the second low-resistance metal element may contain the same metal element.

[0024] At least one of the first low-resistance metal element and the second low-resistance metal element may include at least two of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

[0025] The method for forming an electrode of a semiconductor element may further include a step of spraying a source containing titanium (Ti) and a reactant containing nitrogen (N) to form a TiN thin film layer, and the step of forming the first low-resistance metal thin film layer, the step of forming the second low-resistance metal thin film layer, and the step of forming the TiN thin film layer may be repeated in this order.

[0026] The step of preparing a substrate may include preparing a substrate having a TiN thin film layer formed on an upper surface thereof.

[0027] A method for forming an electrode of a semiconductor device according to an embodiment of the present invention may include the steps of preparing a substrate, spraying a liquid phase precursor containing a low-resistance metal element onto the substrate, and spraying a gas containing hydrogen (H) or oxygen (O) onto the substrate to form a low-resistance metal thin film layer.

[0028] The step of spraying the precursor and the step of forming the low resistance metal thin film layer may be performed multiple times in this order.

[0029] The low-resistance metal element may include at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

[0030] An embodiment of the present invention may be a method of forming an electrode for a semiconductor device, comprising the steps of forming a ruthenium or ruthenium-containing film on a silicon or silicon-containing film, and forming a tungsten-containing film on the ruthenium or ruthenium-containing film.

[0031] The ruthenium film or ruthenium-containing film is preferably formed to a thickness that is 50% or less of the thickness of the tungsten-containing film.

[0032] The ruthenium film or ruthenium-containing film is preferably formed to a thickness of 5 Å to 50 Å.

[0033] The ruthenium film or ruthenium-containing film is preferably formed by atomic layer deposition.

[0034] The ruthenium film or ruthenium-containing film is preferably formed from an organic source containing ruthenium.

[0035] The tungsten-containing film is preferably formed from a tungsten halogen gas.

[0036] The electrode is preferably any one of a memory element electrode, a word line, a bit line, a transistor electrode, a GaN semiconductor electrode, and a GaAs semiconductor electrode.

[0037] The method for forming an electrode of a semiconductor element according to an embodiment of the present invention may include a step of removing oxides or impurities on a surface of the silicon or silicon-containing film before forming the ruthenium film or ruthenium-containing film.

[0038] An electrode of a semiconductor device according to an embodiment of the present invention may include a silicon or silicon-containing film, a ruthenium or ruthenium-containing film formed on the silicon or silicon-containing film, and a tungsten-containing film formed on the ruthenium or ruthenium-containing film.

[0039] The ruthenium film or ruthenium-containing film is preferably formed to a thickness that is 50% or less of the thickness of the tungsten-containing film.

[0040] The ruthenium film or ruthenium-containing film is preferably formed to a thickness of 5 Å to 50 Å.

[0041] The ruthenium film or ruthenium-containing film is preferably formed by atomic layer deposition.

[0042] The ruthenium film or ruthenium-containing film is preferably formed from an organic source containing ruthenium.

[0043] The tungsten-containing film is preferably formed from a tungsten halogen gas.

[0044] The electrode may be any one of an electrode of a memory element, a word line, a bit line, and an electrode of a transistor. Effect of the Invention

[0045] According to an embodiment of the present invention, a precursor containing a low-resistance metal element is injected, followed by injection of a reducing gas, and hydrogen plasma or oxygen plasma is generated before and after injection of the reducing gas.

[0046] Therefore, according to the embodiment of the present invention, it is possible to provide an electrode from which ligand impurities resulting from precursors containing low-resistance metal elements have been removed, and therefore an electrode with low resistance can be provided.

[0047] Furthermore, according to the embodiment of the present invention, the barrier film and the electrode can be formed to reduce damage to the underlying film. [Brief description of the drawings]

[0048] [Figure 1] FIG. 1 is a diagram showing a state in which an electrode according to a first embodiment of the present invention is formed on a substrate. [Diagram 2] FIG. 2 is a conceptual diagram for explaining a method for forming an electrode by the method according to the first embodiment of the present invention. [Diagram 3] FIG. 2 is a process diagram conceptually showing a method for forming an electrode by the method according to the first embodiment of the present invention. [Figure 4] FIG. 11 is a diagram showing a state in which an electrode according to a second embodiment of the present invention is formed on a substrate. [Diagram 5] FIG. 4 is a conceptual diagram for explaining a method for forming an electrode by a method according to a second embodiment of the present invention. [Figure 6] FIG. 13 is a diagram showing a state in which an electrode according to a first modified example of the first embodiment is formed on a substrate. [Figure 7] FIG. 13 is a diagram showing a state in which an electrode according to a second modified example of the first embodiment is formed on a substrate. [Figure 8] FIG. 13 is a diagram illustrating a schematic structure of a semiconductor element according to a third embodiment of the present invention. [Figure 9] 10A to 10C are diagrams illustrating a method for forming a semiconductor device according to a third embodiment of the present invention. [Figure 10]10A to 10C are diagrams illustrating a method for forming a semiconductor device according to a third embodiment of the present invention. [Figure 11] 10A to 10C are diagrams illustrating a method for forming a semiconductor device according to a third embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] Hereinafter, the embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and can be embodied in various different forms. The following embodiments are provided only to complete the disclosure of the present invention and to fully inform those skilled in the art of the scope of the invention. In order to explain the embodiments of the present invention, the drawings may be exaggerated, and the same reference numerals in the drawings refer to the same components.

[0050] The present invention relates to a method for forming an electrode of a semiconductor device, more particularly to a method for forming an electrode of a semiconductor device having improved electrical characteristics, and more particularly to a method for forming an electrode of a semiconductor device, including a method for forming a low-resistance metal thin film layer.

[0051] As a specific example, the semiconductor device may be a NAND flash, and the electrode may be a gate electrode of the NAND flash. Needless to say, the electrode formed by the method according to the embodiment is not limited to a gate electrode, but may be a wide variety of components that require electrical conductivity, such as a word line of a NAND flash. The electrode formed by the method according to the embodiment is not limited to a NAND flash, but may be a thin film that requires electrical conductivity in a wide variety of semiconductor devices.

[0052] FIG. 1 is a diagram showing a state in which an electrode according to a first embodiment of the present invention is formed on a substrate.

[0053] 1, an electrode 100 may be formed on a substrate S. Here, the substrate S may be a wafer, and may be any one of a Si wafer, a GaAs wafer, and a SiGe wafer.

[0054] The electrode 100 may be formed using a low-resistance metal element. Here, the low-resistance metal element may include at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu). Therefore, the electrode may be a thin film formed using at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu) or a thin film including at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu).

[0055] A method for forming an electrode on a substrate by a method according to a first embodiment of the present invention will be described below with reference to FIGS.

[0056] Fig. 2 is a conceptual diagram for explaining a method for forming an electrode by the method according to the first embodiment of the present invention. Fig. 3 is a process diagram conceptually showing the method for forming an electrode by the method according to the first embodiment of the present invention.

[0057] In FIG. 2, "on" means that the raw material for deposition is injected or plasma is generated, and "off" can mean that the injection of the raw material is interrupted or ended, or that plasma is not generated.

[0058] Referring to FIG. 2, the method of forming the electrode 100 may include a process of injecting a precursor containing a low-resistance metal element (precursor injection process) and a process of injecting a reducing gas containing hydrogen (H) or oxygen (O) to form a low-resistance metal thin film layer 110 on the substrate S (reducing gas injection process).

[0059] In addition, the method for forming the electrode 100 may further include a process of generating plasma using a gas containing hydrogen (H) or oxygen (O) after the precursor injection process is completed (first plasma generation process), and a process of generating plasma using a gas containing hydrogen (H) or oxygen (O) after the reducing gas injection process is completed (hereinafter, second plasma) to remove impurities from the low-resistance metal thin film layer 110 (second plasma generation process).

[0060] The method of forming the electrode 100 may further include a process of injecting a purge gas between the precursor injection process and the first plasma generation process (first purge process), and a process of injecting a purge gas between the reducing gas injection process and the second plasma generation process (second purge process).

[0061] That is, the method of forming the electrode 100 may include a precursor injection process, a purge gas injection process (first purge process), a first plasma generation process, a reducing gas injection process, a purge gas injection process (second purge process), and a second plasma generation process.

[0062] Also, the above-mentioned "precursor injection process-first plasma generation process-first purge process-reducing gas injection process-second plasma generation process-second purge process" may be one process cycle CY for forming a low-resistance metal thin film layer 110. The above-mentioned process cycle CY is repeated a number of times to deposit or stack a number of low-resistance metal thin film layers 110 as shown in FIG. 1. Thus, an electrode in which a number of low-resistance metal thin film layers 110 are stacked or an electrode 100 of a semiconductor device including a number of low-resistance metal thin film layers 110 is formed. At this time, the number of times the process cycle CY is repeated can be adjusted according to the target film thickness of the electrode 100 to be formed.

[0063] In FIG. 1, each low-resistance metal thin film layer 110 is shown separately in order to distinguish the thin film layers formed by the multiple process cycles CY, but the multiple stacked low-resistance metal thin film layers 110 may be integral.

[0064] In the following, each step of the process cycle CY will be described in more detail. For ease of explanation, the "low-resistance metal thin film layer 110" formed by the above-mentioned process cycle CY will be abbreviated to "metal thin film layer 110".

[0065] In the process of injecting the precursor, a precursor containing a low-resistance metal element is injected into the chamber in which the substrate S is placed. That is, a material containing a low-resistance metal element is used as the precursor. Here, the low-resistance metal element may be at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu). That is, the precursor containing a low-resistance metal element may be a precursor containing at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu). And the "precursor containing a low-resistance metal element" can be named a "source containing a low-resistance metal element".

[0066] As a precursor containing molybdenum (Mo), for example, a material containing at least one of molybdenum hexacarbonyl and molybdenum pentachloride can be used.

[0067] The precursor containing ruthenium (Ru) is, for example, ethylcyclopentadienyl ruthenium (EtCp) 2 Materials including Bis(ethylcyclopentadienyl)ruthenium (Ru) can be used.

[0068] As a precursor containing copper (Cu), for example, an organometallic compound or a material containing F or Cl can be used. More specifically, as a source of a copper (Cu)-containing precursor, which is an organometallic compound, for example, copper (II)-2,2,6,6-tetramethyl-3,5-heptanedionate [Cu(thd)] can be used. 2](Cu(II)-2,2,6,6-tetramethyl-3,5-heptandionate[Cu(thd) 2 ]) and copper(II) hexafluoroacetylacetonate [Cu(hfac) 2 ](Cu(II) hexafluoroacetylacetonate [Cu(hfac) 2 ]) can be used. As a copper precursor source containing F or Cl, CuCl 1 , CuCl 2 , CuF 1 , CuF 2 , CuBr 1 , CuBr 2 , CuI 1 or CuI 2 It is possible to use a material containing at least one of the following:

[0069] The precursor containing at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu) may be in a solid or liquid phase. Therefore, the precursor in a solid or liquid phase is heated and converted into a gas before being sprayed, and then the precursor in a gaseous state is sprayed onto the substrate S. When the precursor is sprayed toward the substrate S, the precursor or a low-resistance metal element contained in the precursor is adsorbed onto the substrate S, and thus an adsorption layer 111 is formed on the substrate S, as shown in FIG. 3(a). That is, an adsorption layer 111 or a thin film containing at least one metal of molybdenum (Mo), ruthenium (Ru) and copper (Cu) is formed.

[0070] After the precursor injection process is completed, a purge gas is injected into the chamber to purge it (first purge). At this time, the purge gas may be, for example, Ar gas.

[0071] Meanwhile, a precursor containing at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu) may contain at least one ligand of carbon (C), oxygen (O) and hydrogen (H) depending on the type of material. That is, when a precursor containing at least one low-resistance metal element of molybdenum (Mo), ruthenium (Ru) and copper (Cu) is sprayed, at least one ligand of oxygen (C), oxygen (O) and hydrogen (H) acting as an impurity may be adsorbed. These ligands act as impurities that reduce the electrical characteristics of the electrode 100, for example, increasing the resistance.

[0072] Therefore, in an embodiment, after the precursor is injected, a reducing gas containing oxygen (O) or hydrogen (H) is injected to remove impurities caused by the precursor. Also, after the precursor is injected and after the reducing gas is injected, a hydrogen plasma or an oxygen plasma is generated to remove impurities caused by the precursor.

[0073] The first plasma generation process is a step for removing impurities from the adsorption layer 111, and may be performed after the injection of the precursor is completed. More specifically, after the injection of the precursor is completed, a gas for generating plasma is injected toward the inside of the chamber or the substrate S, and a power source for generating plasma is supplied. At this time, for example, a radio frequency (RF) CY power source is supplied to at least one of the chamber, the susceptor on which the substrate S is placed inside the chamber, and the injection unit that injects gas into the chamber. The gas for generating plasma may be, for example, a gas containing hydrogen (H) or a gas containing oxygen (O). More specifically, the gas containing hydrogen (H) is H 2 The gas may be oxygen (O), and the gas may be O 2The first plasma may be a gas. In this manner, by supplying RF power and injecting a gas containing hydrogen (H) or oxygen (O), a plasma containing hydrogen or a plasma containing oxygen can be generated inside the chamber. That is, a hydrogen plasma or an oxygen plasma can be generated. Therefore, the substrate S or the substrate S on which the adsorption layer 111 is formed is exposed to the first plasma.

[0074] The generated hydrogen plasma or oxygen plasma reacts with the adsorption layer 111 adsorbed on the substrate to remove at least one of carbon (C), oxygen (O) and hydrogen (H) from the adsorption layer 111. That is, at least one ligand of carbon (C), oxygen (O) and hydrogen (H) originating from the precursor is contained in the adsorption layer 111, and when the hydrogen plasma or oxygen plasma reacts with the adsorption layer 111, the ligand falls off from the adsorption layer 111. That is, the hydrogen plasma or oxygen plasma breaks the ligand bond of at least one of carbon (C), oxygen (O) and hydrogen (H) contained in the precursor of the adsorption layer 111, and the adsorption layer 111 falls off. In other words, at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) is released from the adsorption layer 111 by the plasma. As a result, the content of at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) contained in the adsorption layer 111 can be reduced or removed.

[0075] The reducing gas injection process is carried out after the first plasma generation process is completed, and the reducing gas is injected toward the substrate S loaded inside the chamber. A gas containing hydrogen (H) or oxygen (O) is used as the reducing gas. More specifically, H 2 Gas or O 2 Gas is available.

[0076] In the following, in order to distinguish between the adsorption layer 111 formed by spraying a precursor onto the substrate S (Figure 3(a)) and the adsorption layer 111 exposed to a reducing gas by spraying a reducing gas onto the substrate S on which the adsorption layer 111 is formed, or the adsorption layer 111 reacted with a reducing gas, the adsorption layer 111 exposed to a reducing gas by spraying a reducing gas onto the substrate S on which the adsorption layer 111 is formed, or the adsorption layer 111 reacted with a reducing gas, will be referred to as a "low-resistance metal thin film layer 110" or "metal thin film layer 110".

[0077] When the reducing gas is injected toward the substrate S, a low-resistance metal thin film layer 110 (hereinafter, metal thin film layer 110) is formed as shown in Fig. 3(c). That is, the metal thin film layer 110 containing at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu) is formed.

[0078] At this time, hydrogen (H) or oxygen (O) contained in the reducing gas removes at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) remaining in the adsorption layer 111 or the metal thin film layer 110. That is, at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) that has not been removed during the generation of the first plasma may remain in the adsorption layer 111. Such ligand impurities may be further removed by hydrogen (H) or oxygen (O) injected during the injection of the reducing gas. In other words, at least one ligand bond of carbon (C), oxygen (O) and hydrogen (H) contained in the precursor of the adsorption layer 111 or the metal thin film layer 110 may be broken and removed by the hydrogen (H) or oxygen (O) contained in the reducing gas. As a result, the content of at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) contained in the metal thin film layer 110 may be reduced or removed.

[0079] The flow rate of the reducing gas injected in such a reducing gas injection process may be greater than that of the gas injected in the first plasma generation process described above and the second plasma generation process described below. That is, it is preferable to adjust the injection flow rate of the gas containing hydrogen (H) or oxygen (O) so that the flow rate injected in the reducing gas injection process is greater than that of the gas injected in the first and second plasma generation processes. Therefore, from the viewpoint of removing impurities, it becomes possible to remove relatively more impurities in the reducing gas injection process than in the first and second plasma generation processes.

[0080] Furthermore, the gas containing hydrogen (H) or oxygen (O) injected during the reducing gas injection process has a flow rate that is greater than the gas injected during the first and second plasma generation processes, but the flow rate may be so small that it does not oxidize the precursor metal.

[0081] The reducing gas as described above can be named a gas for removing impurities.

[0082] After the reduction gas injection process is completed, the inside of the chamber is purged by injecting a purge gas (second purge). At this time, the same gas as that used in the first purge can be used, for example, Ar gas can be used as the purge gas.

[0083] On the other hand, even if impurities are removed from the metal thin film layer 110 by injecting a reducing gas, there is a possibility that some of the impurities may remain in the metal thin film layer 110.

[0084] Therefore, after the injection of the reducing gas, an oxygen plasma or a hydrogen plasma is generated (generation of a second plasma) to further remove impurities.

[0085] The second plasma generation process is a step for further removing impurities from the metal thin film layer 110, and may be performed after the injection of the reducing gas is completed. More specifically, it may be performed after the second purge is completed. At this time, the second plasma may be generated or produced by the same method as the first plasma generation process described above. That is, a gas for plasma generation containing hydrogen (H) or oxygen (O) is injected toward the substrate S, and RF power is supplied. As a result, hydrogen plasma or oxygen plasma is generated inside the chamber (see (d) of FIG. 3). As a result, the metal thin film layer 110 is exposed to the second plasma.

[0086] The generated hydrogen plasma or oxygen plasma reacts with the metal thin film layer 110 formed or deposited on the substrate S. Then, due to the reaction with the plasma, at least one ligand impurity of carbon (C), oxygen (O), and hydrogen (H) originating from the precursor falls off from the metal thin film layer 110. In other words, at least one ligand impurity of carbon (C), oxygen (O), and hydrogen (H) is released from the metal thin film layer 110. As a result, the content of at least one ligand impurity of carbon (C), oxygen (O), and hydrogen (H) contained in the metal thin film layer 110 can be reduced or removed.

[0087] Thereafter, the process cycle CY including the above-mentioned "precursor injection process-primary purge process-first plasma generation process-reducing gas injection process-secondary purge process-second plasma generation process" is repeated multiple times. Therefore, as shown in FIG. 1, multiple metal thin film layers 110 are formed on the substrate S, thereby forming an electrode 100 of a predetermined thickness.

[0088] In the above, the injection of the reducing gas after the process of generating the first plasma has been described. However, the present invention is not limited thereto, and a process of injecting a purge gas may be further performed between the process of generating the first plasma and the process of injecting the reducing gas.

[0089] The deposition apparatus in which the above-mentioned "precursor injection process, primary purge process, first plasma generation process, reducing gas injection process, secondary purge process, and second plasma generation process" are performed may be a deposition apparatus that injects a precursor or gas from the side of a substrate. That is, the deposition apparatus may include a chamber, a susceptor disposed inside the chamber so that a substrate S can be placed on the upper portion, and an injection unit disposed on a side wall of the chamber so that a precursor or gas can be injected from the side of the susceptor toward the substrate S placed on the susceptor. The deposition apparatus may also include a power supply unit that supplies a power source for generating plasma, such as an RF power source, to at least one of the chamber, the susceptor, and the injection unit. When such a deposition apparatus is used, the precursor or gas is injected from the side of the substrate S and flows toward the substrate.

[0090] In the above, the electrode 100 is formed using a deposition apparatus in which the ejection unit is disposed laterally of the susceptor and ejects the precursor or gas laterally of the substrate S. However, the present invention is not limited thereto, and the ejection unit may be disposed on the upper wall of the chamber so as to be located above the susceptor. When such a deposition apparatus is used, the precursor or gas can be ejected from above the substrate S.

[0091] Fig. 4 is a diagram showing a state in which an electrode according to a second embodiment of the present invention is formed on a substrate, and Fig. 5 is a conceptual diagram for explaining a method for forming an electrode by the method according to the second embodiment of the present invention.

[0092] Referring to FIG. 4, the electrode 100 according to the second embodiment may include a first metal thin film layer 110a and a second metal thin film layer 110b, and the first metal thin film layer 110a and the second metal thin film layer 110b may be alternately stacked. In this case, each of the first and second metal thin film layers 110a and 110b may be a layer containing a low-resistance metal element. That is, each of the first and second metal thin film layers 110a and 110b may be a layer containing at least one of molybdenum (Mo), ruthenium (Ru) and copper (Cu). The first metal thin film layer 110a and the second metal thin film layer 110b may be layers containing different low-resistance metal elements from among molybdenum (Mo), ruthenium (Ru) and copper (Cu), or may be layers containing the same low-resistance metal element.

[0093] Here, the first and second low-resistance thin-film metal layers 110a, 110b can be named "first low-resistance thin-film metal layer 110a" and "second low-resistance thin-film metal layer 110b", respectively.

[0094] A method for forming an electrode on a substrate by a method according to a second embodiment of the present invention will be described below with reference to Figures 4 and 5. At this time, the case where the first metal thin film layer and the second metal thin film layer are formed of layers containing different low-resistance metal elements will be described as an example.

[0095] Referring to FIG. 5, the method of forming the electrode 100 includes a first process cycle CY 1 and the second process cycle CY 2 Includes.

[0096] First process cycle CY 1 is a process cycle for forming the first metal thin film layer 110a. Such a first process cycle CY 1 may include a process of "injecting a first precursor, a first purge process, a process of generating a first plasma, a process of injecting a reducing gas, a second purge process, and a process of generating a second plasma." Here, the first precursor may be named a first source. The first process cycle CY1 The first precursor used in the first process cycle CY may be a precursor containing at least one low-resistance metal element selected from the group consisting of molybdenum (Mo), ruthenium (Ru) and copper (Cu). For example, in the first process cycle CY 1 The first precursor used in the first process cycle CY may be a precursor containing molybdenum (Mo). 1 This allows the formation of a first metal thin film layer 110a containing molybdenum (Mo).

[0097] Second process cycle CY 2 is a process cycle for forming the second metal thin film layer 110b, and the second process cycle CY 2 may include "a second precursor injection process-a first purge process-a first plasma generation process-a reducing gas injection process-a second purge process-a second plasma generation process". Here, the second precursor can be named a second source. In this case, the second process cycle CY 2 The second precursor used in the second process cycle CY contains at least one low-resistance metal element selected from molybdenum (Mo), ruthenium (Ru) and copper (Cu) and may be a precursor different from the first precursor. For example, in the second process cycle CY 2 The second precursor used in the second process cycle CY may be a precursor containing ruthenium (Ru). 2 This allows the second metal thin film layer 110b containing ruthenium (Ru) to be formed.

[0098] Also, the first process cycle CY as described above 1 and the second process cycle CY 2 This process is repeated multiple times, so that an electrode is formed in which a first metal thin film layer containing molybdenum (Mo) and a second metal thin film layer containing ruthenium (Ru) are alternately stacked multiple times, as shown in FIG.

[0099] And the first and second process cycles CY 1 , C.Y.2 As disclosed in the first embodiment described above, each of the first and second process cycles CY includes a first plasma generation process, a reducing gas injection process, and a second plasma generation process. That is, the first and second process cycles CY 1 , C.Y. 2 Each of the first and second process cycles CY generates a first plasma after the injection of the precursor and a second plasma after the injection of the reducing gas, and the first and second plasmas may be oxygen plasmas or hydrogen plasmas. 1 , C.Y. 2 Each of the above includes a reducing gas injection process carried out between the first plasma generation process and the second plasma generation process, and uses a gas containing hydrogen (H) or oxygen (O) as the reducing gas.

[0100] This makes it possible to form an electrode 100 from which impurities caused by the precursor containing the low-resistance metal element have been removed. That is, the first process cycle CY 1 After injecting the first precursor in step 3, hydrogen plasma or oxygen plasma is generated in the process of generating the first plasma, thereby removing at least one ligand impurity selected from carbon (C), oxygen (O) and hydrogen (H) from the first adsorption layer formed on the substrate S by adsorption of the first precursor. In addition, by injecting a reducing gas containing hydrogen (H) or oxygen (O) toward the substrate S on which the first adsorption layer is formed, at least one ligand impurity selected from carbon (C), oxygen (O) and hydrogen (H) remaining can be further removed. Then, in the first process cycle CY 2 After injecting the reducing gas in step 3, hydrogen plasma or oxygen plasma is generated in the process of generating the second plasma, whereby at least one ligand impurity of carbon (C), oxygen (O) and hydrogen (H) can be further removed from the first metal thin film layer 110a.

[0101] Also, the second process cycle CY 2Even in the above case, at least one ligand impurity, namely carbon (C), oxygen (O) and hydrogen (H), can be removed from the second adsorption layer and the second metal thin film layer 110b during each of the first plasma generation process, the reducing gas injection process and the second plasma generation process.

[0102] FIG. 6 is a diagram showing a state in which an electrode according to a first modified example of the first embodiment is formed on a substrate.

[0103] In the above-mentioned first embodiment, the electrode 100 is formed on the substrate using a precursor containing at least one low-resistance metal element selected from molybdenum (Mo), ruthenium (Ru) and copper (Cu). However, the present invention is not limited thereto, and the electrode may be formed by alternately laminating metal thin film layers containing metal elements other than the low-resistance metal element. That is, the electrode may be formed by alternately laminating metal thin film layers containing a low-resistance metal element and metal thin film layers containing elements other than the low-resistance metal element.

[0104] The electrodes according to the modified examples will be described below. In order to distinguish the modified examples from the first and second embodiments, the metal thin film layer containing the low-resistance metal element in the first modified example will be named "first metal thin film layer 110a" and the metal thin film layer containing elements other than the low-resistance metal element will be named "third metal thin film layer 110c." The cycle for forming the first metal thin film layer 110a containing the low-resistance metal element will be named "first process cycle CY 1 " and the cycle for forming the third metal thin film layer 110c is named "third process cycle CY 3 " and named it.

[0105] Referring to FIG. 6, the electrode 100 according to the first modification may include a first metal thin film layer 110a including at least one low-resistance metal element among molybdenum (Mo), ruthenium (Ru), and copper (Cu), and a third metal thin film layer 110c including titanium (Ti). Here, the third metal thin film layer 110c including titanium (Ti) may be a TiN thin film layer. As shown in FIG. 6, the first metal thin film layer 110a and the third metal thin film layer 110c may be alternately stacked multiple times to form the electrode 100. That is, the electrode 100 may include a plurality of first metal thin film layers 110a and a plurality of third metal thin film layers 110c, and may be formed by alternately stacking the first metal thin film layer 110a and the third metal thin film layer 110c.

[0106] The process of forming the third metal thin film layer 110c) containing titanium (Ti) may include a process of injecting a source containing titanium (Ti) onto the substrate S (source injection process), a process of injecting a purge gas (first purge process), a process of injecting a reactant gas containing nitrogen (N) (reactant gas injection process), and a process of injecting a purge gas (second purge).

[0107] In addition, the process of "injecting a source containing titanium (Ti)--first purge process--injecting a reactant gas--second purge process" is regarded as one third process cycle CY for forming the third metal thin film layer 110c. 3 The first process cycle CY 1 and the third process cycle CY 3 By alternately switching between these and repeating this process multiple times, an electrode 100 may be formed in which a first metal thin film layer 110a containing a low-resistance metal element and a third metal thin film layer 110c which is a TiN metal thin film layer are alternately stacked.

[0108] Although not shown, the electrode 100 according to the second embodiment shown in Fig. 4 may be formed to include a TiN metal thin film layer. That is, the electrode 100 may be formed to include first and second metal thin film layers 110a and 110b which are low-resistance metal thin film layers and a third metal thin film layer 110c which is a TiN metal thin film layer. In this case, the first metal thin film layer 110a, the second metal thin film layer 110b, and the third metal thin film layer 110c may be repeatedly laminated in this order to form the electrode.

[0109] FIG. 7 is a diagram showing a state in which an electrode according to the second modification of the first embodiment is formed on a substrate.

[0110] In the above-mentioned first modified example, the electrode 100 is formed by alternately stacking the first metal thin film layer 110a containing a low-resistance metal element and the third metal thin film layer 110c containing titanium (Ti). However, the present invention is not limited to this, and as shown in the second modified example shown in Fig. 7, the electrode 100 may be formed by preparing a substrate S having a third metal thin film layer 110c, which is a metal thin film layer containing titanium (Ti), formed on the upper surface, and forming a plurality of first low-resistance metal thin film layers 110a on the third metal thin film layer 110c. That is, the electrode 100 may be formed by preparing a substrate S having a metal thin film layer containing titanium (Ti), for example, a TiN thin film layer, formed on the upper surface, and forming a plurality of first low-resistance metal thin film layers 110a on the TiN thin film layer.

[0111] As shown in the figure, in the first and second embodiments and the first and second modified examples, when forming the electrode 100, a precursor containing a low-resistance metal element is injected, and then a reducing gas containing hydrogen (H) or oxygen (O) is injected. Therefore, when the precursor is injected toward the substrate S, impurities adsorbed on the substrate S can be removed. That is, by breaking the ligand bond of at least one of carbon (C), oxygen (O), and hydrogen (H) contained in the precursor using the reducing gas, impurities can be removed from the adsorption layer 111 adsorbed on the substrate S.

[0112] In addition, hydrogen plasma or oxygen plasma is generated between the process of injecting a precursor containing a low-resistance metal element and the process of injecting a reducing gas (generation of a first plasma), and hydrogen plasma or oxygen plasma is generated after the reducing gas is injected (generation of a second plasma). Therefore, before the reducing gas is injected, at least one ligand impurity among carbon (C), oxygen (O), and hydrogen (H) contained in the adsorption layer 111 can be removed using the first plasma. In addition, after the reducing gas is injected, at least one ligand impurity among carbon (C), oxygen (O), and hydrogen (H) contained in the metal thin film layer 110 may be further removed using the second plasma.

[0113] This makes it possible to provide an electrode 100 from which at least one type of ligand impurity of carbon (C), oxygen (O), and hydrogen (H) resulting from a precursor containing a low-resistance metal element has been removed. This makes it possible to suppress or prevent the deterioration of the electrical characteristics of the electrode 100 caused by the impurities. In other words, it is possible to provide an electrode 100 with improved electrical characteristics, more specifically, an electrode 100 with low resistance.

[0114] Hereinafter, an electrode of a semiconductor element and a method of forming an electrode of a semiconductor element according to a third embodiment of the present invention will be described with reference to FIGS.

[0115] Fig. 8 is a diagram illustrating a structure of a semiconductor device according to a third embodiment of the present invention, and Figs. 9 to 11 are diagrams illustrating a method of forming a semiconductor device according to the third embodiment of the present invention.

[0116] At this time, for ease of explanation, FIG. 8 to FIG. 11 are shown with different reference numerals from those in FIG. 1, FIG. 3, FIG. 6, and FIG.

[0117] A third embodiment of the present invention provides an electrode for a semiconductor device, and a method for forming the same, which can reduce damage to an underlying film that occurs during the process of forming an electrode on a silicon or silicon-containing film.

[0118] In addition, a third embodiment of the present invention provides an electrode for a semiconductor device, including an improved barrier layer for reducing damage to an underlying layer that occurs during the process of forming an electrode on a silicon or silicon-containing layer, and a method for forming the same.

[0119] The third embodiment of the present invention provides an improved electrode for a semiconductor device, which can reduce damage to the surface roughness of an underlying layer that occurs during the process of forming an electrode on a silicon or silicon-containing layer, and a method for forming the same.

[0120] Furthermore, a third embodiment of the present invention provides an improved electrode for a semiconductor device, which can reduce damage to the surface roughness of a barrier film, and a method for forming the electrode, for reducing damage to an underlying film that occurs during the process of forming the electrode on a silicon or silicon-containing film.

[0121] The electrode of the semiconductor element according to the third embodiment may be an electrode formed on an insulating film.

[0122] 9, a substrate (not shown) may be a substrate on which an insulating film 100 made of silicon or a silicon-containing film is formed. Referring to FIG 10, a step of forming a ruthenium (Ru) film or a ruthenium (Ru)-containing film on the insulating film 100 as a barrier film on the substrate may be performed. Referring to FIG 11, a step of forming a tungsten (W) or a tungsten (W)-containing film on the ruthenium (Ru) film or the ruthenium (Ru)-containing film may be performed.

[0123] The ruthenium (Ru) or ruthenium (Ru)-containing film may be formed by chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD), but the present invention is not limited thereto.

[0124] The ruthenium (Ru) or ruthenium (Ru)-containing film in the third embodiment may be formed by atomic layer deposition (ALD). Specifically, the ruthenium (Ru) or ruthenium (Ru)-containing film is formed by injecting a source gas containing ruthenium (Ru) into an insulating film 100 on a substrate, purging the source gas, and purging oxygen (O 2 The atomic layer deposition method may be formed by repeatedly performing a deposition cycle including a step of injecting a gas containing oxygen and a step of purging the gas containing oxygen. The atomic layer deposition method can perform deposition at a lower temperature than other conventional chemical vapor deposition methods (CVD), and is advantageous in forming ultra-thin films.

[0125] The thickness of the ruthenium (Ru) film or ruthenium (Ru)-containing film is preferably 50% or less of the thickness of the electrode to be formed subsequently. When the electrode is formed of a tungsten (W) film or tungsten (W)-containing film, the ruthenium (Ru) film or ruthenium (Ru)-containing film is preferably 50% or less of the thickness of the tungsten (W) film or tungsten (W)-containing film. Specifically, the ruthenium (Ru) film or ruthenium (Ru)-containing film is preferably formed to a thickness of 5 Å to 50 Å. If the deposition is performed to a thickness of 5 Å or less, it is difficult to obtain the effect as a barrier film, and if the ruthenium (Ru) is excessively thicker than 50 Å, the expensive ruthenium (Ru) material is used in a thicker thickness, resulting in high costs.

[0126] The ruthenium (Ru)-containing film may be ruthenium oxide (RuO).

[0127] The ruthenium (Ru) or ruthenium (Ru)-containing film may be formed from an organic source containing ruthenium (Ru). If a barrier film is formed using a ruthenium (Ru) source containing a halogen element (fluorine or chlorine), the underlying film may be damaged by the halogen element contained in the ruthenium (Ru) source when ruthenium (Ru) is formed, which may worsen the surface roughness of the underlying film. When a ruthenium (Ru) or ruthenium (Ru)-containing film is formed using an organic source that does not contain a halogen element (fluorine or chlorine), the underlying film is not damaged.

[0128] Meanwhile, the ruthenium (Ru) or ruthenium (Ru)-containing film itself has strong resistance to halogen elements (fluorine or chlorine), and even if it is exposed to gas for forming an electrode in a subsequent step, damage can be reduced, and improved barrier film properties can be obtained compared to existing titanium nitride (TiN) films.

[0129] The tungsten (W) or tungsten (W)-containing film can be formed by chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition, but the present invention is not limited thereto.

[0130] In the third embodiment, the tungsten (W) or tungsten (W)-containing film may be formed by atomic layer deposition. Both ruthenium (Ru) and tungsten (W) can be formed by atomic layer deposition to ensure uniform film quality.

[0131] In addition, the tungsten (W) or tungsten (W)-containing film may be tungsten hexafluoride (WF 6 ) may be used.

[0132] On the other hand, the electrode of the semiconductor element according to the third embodiment may be an electrode or wiring of a memory or non-memory element. When the active layer of a transistor, which is a semiconductor element, is a silicon-containing film, the electrode may be a gate electrode, a source electrode, or a drain electrode of the transistor.

[0133] On the other hand, when the active layer of the transistor is a metal oxide semiconductor or a Group 3-5 semiconductor, the electrode of the semiconductor element of the present invention may have ruthenium (Ru) or a ruthenium-containing film between the active layer. The electrode of the semiconductor element may have ruthenium (Ru) or a ruthenium-containing film between the active layer containing at least one of indium, gallium, zinc, and tin. The electrode of the semiconductor element may have ruthenium (Ru) or a ruthenium-containing film between the active layer formed of GaN, GaAs, etc.

[0134] The method for forming an electrode of a semiconductor device may include a step of removing oxides or impurities on the surface of the silicon or silicon-containing film before forming the ruthenium (Ru) film or ruthenium (Ru)-containing film, in order to remove impurities present on the upper part of the lower film before forming ruthenium (Ru) and to remove a native oxide film present on the lower film and form a ruthenium (Ru) film or ruthenium (Ru)-containing film to form a high-quality film.

[0135] The structure according to the present invention may include an insulating film 100, a ruthenium (Ru) film 200, and a tungsten (W) film 300. At least one of a bit line 160 and a word line 120 may be formed on the top or bottom of the structure.

[0136] Regarding a schematic formation method of the third embodiment, the method for forming an electrode of a semiconductor device may include the steps of forming a ruthenium film or a ruthenium-containing film on a silicon or silicon-containing film, and forming a tungsten-containing film on the ruthenium film or the ruthenium-containing film.

[0137] The ruthenium film or ruthenium-containing film may be formed to a thickness that is 50% or less of the thickness of the tungsten-containing film.

[0138] The ruthenium film or ruthenium-containing film may be formed to a thickness of 5 Å to 50 Å.

[0139] The ruthenium film or ruthenium-containing film may be formed by atomic layer deposition.

[0140] The ruthenium film or ruthenium-containing film may be formed from an organic source containing ruthenium. The tungsten-containing film may be formed from a tungsten halogen gas. A semiconductor element may be formed in which the electrode is any one of a memory element electrode, a word line, a bit line, a transistor electrode, a GaN semiconductor electrode, and a GaAs semiconductor electrode.

[0141] Although the preferred embodiment of the present invention has been described and illustrated using specific terms, these terms are merely for the purpose of clearly describing the present invention, and it is clear that the embodiments of the present invention and the described terms can be modified and changed in various ways without departing from the technical spirit and scope of the appended claims. These modified embodiments should not be understood separately from the spirit and scope of the present invention, but should be considered to belong to the scope of the claims of the present invention. [Industrial Applicability]

[0142] According to an embodiment of the present invention, an electrode can be provided from which ligand impurities resulting from a precursor containing a low-resistance metal element are removed. Also, according to an embodiment of the present invention, a barrier film and an electrode can be formed to reduce damage to an underlying film.

Claims

1. The steps include preparing the circuit board and The steps include: spraying a precursor containing a low-resistance metal element onto the substrate; The steps include: forming a low-resistance metal thin film layer by injecting a gas containing hydrogen (H) or oxygen (O) onto the substrate; The steps include: after forming the low-resistance metal thin film layer, exposing the low-resistance metal thin film layer to a second plasma to remove impurities; A method for forming electrodes for semiconductor devices, including [the specified element].

2. The process includes, after the step of injecting the precursor, a step of exposing the substrate to a first plasma to remove impurities adsorbed on the substrate, A method for forming an electrode of a semiconductor device according to claim 1, comprising performing the steps of injecting the precursor, exposing the first plasma, and exposing the low-resistance metal thin film layer to a second plasma multiple times in this order.

3. The method for forming an electrode of a semiconductor device according to claim 1, wherein the low-resistance metal element includes at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

4. The method for forming an electrode of a semiconductor device according to claim 2, wherein the first plasma is formed by a plasma containing hydrogen (H) or a plasma containing oxygen (O).

5. The method for forming an electrode of a semiconductor device according to claim 2, wherein the second plasma is formed by a plasma containing hydrogen (H) or a plasma containing oxygen (O).

6. The step further includes forming a TiN thin film layer on the substrate, The step of forming the TiN thin film layer is, The steps include: spraying a titanium (Ti) source onto the substrate; The steps include: injecting a gas containing nitrogen (N) onto the substrate; Includes, A method for forming an electrode of a semiconductor device according to claim 1, comprising performing multiple times in this order the steps of: injecting a precursor containing the low-resistance metal element; forming a low-resistance metal thin film layer; exposing the low-resistance metal thin film layer to a second plasma; and forming the TiN thin film layer.

7. The method for forming electrodes for a semiconductor device according to claim 1, wherein in the step of preparing the substrate, a substrate is prepared having a TiN thin film layer formed on its upper surface.

8. The steps include preparing the circuit board and The steps include: injecting a source containing a first low-resistance metal element and injecting a gas containing hydrogen (H) or oxygen (O) to form a first low-resistance metal thin film layer; The first low-resistance metal thin film layer is formed, followed by the step of exposing the first low-resistance metal thin film layer to plasma to remove impurities. The steps include: injecting a source containing a second low-resistance metal element and injecting a gas containing hydrogen (H) or oxygen (O) to form a second low-resistance metal thin film layer; The steps include: after forming the second low-resistance metal thin film layer, exposing the second low-resistance metal thin film layer to plasma to remove impurities; The steps include: injecting a titanium (Ti)-containing source and injecting a nitrogen (N)-containing reactant to form a TiN thin film layer; Includes, A method for forming electrodes for a semiconductor device, comprising repeatedly performing in this order the steps of forming a first low-resistance metal thin film layer, exposing the first low-resistance metal thin film layer to plasma, forming a second low-resistance metal thin film layer, exposing the second low-resistance metal thin film layer to plasma, and forming the TiN thin film layer.

9. The method for forming electrodes for a semiconductor device according to claim 8, wherein the first low-resistance metal element and the second low-resistance metal element include at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

10. The method for forming electrodes for a semiconductor device according to claim 8, wherein the first low-resistance metal element and the second low-resistance metal element include the same metal element.

11. The method for forming electrodes for a semiconductor device according to claim 8, wherein at least one of the first low-resistance metal element and the second low-resistance metal element includes at least two of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

12. The method for forming electrodes for a semiconductor device according to claim 8, wherein in the step of preparing the substrate, a substrate is prepared having a TiN thin film layer formed on its upper surface.

13. The steps include preparing the circuit board and The steps include: spraying a liquid-phase precursor containing a low-resistance metal element onto the substrate; The steps include: forming a low-resistance metal thin film layer by injecting a gas containing hydrogen (H) or oxygen (O) onto the substrate; The steps include: after forming the low-resistance metal thin film layer, exposing the low-resistance metal thin film layer to plasma to remove impurities; A method for forming electrodes for semiconductor devices, including [the specified element].

14. A method for forming an electrode of a semiconductor device according to claim 13, comprising performing the steps of injecting the precursor, forming a low-resistance metal thin film layer, and exposing the low-resistance metal thin film layer to plasma multiple times in this order.

15. The method for forming an electrode of a semiconductor device according to claim 13, wherein the low-resistance metal element includes at least one of molybdenum (Mo), ruthenium (Ru), and copper (Cu).

16. A method for forming electrodes for semiconductor devices, The steps include: preparing a substrate on which silicon or a silicon-containing film is formed; The steps include removing oxides or impurities from the surface of the silicon or silicon-containing film, The steps include forming a ruthenium film or ruthenium-containing film on silicon or a silicon-containing film, The steps include forming a tungsten-containing film on the ruthenium film or ruthenium-containing film, A method for forming electrodes for semiconductor devices, including [the specified element].

17. The method for forming an electrode for a semiconductor device according to claim 16, wherein the ruthenium film or ruthenium-containing film is formed to a thickness of 50% or less of the thickness of the tungsten-containing film.

18. The method for forming an electrode for a semiconductor device according to claim 16, wherein the ruthenium film or ruthenium-containing film is formed to a thickness of 5 Å to 50 Å.

19. The method for forming an electrode of a semiconductor device according to claim 16, wherein the ruthenium film or ruthenium-containing film is formed by an atomic layer deposition method.

20. The method for forming an electrode of a semiconductor device according to claim 16, wherein the ruthenium film or ruthenium-containing film is formed from an organic source containing ruthenium.

21. The method for forming an electrode for a semiconductor device according to claim 16, wherein the tungsten-containing film is formed with a tungsten halogen gas.

22. The method for forming an electrode for a semiconductor device according to claim 16, wherein the electrode is one of the following: an electrode for a memory element, a word line, a bit line, an electrode for a transistor, an electrode for a GaN semiconductor, or an electrode for a GaAs semiconductor.

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