Method for manufacturing ruthenium-containing thin films

Abstract

The process includes the steps of supplying a transport gas and a ruthenium precursor represented by the following chemical formula 1 into a chamber in which a substrate is mounted, and depositing a ruthenium-containing thin film onto the substrate while injecting a reducing reaction gas into the chamber; and a post-processing step including at least one of the steps of heat treatment in a reducing reaction gas atmosphere and plasma treatment in a reducing reaction gas atmosphere. The present invention provides a method for producing a ruthenium-containing thin film, wherein the reducing reaction gas is at least one selected from H2, hydrazine (NH2NH2), NH3, and BH3.

Description

Technical Field

[0001] This description relates to a method for manufacturing a ruthenium-containing thin film. More specifically, it relates to a method for manufacturing a ruthenium-containing thin film including a step of depositing a ruthenium-containing thin film using a ruthenium precursor having a specific structure and a reducing reaction gas, a step of heat-treating in a reducing reaction gas atmosphere, and a post-treatment step including at least one of a step of plasma-treating in a reducing reaction gas atmosphere.

Background Art

[0002] Ruthenium (Ru) thin films are used as seed layers in the wiring structure of semiconductor devices or as electrodes such as gates or capacitors of transistors. With the high integration and miniaturization of semiconductor devices, improved uniformity and coating properties are required for the ruthenium (Ru) thin films used in semiconductor devices.

[0003] On the other hand, in semiconductor devices, as thin film deposition methods, methods using molecular beam epitaxy (MBE), chemical vapor deposition (CVD), physical vapor deposition (PVD), etc. have been studied. Recently, as the design rules decrease due to the downsizing of semiconductor devices, thin film formation using atomic layer deposition (ALD) based on a self-limiting surface reaction mechanism has been widely studied as a deposition method that satisfies low temperature processes, precise thickness control, and the uniformity and coating properties of thin films.

[0004] In methods for producing ruthenium thin films using atomic layer deposition, conventional ruthenium raw materials have included Ru(OD)3 [tris(2,4-octanedionato)Ruthenium(III)] and Ru(EtCP)2 [bis(ethylcyclopentadienyl)Ruthenium(II)]. However, among these, Ru(OD)3 contains oxygen, making it difficult to deposit pure ruthenium onto the reaction substrate, and RuO2 is used in part of the substrate. x There are problems with the formation of this.

[0005] Furthermore, in the case of Ru(EtCP)2, due to the properties of the cyclopentadiene system, ruthenium atoms do not easily break chemical bonds and exist independently. This results in the problem of many impurities remaining in the ruthenium thin film, and because decomposition is not easy, a RuO2 film is produced by deposition using O2 plasma. Therefore, in order to obtain a Ru film, a reduction process using H2 is required again, which presents another problem.

[0006] A process for manufacturing ruthenium thin films using chemical vapor deposition is currently under development. However, the ruthenium raw material used, (cyclohexadiene)Ru(CO)3, suffers from significantly reduced thermal stability, leading to decomposition during the deposition process. Even if a material with improved thermal stability is used, problems such as reduced volatility or poor resistivity of the thin film may occur.

[0007] Therefore, there is a need for a method to produce a highly pure ruthenium-containing thin film by reducing the impurity content, while also improving physical properties, including room-temperature thermal stability, and thin-film resistivity. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] One aspect of this disclosure provides a method for preventing decomposition under storage and use conditions by improving the thermal stability of the ruthenium precursor, improving the thin film resistivity through a post-processing step, and producing a high-purity ruthenium-containing thin film. [Means for solving the problem]

[0009] One embodiment of the present invention provides a method for producing a ruthenium-containing thin film, comprising the steps of: supplying a transport gas and a ruthenium precursor represented by the following chemical formula 1 into a chamber in which a substrate is mounted, and depositing a ruthenium-containing thin film onto the substrate while injecting a reducing reaction gas into the chamber; and a post-treatment step comprising at least one of the steps of heat treatment in a reducing reaction gas atmosphere and plasma treatment in a reducing reaction gas atmosphere, wherein the reducing reaction gas is at least one selected from H2, hydrazine (NH2NH2), NH3, and BH3:

[0010] [ka] In the above chemical formula 1, R is a substituted or unsubstituted C1 to C5 alkyl group.

[0011] In the supply step, the temperature of the substrate may be maintained at 80°C to 300°C.

[0012] The reducing reaction gas may be injected at a rate of 0.1 to 500 moles per mole of the ruthenium-containing compound.

[0013] The heat treatment may be carried out at a temperature of 200°C to 1000°C.

[0014] The plasma treatment may be performed with an RF power of 50 to 1000 W.

[0015] The method for producing the ruthenium-containing thin film may further include a step of supplying an inert gas and purging.

[0016] The resistivity of the ruthenium-containing thin film may be 25 μΩ·cm or less.

[0017] The ruthenium-containing thin film may have a carbon content of 2 at% or less.

[0018] The ruthenium-containing thin film may have an oxygen content of 1 at% or less.

[0019] The ruthenium-containing thin film may have a nitrogen content greater than 0 and less than 3 at%.

[0020] The ruthenium-containing thin film may have a hydrogen content of 7 at% or less.

Advantages of the Invention

[0021] In an embodiment of the present invention, by using a ruthenium precursor having a specific structure, the thermal stability is improved, decomposition under storage and use conditions is prevented, and a ruthenium-containing thin film with improved thin film specific resistance and high purity can be provided by a post-treatment step.

Brief Description of the Drawings

[0022] [Figure 1] FIG. 1 is a schematic diagram for explaining a method for manufacturing a ruthenium-containing thin film according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram for explaining a method for manufacturing a ruthenium-containing thin film according to Comparative Example 1. [Figure 3] FIG. 3 is a graph showing the TGA analysis results of a ruthenium precursor. [Figure 4] FIG. 4 is a graph obtained by measuring the heat flow with respect to temperature using a differential scanning calorimeter (SETARAM Instrumentation, Sensys evo DSC) of a ruthenium precursor. [Figure 5] FIG. 5 is a graph showing the ambient temperature storage stability of ruthenium precursor compound 1 of the present invention. [Figure 6] FIG. 6 is a diagram showing the evaluation results of the step coverage characteristics by TEM analysis of the ruthenium thin film according to Example 1.

Explanation of Reference Numerals

[0023] (A): Step of depositing a ruthenium-containing thin film. (B): Post-processing step (C): Steps to purge (D): Repeat cycle [Modes for carrying out the invention]

[0024] The following describes various embodiments of the present invention in detail, with reference to the attached drawings, so that those with ordinary skill in the art to which the present invention pertains can easily implement them. The present invention can be realized in a variety of different forms and is not limited to the embodiments described herein.

[0025] To clearly explain the present invention, unnecessary explanatory parts have been omitted, and the same or similar reference numerals are used throughout the specification for identical or similar components.

[0026] Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrary for the sake of explanation and are not necessarily limited to those shown in the present invention. Thicknesses are shown enlarged in the drawings to clearly represent multiple layers and regions. In addition, the thicknesses of some layers and regions are exaggerated in the drawings for the sake of explanation.

[0027] Furthermore, when a part such as a layer, membrane, region, or plate is said to be "on top of" another part, this includes not only the case where it is "directly above" the other part, but also the case where the other part is in between. Conversely, when one part is said to be "directly above" another part, it means that there is no other part in between. Also, being "on top of" a reference part means being located above or below the reference part, and does not necessarily mean being located "above" in the opposite direction of gravity.

[0028] Furthermore, when a specification states that a part of it "includes" a certain component, unless otherwise specified, this does not mean that other components are excluded, but rather that other components may be included.

[0029] Unless otherwise defined herein, “substituted” means that the hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, or I), hydroxyl group, alkoxy group, nitro group, cyano group, amino group, azide group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group or its salts, sulfonic acid group or its salts, phosphoric acid or its salts, vinyl group, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 a This means that the substituents are selected from a lucinyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C6 to C30 allyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

[0030] Furthermore, unless otherwise defined herein, "hetero" means a material containing one to ten heteroatoms independently selected from N, O, S, and P.

[0031] Furthermore, in this specification, the term "acrylic polymer" refers to both acrylic polymers and methacrylic polymers.

[0032] The following describes a method for producing a ruthenium-containing thin film according to one embodiment.

[0033] A method for producing a ruthenium-containing thin film according to one embodiment includes the steps of: supplying a transport gas and a ruthenium precursor represented by the following chemical formula 1 into a chamber in which a substrate is attached, and depositing a ruthenium-containing thin film onto the substrate while injecting a reducing reaction gas into the chamber; and a post-treatment step including at least one of the steps of heat treatment in a reducing reaction gas atmosphere and plasma treatment in a reducing reaction gas atmosphere. The reducing reaction gas may include at least one selected from H2, hydrazine (NH2NH2), NH3, and BH3.

[0034] [ka] In the aforementioned chemical formula 1, R is a substituted or unsubstituted C1 to C5 alkyl group.

[0035] The present invention provides a method for producing a high-purity ruthenium-containing thin film with improved thermal stability, preventing the decomposition of the ruthenium precursor under storage and use conditions, and enabling the production of a thin film with a uniform surface. This method includes a post-treatment step in which a ruthenium precursor represented by the above chemical formula 1 is used and simultaneously subjected to heat treatment and / or plasma treatment in a reducing reaction gas atmosphere of H2, hydrazine (NH2NH2), NH3, BH3, or a mixture thereof.

[0036] The following explanation of the method for producing the ruthenium-containing thin film described above will be given with reference to Figure 1 and in comparison to Figure 2, which illustrates the method for producing the ruthenium-containing thin film according to Comparative Example 1. Figure 1 is a schematic diagram illustrating the method for producing the ruthenium-containing thin film according to one embodiment of the present invention, and Figure 2 is a schematic diagram illustrating the method for producing the ruthenium-containing thin film according to Comparative Example 1.

[0037] Referring to Figure 1, the production of a ruthenium-containing thin film may include a step (A) in which a transport gas and a ruthenium precursor represented by the above chemical formula 1 are supplied into a chamber in which a substrate is mounted, and a ruthenium-containing thin film is deposited onto the substrate while injecting a reducing reaction gas into the chamber; a post-treatment step (B) which includes at least one of a step of heat treatment in a reducing reaction gas atmosphere and a step of plasma treatment in a reducing reaction gas atmosphere; and a step (C) in which an inert gas is supplied to purge.

[0038] The method for producing the ruthenium-containing thin film can be repeated in cycles (D) until a desired thin film thickness is obtained, with each cycle comprising a deposition step (A), a post-treatment step (B), and a purging step (C).

[0039] In contrast, referring to Figure 2, the production of a ruthenium-containing thin film can be carried out in a cycle (D) which consists of the following steps: (A) supplying a transport gas and a ruthenium precursor represented by the aforementioned chemical formula 1 into a chamber in which a substrate is attached, depositing a ruthenium-containing thin film onto the substrate while injecting a reducing reaction gas into the chamber, and then proceeding to the step (C) of supplying an inert gas for purging without any separate post-treatment steps.

[0040] If further post-processing steps are included, it is possible to improve the thin film resistivity and produce ruthenium-containing thin films with high purity.

[0041] At this time, the purging step (C) may be included selectively as needed.

[0042] The deposition method can be atomic layer deposition (ALD), vapor deposition (CVD), metal-organic vapor deposition (MOCVD), low-pressure vapor deposition (LPCVD), plasma-enhanced vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). From the viewpoint of obtaining high purity and excellent physical properties, atomic layer deposition (ALD) or vapor deposition (CVD) can be used.

[0043] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium precursor used as the precursor may be changed to a gaseous state by heating or other means for thin film deposition and then introduced into the processing chamber.

[0044] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the reducing reaction gas may be changed to a gaseous state by a method such as heating and introduced into a processing chamber containing a substrate on which a ruthenium precursor has been adsorbed.

[0045] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium precursor and the reducing reaction gas may be supplied to the chamber organically or independently of each other, and the ruthenium precursor and the reducing reaction gas may be supplied simultaneously or sequentially.

[0046] Furthermore, the ruthenium precursor and the reducing reaction gas may be supplied to the chamber continuously or discontinuously, and the discontinuous supply may include pulsed form.

[0047] In one embodiment of the present invention, the deposition method may be vapor deposition (CVD), in which case the supply of the ruthenium precursor and the injection of the reducing reaction gas may be carried out simultaneously.

[0048] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the purging step (C) may be performed in at least one of the post-treatment step and / or a step after the post-treatment step.

[0049] In other words, the purging step (C) may be performed before the post-treatment step, after the post-treatment step, or both before and after the post-treatment step, and may be a step of selective purging by supplying an inert gas into the chamber to exhaust unreacted ruthenium precursor gas, by-product gas, or unreacted reducing reaction gas. The inert gas may be one or more selected from nitrogen (N2), argon, and helium. The injection volume of the purging gas is not limited, but may be provided in the range of 800 to 5,000 sccm, and more specifically, in the range of 1,000 to 3,000 sccm.

[0050] The substrate according to one embodiment of the present invention can be any usable substrate within the range recognized by those skilled in the art, and the temperature of the substrate is not limited to this, but can be maintained at 300°C or below in the chamber, preferably at a temperature of 80°C to 300°C. This temperature range is due to the decomposition characteristics of the ruthenium compound used as a precursor itself and the reaction characteristics with other substances used as reducing reaction gases, such as H2, hydrazine (NH2NH2), NH3, BH3, or mixtures thereof.

[0051] In one embodiment of the present invention, the substrates that can be used include, but are not limited to, substrates containing one or more semiconductor materials from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; SOI (Silicon On Insulator) substrates; quartz substrates; or glass substrates for displays; flexible plastic substrates such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), and polyester; and tungsten substrates.

[0052] In one preferred embodiment of the ruthenium precursor, R in the above chemical formula 1 may be a substituted or unsubstituted C1 to C4 alkyl group, more preferably R may be a substituted or unsubstituted C1 to C3 alkyl group, or R may be a substituted or unsubstituted C1 to C2 alkyl group. In one most preferred embodiment, the ruthenium precursor may be (isoprene)Ru(CO)3.

[0053] In one embodiment of the present invention, a method for producing a ruthenium-containing thin film uses (isoprene)Ru(CO)3 as a precursor and a reducing reaction gas which is H2, hydrazine (NH2NH2), NH3, BH3, or a mixture thereof. The thin film deposition conditions can be adjusted according to the structure or thermal properties of the target thin film.

[0054] Examples of deposition conditions according to one embodiment of the present invention include the flow rate of the bubbler transport gas used to transfer the precursor (isoprene)Ru(CO)3 vaporized in a bubbler container, the pressure, RF power, and substrate temperature. A non-limiting example of such deposition conditions is that the flow rate of the transport gas introduced into the (isoprene)Ru(CO)3 bubbler container may be 1 to 1000 cc / min, the flow rate of the reducing reaction gas may be 1 to 3000 cc / min, the pressure may be 0.1 to 100 torr, the RF power may be 50 to 1000 W, and the substrate temperature may be adjusted to 80 to 300°C, preferably in the range of 100 to 300°C, but is not limited thereto.

[0055] Preferably, the reducing reaction gas according to one embodiment of the present invention may be used in an amount of 0.1 to 500 moles per 31 moles of (isoprene)Ru(CO), but is not limited thereto and can be adjusted by the thin film deposition conditions. For example, in the case of atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), or vapor deposition (CVD), it may be used in an amount of 1 to 100 moles, more preferably 1 to 50 moles, and even more preferably 2 to 30 moles per 31 moles of (isoprene)Ru(CO).

[0056] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the post-treatment step (B) may be carried out in a reducing gas atmosphere.

[0057] The reducing gas is as described above.

[0058] The post-processing step may be heat treatment or plasma treatment, and the heat treatment and plasma treatment may be performed at a temperature of 200 to 1000°C or an RF power of 50 to 1000W for 1 minute to 4 hours, preferably at a temperature of 200 to 800°C or an RF power of 100 to 500W for 1 minute to 1 hour.

[0059] When a deposited thin film undergoes post-treatment steps such as heat treatment and / or plasma treatment, its resistivity decreases through increased film density, improved crystallinity, and removal of impurities, resulting in the formation of a ruthenium thin film with a resistivity of 25 μΩ·cm or less.

[0060] The ruthenium thin film deposition step (A) and the post-treatment step (B) may be repeated until a ruthenium thin film of the desired thickness is formed.

[0061] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the most preferred precursor, (isoprene)Ru(CO)3, may be supplied to the chamber together with the transport gas. Specifically, the transport gas may be one or more selected from nitrogen (N2), hydrogen, argon, and helium, and may be one or more inert gases selected from nitrogen (N2), argon, and helium as a preferred combination with the specific reducing reaction gas of the present invention.

[0062] Ruthenium-containing thin films can be any thin film that can be manufactured within the scope recognized by those skilled in the art by supplying a ruthenium precursor in the gas phase. As a specific and substantial example, ruthenium-containing thin films may be ruthenium, ruthenium oxide films, or hybrid films thereof, which are normally conductive. In addition, a variety of high-quality thin films containing ruthenium can be manufactured within the scope recognized by those skilled in the art.

[0063] A ruthenium-containing thin film can be formed by repeating a process comprising the deposition step (A), the post-treatment step (B), and the selective purging step (C) for 1 to 400 cycles, with each cycle comprising one step.

[0064] Furthermore, the ruthenium-containing thin film produced according to one embodiment of the present invention may have a resistivity of 25 μΩ·cm or less, preferably 24 μΩ·cm or less, more preferably 23 μΩ·cm or less, and a carbon content of 2 at% or less, preferably 1.8 at% or less, more preferably 1.6 at% or less.

[0065] Furthermore, the ruthenium-containing thin film according to one embodiment of the present invention may have an oxygen content of 1 at% or less, preferably 0.8 at% or less, and more preferably 0.5 at% or less.

[0066] Furthermore, the ruthenium-containing thin film according to one embodiment of the present invention has a nitrogen content greater than 0 and less than 3 at%.

[0067] Furthermore, the ruthenium-containing thin film according to one embodiment of the present invention may have a hydrogen content of 7 at% or less, preferably 6.5 at% or less, and more preferably 6.2 at% or less.

[0068] The present invention provides a method for producing a ruthenium-containing thin film that has high purity, high density, and high durability. This method involves a deposition step using a ruthenium-based hydrocarbon compound represented by chemical formula 1, which is a specific ruthenium precursor, and a reduction reaction gas such as H2, hydrazine (NH2NH2), NH3, BH3, or a mixture thereof, followed by a post-treatment step of heat treatment or plasma treatment.

[0069] In particular, by using a ruthenium-based hydrocarbon compound represented by chemical formula 1, which is a ruthenium precursor, in combination with a reducing reaction gas such as H2, hydrazine (NH2NH2), NH3, BH3, or a mixture thereof, thermal stability is significantly improved, and by making a post-treatment step essential, high-purity ruthenium-containing thin films can be produced.

[0070] By using a reducing reaction gas during the production of ruthenium-containing thin films, the amount of impurities that may be present in the ruthenium-containing thin film can be minimized. When a gas other than the reducing reaction gas is used as the reaction gas, substances contained in the reaction gas may remain as impurities in the ruthenium-containing thin film, potentially reducing its purity.

[0071] As a result, the ruthenium content in the ruthenium thin film can be increased to 90 at% or more, while other impurities, such as carbon (2 at% or less), oxygen (1 at% or less), nitrogen (less than 3 at%), and hydrogen (7 at% or less), can be reduced.

[0072] Furthermore, the resistivity of the ruthenium-containing thin film produced by the process described above can be reduced to 25 μΩ·cm or less, preferably 23 μΩ·cm or less, and more preferably 21 μΩ·cm or less.

[0073] The present invention will be described more specifically below by the following embodiments. Prior to this, the terms and words used in this specification and claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical concept of the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best describe their invention.

[0074] Therefore, the embodiments and configurations shown in the drawings described herein represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the present invention. It should be understood that, at the time of filing, there are various equivalents and modifications that can be substituted for these embodiments.

[0075] Furthermore, all the following examples were performed using a commercially available showerhead-type 200mm single-wafer CVD (PECVD) equipped system (CN1, Atomic Premium) and known chemical vapor deposition (CVD) methods. Alternatively, these methods can be performed using a commercially available showerhead-type 200mm single-wafer CVD (ALD) equipped system (CN1, Atomic Premium) and known atomic layer deposition (ALD) methods.

[0076] The deposited ruthenium-containing thin film was subjected to resistivity measurement using a surface resistance meter (4-point probe, DASOLENG, ARMS-200C), and then subjected to a transmission electron microscope (FEI (Netherlands) Tecnai G). 2 The thickness was measured using the F30S-Twin, and the composition of the thin film was analyzed using Time of Flight-Elastic Recoil Detection (TOF-ERD, NEC).

[0077] [Examples] Example: Fabrication of ruthenium-containing thin film Example 1: Preparation of a ruthenium-containing thin film to which compound 1 is applied (including post-processing steps) Ru-containing precursor compounds include isoprene Ru(CO)3, compound 1:

[0078] [ka] Using hydrogen gas (H2) as the reducing reaction gas, a ruthenium-containing thin film was formed by chemical vapor deposition. Subsequently, post-treatment was performed using hydrogen plasma, and this process was repeated to form a ruthenium-containing thin film.

[0079] A silicon oxide film was used as a substrate and maintained at 250°C. Compound 1 was then packed into a stainless steel bubbler container and maintained at 24°C. The vaporized compound 1 in the stainless steel bubbler container was transferred into the reaction chamber by supplying argon gas (50 sccm) as the transport gas for 20 seconds (0.016 g). Simultaneously, hydrogen gas (2000 sccm) was supplied for 20 seconds to form a ruthenium-containing thin film. During this time, the pressure in the reaction chamber was maintained at 1.4 Torr. Next, reaction by-products and residual reaction gases were removed using argon gas (3000 sccm) for 30 seconds. The substrate with the formed ruthenium-containing thin film was then subjected to hydrogen plasma post-treatment in the same reaction chamber. The substrate temperature was maintained at 250°C, and hydrogen gas (2000 sccm) and argon gas (400 sccm) were supplied for 120 seconds. During this time, the pressure in the reaction chamber was maintained at 5 Torr, and a 13.56 MHz RF power of 100 W was supplied. Finally, reaction by-products and residual reaction gases were removed using argon gas (3000 sccm) for 30 seconds. The entire process described above was repeated 20 times to produce a ruthenium-containing thin film. TEM analysis was performed on the formed ruthenium thin film, and the results of the thickness evaluation of the ruthenium-containing thin film and the TOF-ERD analysis, along with the detailed reaction conditions, are shown in Table 1 below.

[0080] Comparative Example 1: Production of a ruthenium-containing thin film to which Compound 1 is applied (excluding post-processing steps) A ruthenium-containing thin film was manufactured in the same manner as in Example 1, except that hydrogen plasma post-treatment was not performed.

[0081] TEM analysis was performed on the formed ruthenium thin film, and the results of the thickness evaluation of the ruthenium-containing thin film, as well as the TOF-ERD analysis results, are shown in Table 1 below, along with detailed reaction conditions.

[0082] Comparative Example 2: Production of a ruthenium-containing thin film to which Compound 2 is applied. As a Ru-containing precursor compound, instead of compound 1, use compound 2:

[0083] [ka] A ruthenium-containing thin film was prepared in the same manner as in Example 1, except that a different material was used. The formed ruthenium thin film was subjected to TEM analysis, and the results of the thickness evaluation of the ruthenium-containing thin film by TEM, as well as the TOF-ERD analysis results, are shown in Table 1 below, along with the detailed reaction conditions.

[0084] [Table 1] Evaluation 1: Analysis of TGA and vapor pressure TGA used the Linseis STA PT100 (Germany) model to measure the weight change per unit temperature (%) for compound 1 and compound 2, increasing the temperature by 10°C per minute up to 500°C in a nitrogen atmosphere. The results are shown in Table 2 and Figure 3 below.

[0085] Furthermore, the temperature at which a vapor pressure of 1 torr is observed was measured and is shown in Table 2 below.

[0086] Figure 3 is a graph showing the TGA analysis results of the ruthenium precursor.

[0087] Referring to Figure 3 and Table 2, a comparison of the TGA50% temperature, which is the temperature at which a 50% weight reduction occurs, revealed that while the TG50% temperature of compound 2 is 130°C, compound 1 according to the present invention exhibits improved volatility at a TG50% temperature of 115°C.

[0088] Furthermore, the vapor pressure (VP) with respect to temperature also showed results consistent with volatility. Comparing the temperatures at which a vapor pressure of 1 torr was observed, compound 1 exhibited a high vapor pressure at 24°C, a significantly lower temperature than compound 2 (54°C, 1 torr).

[0089] Evaluation 2: DSC analysis Heat flow was measured using a differential scanning calorimetry (Mettler Toledo DSC3), and the results are shown in Table 2 and Figure 4 below.

[0090] The temperature range for DSC analysis was set to 25°C to 500°C, with a heating rate of 10°C / min.

[0091] Figure 4 is a graph showing the heat flow with respect to temperature measured using a differential scanning calorimetry (SETARAM Instrumentation, Sensys evo DSC) on a ruthenium precursor.

[0092] Referring to Figure 4 and Table 2, it can be seen that during thermal analysis by differential scanning calorimetry (DSC), compound 1's main peak, which represents the maximum heat flow rate, can be measured at 205°C or higher. This confirms that compound 2 exhibits superior thermal stability, as its main peak, which represents the maximum heat flow rate, is measured at 197°C or higher.

[0093] [Table 2] Evaluation 3: Evaluation of storage stability at room temperature Six samples, each containing 1 ml of ruthenium precursor compound 1 in a stainless steel container, were stored at room temperature in a glove box under an argon atmosphere. Each sample was analyzed after 1 month, 2 months, 3 months, 6 months, 9 months, and 12 months, and the degree of decomposition and purity were confirmed by 1H-NMR, as shown in Table 3 and Figure 5 below.

[0094] Figure 5 is a graph showing the room-temperature storage stability of ruthenium precursor compound 1 of the present invention.

[0095] Referring to Figure 5 and Table 3, it was confirmed that the same 3N quality (>99.9%) as the initial quality immediately after production was maintained for 12 months, demonstrating excellent long-term storage stability.

[0096] Room temperature refers to a temperature range between 22°C and 27°C.

[0097] [Table 3] Evaluation 4: Evaluation of step-level covering characteristics As a Ru-containing precursor compound, isopreneRu(CO)3:

[0098] [ka] Using hydrogen gas (H2) as the reducing reaction gas, a ruthenium-containing thin film was formed by chemical vapor deposition. Subsequently, post-treatment was performed using hydrogen plasma, and this process was repeated to form a ruthenium-containing thin film.

[0099] A titanium nitride film pattern with an aspect ratio of 7:1 was used as a substrate and maintained at 250°C. Compound 1 was then packed into a stainless steel bubbler container and maintained at 24°C. The vaporized compound 1 in the stainless steel bubbler container was transferred into the reaction chamber by supplying argon gas (50 sccm) as the transport gas for 20 seconds (0.016 g). Simultaneously, hydrogen gas (2000 sccm) was supplied for 20 seconds to form a ruthenium-containing thin film. During this time, the pressure in the reaction chamber was maintained at 1.4 Torr. Next, reaction by-products and residual reaction gases were removed using argon gas (3000 sccm) for 5 seconds. The substrate with the formed ruthenium-containing thin film was then subjected to hydrogen plasma post-treatment in the same reaction chamber. The substrate temperature was maintained at a constant 250°C, and hydrogen gas (2000 sccm) and argon gas (400 sccm) were supplied for 120 seconds. During this time, the pressure in the reaction chamber was maintained at 5 Torr, and a 13.56 MHz RF power of 100 W was supplied. Finally, reaction byproducts and residual reaction gases were removed using argon gas (3000 sccm) for 5 seconds. The entire process described above was repeated four times to form a ruthenium-containing thin film.

[0100] Detailed thin film manufacturing conditions are shown in Table 4 below. TEM analysis was performed on the formed ruthenium thin films, and the results of evaluating the thickness and step coverage characteristics of the ruthenium-containing thin films are shown in Table 5 and Figure 6.

[0101] [Table 4]

[0102] [Table 5] Referring to Table 5 and Figure 6, it can be seen that highly uniform thin films can be formed even with thin film thicknesses of 22 Å to 25 Å.

[0103] Although embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art using the basic concepts of the present invention as defined in the following claims also fall within the scope of the present invention.

Claims

1. A step of supplying a transport gas and a ruthenium precursor represented by the following chemical formula 1 into a chamber in which a substrate is mounted, and depositing a ruthenium-containing thin film onto the substrate while injecting a reducing reaction gas into the chamber; and A post-treatment step comprising at least one of the steps of heat treatment in a reducing reaction gas atmosphere and plasma treatment in a reducing reaction gas atmosphere; Includes, The reducing reaction gas is H ２ , hydrazine (NH ２ NH ２ ), NH ３ and BH ３ A method for producing a ruthenium-containing thin film, which is at least one selected from: 【Chemistry 1】 In the above chemical formula 1, R is a substituted or unsubstituted C1 to C5 alkyl group.

2. The method for producing a ruthenium-containing thin film according to claim 1, wherein in the supply step, the temperature of the substrate is maintained at 80°C to 300°C.

3. The method for producing a ruthenium-containing thin film according to claim 1, wherein the reducing reaction gas is injected in an amount of 0.1 to 500 moles per mole of the ruthenium precursor.

4. The heat treatment is carried out at a temperature of 200 to 1000°C. The method for producing a ruthenium-containing thin film according to claim 1, wherein the plasma treatment is performed with an RF power of 50 to 1000 W.

5. A method for producing a ruthenium-containing thin film according to claim 1, further comprising the step of supplying an inert gas and purging.

6. The method for producing a ruthenium-containing thin film according to claim 1, wherein the resistivity of the ruthenium-containing thin film is 25 μΩ·cm or less.

7. A method for producing a ruthenium-containing thin film according to claim 1, wherein the carbon content is 2 at% or less.

8. A method for producing a ruthenium-containing thin film according to claim 1, wherein the oxygen content is 1 at% or less.

9. A method for producing a ruthenium-containing thin film according to claim 1, wherein the nitrogen content is greater than 0 and less than 3 at%.

10. A method for producing a ruthenium-containing thin film according to claim 1, wherein the hydrogen content is 7 at% or less.

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