Ruthenium precursor composition, method for preparing the same, and method for forming a ruthenium-containing film using the same

Abstract

This invention relates to a ruthenium precursor composition, a method for preparing it, and a method for using it to form a ruthenium-containing thin film. According to one embodiment of the invention, since the method involves reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, wherein the contents of the compounds represented by Formula 1, Formula 2, and Formula 3 are each controlled within specific ranges, the desired thermally stable ruthenium precursor composition can be prepared economically and efficiently. Furthermore, when using the ruthenium precursor composition to form a ruthenium-containing thin film, it is possible to prevent changes in the composition of the ruthenium precursor composition during or after its vaporization process and to minimize the formation of byproducts such as thermally decomposed materials. Therefore, it is possible to obtain physically stable and consistent deposition results in semiconductor processes, thereby providing ruthenium-containing thin films with guaranteed reproducibility and reliability.

Description

Technical Field

[0001] Invention Field

[0002] This invention relates to a ruthenium precursor composition, a method for preparing the precursor, and a method for using the precursor to form a ruthenium-containing thin film. Prior Technology

[0003] Background of the Invention

[0004] Because ruthenium (Ru) metal has low resistivity (ρ bulk = 7.6 μΩ·cm) and high work function (Φ bulk = 4.71 eV), it can be used as the gate electrode of transistors; or as the capacitor electrode material for dynamic random access memory (DRAM) or ferroelectric random access memory (FeRAM). In particular, since ruthenium (Ru) metal has good conductivity like copper (Cu), tungsten (W), and cobalt (Co), it can be used as a wiring material for semiconductor devices.

[0005] Generally, as semiconductor devices become more integrated and metal wiring becomes narrower, the resistance of metal wiring may increase. However, if ruthenium is used for wiring in semiconductor devices with very narrow metal wiring widths (approximately 40 nm or less), the increase in resistance is less than that of copper or cobalt; therefore, it can be advantageously used as a next-generation wiring material.

[0006] Meanwhile, in order to fill the narrow trenches required for wiring in next-generation semiconductor devices with ruthenium metal, it is advantageous to supply gaseous ruthenium compounds to the substrate surface to form ruthenium-containing thin films by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0007] For this purpose, various ruthenium precursor compositions that can be used in CVD or ALD have recently been developed.

[0008] However, when such ruthenium precursor compositions are applied to semiconductor devices, the ruthenium precursor compositions may change during vaporization or over time, and they may be thermally unstable, leading to the formation of byproducts such as thermally decomposed materials. Therefore, serious problems arise because stable and consistent deposition results cannot be obtained in semiconductor processes, and reproducibility cannot be guaranteed.

[0009] Therefore, there is a need to develop a thermally stable ruthenium precursor composition that is not easily altered even at vaporization temperatures and that minimizes the formation of byproducts. [Previous Technical Documents] [Non-patent documents]

[0010] (Non-patent document 1) LG Wen et al., “Ruthenium metallization for advanced interconnects,” 2016 IEEE International Interconnect Technology Conference / Advanced Metallization Conference (IITC / AMC), doi:10.1109 / iitc-amc.2016.7507651, 2016.

[0011] (Non-patent document 2) YM Wuu et al., Inorganic Chemistry 1988, 27(17), 3039-3044, doi: 10.1021 / ic00290a028. Summary of the Invention

[0012] Invention Summary [Technical Issues]

[0013] One object of the present invention is to provide a thermally stable ruthenium precursor composition, such that its composition is not easily changed even at vaporization temperatures, and the formation of byproducts such as thermally decomposed materials can be minimized.

[0014] Another object of the present invention is to provide an economical and efficient method for preparing ruthenium precursor compositions that are thermally stable, such that their composition is not easily altered even at vaporization temperatures, and that the formation of byproducts such as thermally decomposed materials is minimized.

[0015] Another object of the present invention is to provide a method for forming a ruthenium-containing thin film, wherein the ruthenium-containing thin film is formed in a stable and efficient manner using a ruthenium precursor composition.

[0016] Another object of the present invention is to provide a ruthenium-containing film that has uniform thickness and excellent quality even on various substrates formed using ruthenium precursor compositions.

[0017] However, the problems to be solved by the present invention are not limited to those described above, and those skilled in the art will clearly understand from the following description other problems not mentioned. [Problem Solution]

[0018] This invention provides a ruthenium precursor composition comprising 20% ​​to 60% by weight of a compound represented by Formula 1, 20% to 50% by weight of a compound represented by Formula 2, and 0% to 55% by weight of a compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [[] [Mode] [1] [[] [Mode] [2] [, , ] [[] [Mode] [3] .

[0019] This invention provides a method for preparing a ruthenium precursor composition, comprising reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, wherein the ruthenium precursor composition comprises 20 wt% to 60 wt% of a compound represented by Formula 1, 20 wt% to 50 wt% of a compound represented by Formula 2, and 0 wt% to 55 wt% of a compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [[] [Mode] [1] [[] [Mode] [2] [[] [Mode] [3] [, , ] [[] [Mode] [4] [[] [Mode] [5] M 2CO 3

[0020] In the above formula, the M series is selected from the group consisting of Li, Na and K, and the X series is selected from the group consisting of Cl, Br and I.

[0021] Furthermore, the present invention provides a method for forming a ruthenium-containing thin film, comprising preparing a ruthenium precursor composition; and using the ruthenium precursor composition to form a ruthenium-containing thin film, wherein the ruthenium precursor composition is prepared by reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, and comprises 20% to 60% by weight of the compound represented by Formula 1, 20% to 50% by weight of the compound represented by Formula 2, and 0% to 55% by weight of the compound represented by Formula 3, based on the total weight of the ruthenium precursor composition.

[0022] Furthermore, the present invention provides a ruthenium-containing thin film formed using a ruthenium precursor composition. [Advantages of the Invention]

[0023] According to one embodiment of the present invention, by controlling the contents of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 within a specific range, a very thermally stable ruthenium precursor composition can be provided in an economical and efficient manner.

[0024] When forming ruthenium-containing thin films using a ruthenium precursor composition according to one embodiment of the present invention, it is possible to prevent changes in the composition of the ruthenium precursor composition during or after its vaporization process and to minimize the formation of byproducts such as thermally decomposed materials. Therefore, it is possible to obtain physically stable and consistent deposition results in semiconductor processes, thereby providing ruthenium-containing thin films with guaranteed reproducibility and reliability.

[0025] Furthermore, according to another embodiment of the present invention, even on substrates with patterns (grooves), porous substrates, or plastic substrates, it is possible to uniformly form ruthenium-containing films with thicknesses ranging from a few nanometers to a few micrometers within a variety of temperature ranges, thereby potentially obtaining high-quality ruthenium-containing films. Simple Explanation of the Diagram

[0026] Figure 1 is a graph showing the static thermal stability test results of the ruthenium precursor composition of Example 1 of the present invention measured by NMR at 120°C.

[0027] Figure 2 is a graph showing the static thermal stability test results of the ruthenium precursor composition of Example 5 of the present invention measured by NMR at 120°C. Implementation

[0028] The present invention will be described in detail below.

[0029] The advantages and features of the present invention, as well as the methods for achieving them, will become apparent from the embodiments described below. However, the present invention is not limited to the embodiments described below, but may be implemented in various different forms. These embodiments are provided so that the disclosure of the invention is thorough and complete, and fully conveys the scope of the invention to those skilled in the art. The invention is defined only by the scope of the claims.

[0030] Furthermore, in this specification, when it is mentioned that an element is formed "on" another element, it means not only that an element is formed directly "on" another element, but also that other elements are inserted between them.

[0031] Unless otherwise specified, when a component is referred to as "comprising" an element in this specification, it should be understood that the component may also include other elements, rather than excluding other elements.

[0032] Unless otherwise stated, all figures and expressions relating to the amount of components, reaction conditions and their analogues used herein should be understood as modified by the term "about". [[] [Ruthenium precursor components]

[0033] According to one embodiment of the present invention, a ruthenium precursor composition comprises 20% to 60% by weight of a compound represented by Formula 1, 20% to 50% by weight of a compound represented by Formula 2, and 0% to 55% by weight of a compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [[] [Mode] [1] [[] [Mode] [2] [[] [Mode] [3] .

[0034] Since the contents of the compounds represented by Formula 1, Formula 2, and Formula 3 are each controlled within a specific range, the thermal stability of the ruthenium precursor composition can be greatly enhanced.

[0035] When forming ruthenium-containing thin films using the ruthenium precursor composition of the present invention, which has excellent thermal stability, it is possible to minimize the changes in the composition of the ruthenium precursor composition at high temperatures of 100°C or higher, during its vaporization process, and over time, as well as the formation of byproducts such as thermally decomposed materials.

[0036] Therefore, the significant technical significance of this invention lies in the fact that, since it provides a ruthenium precursor composition with the above-mentioned characteristics, it is possible to obtain deposition results with more stable and consistent physical properties in semiconductor manufacturing processes, thereby providing ruthenium-containing thin films with guaranteed reproducibility and reliability.

[0037] According to one embodiment of the present invention, it is very important to control the content range and content ratio of each compound in order to achieve the above-mentioned characteristics.

[0038] The ruthenium precursor composition may contain the compound represented by Formula 1 in the following amounts: for example, 22 wt% to 60 wt%, for example, 25 wt% to 60 wt%, for example, 28 wt% to 60 wt%, for example, 30 wt% to 60 wt%, for example, 35 wt% to 60 wt%, for example, 40 wt% to 60 wt%, for example, 45 wt% to 60 wt%, for example, 50 wt% to 60 wt%, or for example, 55 wt% to 60 wt%, based on the total weight of the ruthenium precursor composition. If the compound represented by Formula 1 satisfies the above content range, the thermal stability can be further enhanced, and the formation of byproducts such as thermally decomposable materials can be minimized.

[0039] Furthermore, the ruthenium precursor composition may contain the compound represented by Formula 2 in the following amounts: for example, 22 wt% to 50 wt%, for example, 25 wt% to 50 wt%, for example, 28 wt% to 50 wt%, for example, 30 wt% to 50 wt%, or for example, 35 wt% to 50 wt%, based on the total weight of the ruthenium precursor composition. If the compound represented by Formula 2 meets the above content range, the thermal stability can be further enhanced, and the formation of byproducts such as thermally decomposable materials can be minimized.

[0040] In addition, the ruthenium precursor composition may contain compounds represented by Formula 3 in the following amounts: for example, 0 wt% to 25 wt%, for example, 0 wt% to 20 wt%, for example, 0 wt% to 18 wt%, for example, 0 wt% to 15 wt%, for example, 0 wt% to 10 wt%, for example, 0 wt% to 8 wt%, for example, 0 wt% to 7 wt%, for example, 0 wt% to 6 wt%, for example, 0 wt% to 5 wt%, for example, 0 wt% to 4 wt%, for example, 0 wt% to 3 wt%, for example, 0 wt% to 2 wt%, or for example, 0 wt% to 1 wt%, based on the total weight of the ruthenium precursor composition.

[0041] The ruthenium precursor composition may contain the following amounts of the compound represented by Formula 3: 10% or less by weight, 9% or less by weight, 8% or less by weight, 5% or less by weight, 3% or less by weight, 2% or less by weight, or 1% or less by weight, based on the total weight of the ruthenium precursor composition.

[0042] If the compound represented by Formula 3 meets the above content range, the ruthenium precursor composition is very thermally stable, and the formation of byproducts such as thermally decomposed materials can be minimized at temperatures of 100°C or higher.

[0043] The compounds represented by Formula 1, Formula 2, and Formula 3 can be isomers with the same molecular weight.

[0044] The contents of the compounds represented by Formula 1, Formula 2, and Formula 3 are calculated, for example, by obtaining the integral ratio of the NMR peaks to the sum of the integral values ​​of the NMR peaks. When measured by 1H-NMR (400 MHz, C 6D 6, 25 °C), the sum of these integral values ​​is 100%. Since the ruthenium precursor composition comprises a mixture of the compounds represented by Formula 1, Formula 2, and Formula 3, as a mixture of three isomers with the same molecular weight, their contents can be expressed as weight percent.

[0045] In particular, according to one embodiment of the invention, it is very important to control the content of the compound represented by formula 3.

[0046] In other words, when the compound represented by Formula 3 meets a specific content range or lower, it exhibits excellent thermal stability, resulting in minimal changes in composition during vaporization and minimizing thermal decomposition, thereby preventing the formation of byproducts. However, if the compound represented by Formula 3 does not meet the specific content range and is used in excess, the composition is prone to change during vaporization, making it easy for the composition at a certain temperature or higher to change over time, and increasing the formation of byproducts. This makes it difficult to obtain characteristically stable and consistent deposition results, leading to difficulties in achieving reproducibility and reliability.

[0047] Furthermore, ruthenium precursor compositions may not contain compounds represented by Formula 3.

[0048] In this case, it may be more conducive to achieving the goal because the ruthenium precursor composition is very thermally stable.

[0049] The ratio (by weight) of the total content of the compound represented by Formula 1 and the compound represented by Formula 2 to the content of the compound represented by Formula 3 is, for example, 100:0 to 80:20, 100:0 to 85:15, 100:0 to 90:10, 100:0 to 95:5, or 100:0 to 97:3.

[0050] If the ratio of the total content of the compound represented by Formula 1 and the compound represented by Formula 2 to the content of the compound represented by Formula 3 meets the above range, it may be more conducive to achieving the goal, because the ruthenium precursor composition is very thermally stable.

[0051] Furthermore, the weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is, for example, 7:3 to 5:5, 7:3 to 5.5:4.5, 6.5:3.5 to 5.5:4.5, 6:4 to 5:5, or 5.5:4.5 to 5:5. If the weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 meets the above range, it may be more advantageous to achieve the goal because the ruthenium precursor composition is very thermally stable.

[0052] According to another embodiment of the invention, the ruthenium precursor composition may contain more compounds represented by Formula 1 than compounds represented by Formula 2. In this case, it may be more advantageous to further enhance thermal stability and minimize the formation of byproducts due to thermal decomposition.

[0053] According to another embodiment of the present invention, the weight ratio of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 can be, for example, 20 to 60:20 to 50:0 to 50, for example, 30 to 60:25 to 50:0 to 30, for example, 35 to 60:30 to 50:0 to 20, or for example, 40 to 60:30 to 50:0 to 10. If the ratio of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 satisfies the above ranges, it may be more advantageous to achieve the objectives of the present invention because the ruthenium precursor composition is very thermally stable.

[0054] Meanwhile, the ruthenium precursor composition may contain byproducts. Byproducts may include unreacted materials formed during the preparation of the ruthenium precursor composition, impurities formed by thermal decomposition, and similar substances.

[0055] The byproduct content in the ruthenium precursor composition may be 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.2% by weight or less, or 0% by weight, based on the total weight of the ruthenium precursor composition.

[0056] Specifically, ruthenium precursor compositions may include one or more byproducts. For example, byproducts may include a first byproduct or a second byproduct with different components, or a combination thereof.

[0057] Furthermore, according to one embodiment of the present invention, it may not contain byproducts.

[0058] Specifically, when the ruthenium precursor composition is placed in a sealed stainless steel container, heated, cooled to room temperature, and measured by 1H-NMR (400 MHz, C 6D 6, 25 °C), and the sum of the integrated values ​​of the NMR peaks at approximately 2.01 ppm (Equation 1), approximately 1.97 ppm (Equation 2), approximately 1.95 ppm (byproduct A), approximately 1.86 ppm (byproduct B), and approximately 1.84 ppm (Equation 3) is 100%, the sum of the integrated values ​​of the two integrated peaks at 1.95 ppm (byproduct A) and 1.86 ppm (byproduct A) that did not appear in the NMR spectrum before heating is 30% or less, or the NMR peaks do not appear at 1.95 ppm, 1.86 ppm, or both. Preferably, no NMR spikes were measured at 1.95 ppm, 1.86 ppm, or both, more specifically at 1.95 ppm and 1.86 ppm.

[0059] Materials exhibiting NMR spikes at 1.95 ppm and 1.86 ppm are impurities formed through thermal decomposition due to prolonged heating. Since the thermal stability of the ruthenium precursor composition according to the present invention is greatly enhanced, it is preferable that the aforementioned NMR spikes are not observed.

[0060] NMR spectroscopy is used for thermal stability analysis. For example, ruthenium precursor components vaporized by heating to approximately 120 °C under vacuum with an argon carrier gas flow rate of approximately 200 sccm can be recovered by cooling to approximately -76 °C. Components recovered by vaporization during the first 7 days (week 1) and from day 8 to day 14 (week 2) can be measured by 1H-NMR (400 MHz, C 6D 6, 25 °C), respectively.

[0061] Therefore, since the ruthenium precursor composition according to the present invention can achieve stable and consistent deposition results in semiconductor processes, it may be advantageous in terms of reliability and reproducibility. [[] [Method for preparing ruthenium precursor compositions]

[0062] A method for preparing a ruthenium precursor composition according to an embodiment of the present invention comprises reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, wherein the ruthenium precursor composition comprises 20 wt% to 60 wt% of a compound represented by Formula 1, 20 wt% to 50 wt% of a compound represented by Formula 2, and 0 wt% to 55 wt% of a compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [[] [Mode] [1] [[] [Mode] [2] [[] [Mode] [3] [[] [Mode] [4] [[] [Mode] [5] M 2CO 3 In the above formula, the M series is selected from the group consisting of Li, Na and K, and the X series is selected from the group consisting of Cl, Br and I.

[0063] According to one embodiment of the present invention, since the method involves reacting the compound represented by Formula 4 with the alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, the desired thermally stable ruthenium precursor composition can be prepared in an economical and efficient manner.

[0064] Specifically, as shown in the following reaction flow 1, a method for preparing a ruthenium precursor composition according to an embodiment of the present invention may include reacting the compound represented by Formula 4 with the alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent: [[] [Reaction Flow 1]

[0065] In reaction process 1, X is as defined above.

[0066] In a method for preparing a ruthenium precursor composition according to one embodiment of the present invention, the reaction may be a reflux reaction, but is not limited thereto.

[0067] Specifically, the reaction may be a reflux reaction carried out at, for example, 60 to 160°C, 70 to 150°C, or 80 to 140°C for about 10 to 100 hours, about 20 to 100 hours, or about 20 to 80 hours.

[0068] In one embodiment of the present invention, the organic solvent may comprise a primary alcohol or a secondary alcohol having five or fewer carbon atoms, but is not limited thereto.

[0069] Primary or secondary alcohols having five or fewer carbon atoms can act as both solvents and reducing agents. Therefore, the ruthenium compounds according to the present invention can be manufactured using an economical and simple method that does not require a separate reducing agent.

[0070] Primary or secondary alcohols may be selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, and combinations thereof, but may not be limited thereto.

[0071] Alkali metal carbonates may include at least one of the following groups: Na₂CO₃, Li₂CO₃, and K₂CO₃.

[0072] Furthermore, in methods for preparing ruthenium precursor compositions, 1,5-hexadiene can be used as a material for reaction with compounds represented by Formula 4 and alkali metal carbonates represented by Formula 5. 1,5-hexadiene is highly advantageous for commercial applications because it is cost-effective and readily available in large quantities compared to, for example, 2,4-hexadiene or 1,3-hexadiene.

[0073] Specifically, 2,4-hexadiene or 1,3-hexadiene is not readily available commercially, and the quantity and availability of these materials are very limited (e.g., limited to a few grams or tens of grams). Therefore, the use of 2,4-hexadiene or 1,3-hexadiene for large-scale production of the required ruthenium precursor compositions may be restricted. In contrast, 1,5-hexadiene is readily available in large quantities at a low cost. Furthermore, when used to prepare ruthenium precursor compositions, particularly when used to prepare ruthenium precursor compositions that do not contain compounds represented by Formula 3, the desired effects can be easily and effectively achieved. That is, the use of 1,5-hexadiene may be highly advantageous in terms of cost, productivity, efficiency, and quality in the preparation of ruthenium precursor compositions and in semiconductor manufacturing processes.

[0074] Meanwhile, in the method for preparing a ruthenium precursor composition according to one embodiment of the present invention, the molar ratio of the compound represented by Formula 4, the alkali metal carbonate, and 1,5-hexadiene may be, for example, 1:2 to 10:1 to 8, for example, 1:2 to 10:2 to 8, or for example, 1:4 to 10:3 to 7.

[0075] If the molar ratio of the compound represented by Formula 4, the alkali metal carbonate, and 1,5-hexadiene satisfies the above range, it may be more conducive to achieving the desired effect of the present invention.

[0076] Meanwhile, in one embodiment of the present invention, the compound of formula 4 can be prepared as shown in reaction flow 2 below. [Reaction Process 2]

[0077] In reaction process 2, X is as defined above, and n is an integer of 0, 10, or less.

[0078] Specifically, the compound represented by Formula 4, [RuX 2 (p-isopropyltoluene)] 2, can be prepared by reacting α-terpinene represented by Formula 6 or γ-terpinene represented by Formula 7 with ruthenium trichloride hydrate (RuX 3·nH 2O) in an organic solvent such as an alcohol.

[0079] In this case, β-terpinene, δ-terpinene, α-phellandrene, β-phellandrene, or their isomers, may be used instead of α-terpinene or γ-terpinene. In one embodiment of the invention, the reaction for preparing the compound represented by Formula 4 may be a reflux reaction, but is not limited thereto.

[0080] In a method for preparing a ruthenium precursor composition according to one embodiment of the present invention, the reflux reaction may be carried out once or at least twice.

[0081] Specifically, it may involve a first reflux reaction in an organic solvent involving the compound represented by Formula 4, an alkali metal carbonate represented by Formula 5, and 1,5-hexadiene.

[0082] Furthermore, after the compound represented by Formula 4 is subjected to, for example, a first reflux reaction with the alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, the method for preparing the ruthenium precursor composition may further include distillation under reduced pressure of 0.1 Torr to 1 Torr, 0.1 Torr to 0.7 Torr, 0.1 Torr to 0.5 Torr, or 0.2 Torr to 0.4 Torr and at temperatures of 50°C to 200°C, 70°C to 150°C, 70°C to 140°C, or 80°C to 120°C.

[0083] Furthermore, the composition of the ruthenium precursor can be adjusted by changing the distillation conditions. Specifically, by changing the distillation conditions to 0.2 Torr to 0.4 Torr and 100°C to 120°C, the content of the compound represented by Formula 3 can be adjusted to, for example, about 10% by weight or less.

[0084] Meanwhile, in another embodiment of the present invention, in a method for preparing a ruthenium precursor composition, the reflux reaction may be carried out at least twice, for example twice.

[0085] Specifically, as shown in the following reaction flow 3, the reaction may include a first reflux reaction of the compound represented by Formula 4 with a first alkali metal carbonate and 1,5-hexadiene in an organic solvent; and a second reflux reaction of the product obtained from the first reflux reaction with a second alkali metal carbonate. [[] [Reaction Process 3]

[0086] In reaction process 3, X is as defined above.

[0087] In reaction process 3, the first reflux reaction may be carried out at 60 to 160°C, for example 70 to 140°C, or for example 90 to 120°C for about 10 to 40 hours, about 15 to 35 hours, or about 20 to 25 hours.

[0088] In reaction process 3, the second reflux reaction may be carried out at 60 to 160°C, for example 70 to 140°C, or for example 90 to 120°C for about 10 to 60 hours, about 15 to 55 hours, or about 20 to 50 hours.

[0089] The first alkali metal carbonate may contain Li₂CO₃. If Li₂CO₃ is used as the first alkali metal carbonate, it can be confirmed by NMR analysis during the first reflux reaction that the NMR peak corresponding to 1,5-hexadiene decreases and then disappears completely. Isomerization reactions are known, in which hydrogens bonded to the double-bonded carbon coordinated with the Ru-centered metal are transferred to another carbon [YM Wuu et al., Inorganic Chemistry 1988, 27(17), 3039-3044, doi: 10.1021 / ic00290a028]. It is presumed that 1,5-hexadiene used as a raw material is transformed into 2,4-hexadiene and 1,3-hexadiene through such isomerization reactions. Therefore, it may be more advantageous to control the ruthenium precursor composition within the specific range required by the present invention.

[0090] Furthermore, the second alkali metal carbonate may contain Na₂CO₃, K₂CO₃, or a combination thereof, preferably Na₂CO₃. Using Na₂CO₃ as the second alkali metal carbonate results in a high yield; therefore, it is more advantageous to control the ruthenium precursor composition within the specific range required by this invention.

[0091] The molar ratio of the first alkali metal carbonate to the second alkali metal carbonate can be, for example, 1:0.2 to 3.0, 1:0.5 to 2.5, 1:0.5 to 2.0, or 1:0.5 to 2.0. If the molar ratio of the first alkali metal carbonate to the second alkali metal carbonate satisfies the above range, it is more advantageous to obtain the ruthenium precursor composition required by the present invention.

[0092] Meanwhile, the method for preparing ruthenium precursor composition according to one embodiment of the present invention may further include cooling the product to room temperature before carrying out the second reflux reaction.

[0093] Specifically, it may include a first reflux reaction of the compound represented by Formula 4 with a first alkali metal carbonate and 1,5-hexadiene in an organic solvent; cooling the product obtained from the first reflux reaction to room temperature; and a second reflux reaction of the product with a second alkali metal carbonate.

[0094] Furthermore, according to one embodiment of the present invention, the method for preparing the ruthenium precursor composition may further include distillation and / or filtration after the second reflux reaction.

[0095] Distillation and / or filtration are as described above.

[0096] According to one embodiment of the present invention, since a method for preparing ruthenium precursor compositions is used, the compounds represented by Formula 1, Formula 2, and Formula 3 can each be adjusted to have specific content ranges. In particular, the content of the compound represented by Formula 3 can be adjusted to 10% by weight or lower.

[0097] Furthermore, according to one embodiment of the present invention, since a method for preparing ruthenium precursor compositions is used, it is possible to control the composition so that it does not contain the compound represented by formula 3.

[0098] In this context, it is possible to provide a highly thermally stable ruthenium precursor composition. When used to form ruthenium-containing thin films, it is possible to prevent changes in the composition of the ruthenium precursor composition during or after its vaporization and to minimize the formation of byproducts such as thermally decomposed materials. Therefore, it is possible to obtain physically stable and consistent deposition results in semiconductor processes, thereby providing ruthenium-containing thin films with guaranteed reproducibility and reliability. [[] [Method for forming ruthenium-containing thin films]

[0099] According to one embodiment of the present invention, a ruthenium-containing thin film can be formed using a ruthenium precursor composition prepared by the above method.

[0100] Specifically, the method for forming a ruthenium-containing thin film includes preparing a ruthenium precursor composition (first step); and using the ruthenium precursor composition to form a ruthenium-containing thin film (second step), wherein the ruthenium precursor composition is prepared by reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, and includes 20% to 60% by weight of the compound represented by Formula 1, 20% to 50% by weight of the compound represented by Formula 2, and 0% to 55% by weight of the compound represented by Formula 3, based on the total weight of the ruthenium precursor composition.

[0101] In the method for forming a ruthenium-containing thin film, the step of preparing the ruthenium precursor composition (the first step) is as described above.

[0102] A method for forming a ruthenium-containing thin film may include forming a ruthenium-containing thin film using a ruthenium precursor composition (second step).

[0103] Specifically, the second step is to deposit a ruthenium-containing thin film on a substrate using a ruthenium precursor composition. This may include forming a ruthenium-containing thin film on the substrate by supplying the ruthenium precursor composition in a gaseous state.

[0104] In one embodiment of the present invention, the ruthenium-containing thin film may be formed on one or more substrates selected from: conventional semiconductor wafers, composite semiconductor wafers, and plastic substrates (PI, PET, PES, and PEN), but is not limited thereto. Furthermore, substrates with holes or trenches may be used, and porous substrates with large surface areas may be used, but is not limited thereto. Additionally, the ruthenium-containing thin film may be formed simultaneously or sequentially on all or part of the substrates, wherein two or more different types of substrates are in contact or connected to each other, but is not limited thereto.

[0105] According to one embodiment of the present invention, in a method for depositing a ruthenium-containing thin film, a substrate is contained in a reaction chamber, and then a carrier gas or diluent gas is used to transfer a ruthenium precursor composition onto the substrate to deposit the ruthenium-containing thin film.

[0106] Specifically, the deposition can be formed within the following temperature ranges: room temperature to 550°C, room temperature to about 500°C, room temperature to about 450°C, room temperature to about 400°C, room temperature to about 350°C, room temperature to about 300°C, room temperature to about 250°C, room temperature to about 200°C, room temperature to about 150°C, room temperature to about 100°C, about 100°C to about 550°C, about 100°C to about 500°C, about 100°C to about 450°C, about 100°C to about 400°C, about 100°C to about 350°C, about 100°C to about 300°C, about 100°C to about 250°C, about 100°C to about 200°C, about 100°C to about 150°C, about 150°C to about 550°C, about 150°C to about 550°C, about 150°C to about 1 ... 0°C to about 500°C, about 150°C to about 450°C, about 150°C to about 400°C, about 150°C to about 350°C, about 150°C to about 300°C, about 150°C to about 250°C, about 150°C to about 200°C, about 200°C to about 400°C, about 200°C to about 350°C, about 200°C to about 300°C, about 200°C to about 250°C, about 250°C to about 400°C, about 250°C to about 350°C, about 250°C to about 300°C, about 300°C to about 400°C, about 300°C to about 550°C, about 300°C to about 500°C, about 300°C to about 350°C, or about 350°C to about 400°C, but not limited to these. In one embodiment of the present invention, a ruthenium-containing thin film can be formed in the following temperature range: about 200°C to about 500°C or about 300°C to about 500°C.

[0107] In one embodiment of the present invention, ruthenium-containing thin films can be deposited by chemical vapor deposition (CVD), specifically metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but are not limited thereto. In one embodiment of the present invention, the chemical vapor deposition or atomic layer deposition of ruthenium-containing thin films can be performed using deposition equipment, deposition conditions, and one or more additional reactive gases known in the art, but are not limited thereto.

[0108] In one embodiment of the present invention, hydrogen (H2), ammonia (NH3), oxygen (O2), or ozone (O3) gas used in semiconductor manufacturing processes can be used as reaction gases in ALD and CVD methods to form ruthenium-containing thin films, but is not limited thereto.

[0109] For example, if hydrogen and / or ammonia are used in ALD and CVD processes to form thin films, ruthenium-containing thin films with fewer impurities can be formed. For example, if oxygen or ozone gas is used in ALD and CVD processes to form thin films, ruthenium metal thin films or ruthenium oxide thin films can be formed, but these are not limited to these methods.

[0110] In one embodiment of the present invention, the method for forming a ruthenium-containing thin film includes supplying a ruthenium precursor composition in a gaseous state onto a substrate located in a deposition chamber to form a ruthenium-containing thin film on the surface of the substrate, but is not limited thereto.

[0111] In one embodiment of the present invention, the thickness of the ruthenium-containing thin film can be formed in the range of about 1 nm to about 500 nm. Although there are many possible applications depending on the application purpose, it is not limited to this. For example, ruthenium-containing thin films can be formed with thicknesses ranging from about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, about 10 nm to about 40 nm, about 10 nm to about 30 nm, about 10 nm to about 20 nm, about 20 nm to about 500 nm, about 20 nm to about 400 nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, about 20 nm to about 500 nm. nm, about 20 nm to about 40 nm, about 20 nm to about 30 nm, about 30 nm to about 500 nm, about 30 nm to about 400 nm, about 30 nm to about 300 nm, about 30 nm to about 200 nm, about 30 nm to about 100 nm, about 30 nm to about 50 nm, about 30 nm to about 40 nm, about 40 nm to about 500 nm, about 40 nm to about 400 nm, about 40 nm to about 300 nm, about 40 nm to about 200 nm, about 40 nm to about 100 nm, about 40 nm to about 50 nm, about 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 100 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm The thickness of the ruthenium-containing thin film can range from about 1 nm to about 50 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, or about 400 nm to about 500 nm, but is not limited thereto. In one embodiment of the invention, the thickness of the ruthenium-containing thin film can be formed in the range of about 1 nm to about 50 nm.

[0112] In one embodiment of the invention, a ruthenium-containing thin film may be formed on a substrate comprising irregularities (grooves) having a depth-to-width ratio of about 1 to about 100 and a width of about 10 nm to about 1 μm, but is not limited thereto. The irregularities (grooves) may be in the form of holes or recesses. For example, the depth-to-width ratio can be about 1 or more, about 10 or more, about 30 or more, about 50 or more, about 1 to about 100, about 1 to about 90, about 1 to about 80, about 1 to about 70, about 1 to about 60, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 10 to about 100, about 10 to about 90, about 10 to about 80, about 10 to about 70, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 100, about 20 to about 90, about 20 to about 80, about 20 to about 70, about 20 to about 60, about 20 to about 50, about 20 to about 40, about 20 to Approximately 30, approximately 30 to approximately 100, approximately 30 to approximately 90, approximately 30 to approximately 80, approximately 30 to approximately 70, approximately 30 to approximately 60, approximately 30 to approximately 50, approximately 30 to approximately 40, approximately 40 to approximately 100, approximately 40 to approximately 90, approximately 40 to approximately 80, approximately 40 to approximately 70, approximately 40 to approximately 60, approximately 40 to approximately 50, approximately 50 to approximately 100, approximately 50 to approximately 90, approximately 50 to approximately 80, approximately 50 to approximately 70, approximately 50 to approximately 60, approximately 60 to approximately 100, approximately 60 to approximately 90, approximately 60 to approximately 80, approximately 60 to approximately 70, approximately 70 to approximately 100, approximately 70 to approximately 90, approximately 70 to approximately 80, approximately 80 to approximately 100, approximately 80 to approximately 90, or approximately 90 to approximately 100, but not limited to these. Furthermore, for example, the width can be approximately 10 nm to approximately 1 µm, approximately 10 nm to approximately 900 nm, approximately 10 nm to approximately 800 nm, approximately 10 nm to approximately 700 nm, approximately 10 nm to approximately 600 nm, approximately 10 nm to approximately 500 nm, approximately 10 nm to approximately 400 nm, approximately 10 nm to approximately 300 nm, approximately 10 nm to approximately 200 nm, approximately 10 nm to approximately 100 nm, approximately 10 nm to approximately 90 nm, approximately 10 nm to approximately 80 nm, approximately 10 nm to approximately 70 nm, approximately 10 nm to approximately 60 nm, approximately 10 nm to approximately 50 nm, approximately 10 nm to approximately 40 nm, approximately 10 nm to approximately 30 nm, approximately 10 nm to approximately 20 nm, approximately 20 nm to approximately 1 µm, approximately 20 nm to approximately 900 nm, approximately 20 nm to approximately 800 nm, approximately 20 nm to approximately 700 nm, approximately 20 nm to approximately 600 nm, approximately 20 nm to approximately 500 nm, approximately 20 nm to approximately 400 nm. nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, about 20 nm to about 90 nmnm, about 20 nm to about 80 nm, about 20 nm to about 70 nm, about 20 nm to about 60 nm, about 20 nm to about 50 nm, about 20 nm to about 40 nm, about 20 nm to about 30 nm, about 30 nm to about 1 µm, about 30 nm to about 900 nm, about 30 nm to about 800 nm, about 30 nm to about 700 nm, about 30 nm to about 600 nm, about 30 nm to about 500 nm, about 30 nm to about 400 nm, about 30 nm to about 300 nm, about 30 nm to about 200 nm, about 30 nm to about 100 nm, about 30 nm to about 90 nm, about 30 nm to about 80 nm, about 30 nm to about 70 nm, about 30 nm to about 60 nm, about 30 nm to about 50 nm, about 30 nm to about 40 nm, about 40 nm to about 1 µm, about 40 nm to about 900 nm, about 40 nm to about 800 nm, about 40 nm to about 700 nm nm, about 40 nm to about 600 nm, about 40 nm to about 500 nm, about 40 nm to about 400 nm, about 40 nm to about 300 nm, about 40 nm to about 200 nm, about 40 nm to about 100 nm, about 40 nm to about 90 nm, about 40 nm to about 80 nm, about 40 nm to about 70 nm, about 40 nm to about 60 nm, about 40 to about 50 nm, about 50 nm to about 1 µm, about 50 nm to about 900 nm, about 50 nm to about 800 nm, about 50 nm to about 700 nm, about 50 nm to about 600 nm, about 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 100 nm, about 50 nm to about 90 nm, about 50 nm to about 80 nm, about 50 nm to about 70 nm, about 50 nm to about 60 nm, about 100 nm to 1 µm, about 100 nm to 900 nm, about 100 nm to 800 nm, about 100 nm to 700 nm, about 100 nm to 600 nm, about 100 nm to 500 nm, about 100 nm to 400 nm, about 100 nm to 300 nm, about 100 nm to 200 nm, about 200 nm to 1 µm, about 200 nm to 900 nm, about 200 nm to 800 nm, about 200 nm to 700 nm, about 200 nm to 600 nm, about 200 nm to 500 nm, about 200 nm to 400 nm, about 200 nm to 300 nmnm, about 300 nm to about 1 µm, about 300 nm to about 900 nm, about 300 nm to about 800 nm, about 300 nm to about 700 nm, about 300 nm to about 600 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, about 400 nm to about 1 µm, about 400 nm to about 900 nm, about 400 nm to about 800 nm, about 400 nm to about 700 nm, about 400 nm to about 600 nm, about 400 nm to about 500 nm, about 500 nm to about 1 µm, about 500 nm to about 900 nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 1 µm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm The range is approximately 1 µm to 700 nm to 900 nm, approximately 700 nm to 800 nm, approximately 800 nm to 1 µm, approximately 800 nm to 900 nm, or approximately 900 nm to 1 µm, but may not be limited thereto.

[0113] In one embodiment of the present invention, the ruthenium precursor composition contained in the ruthenium-containing thin film can be used as a precursor for atomic layer deposition or chemical vapor deposition to form the ruthenium-containing thin film through its low density and high thermal stability. In particular, within a temperature range of room temperature to 550°C, it is possible to uniformly form ruthenium-containing thin films with a thickness of several micrometers to several nanometers even on substrates with patterned (grooved) surfaces, porous substrates, or plastic substrates.

[0114] In one embodiment of the present invention, in a method for forming a ruthenium-containing thin film, it is preferred to contain a substrate in a reaction chamber, deliver a ruthenium precursor composition onto the substrate using a carrier gas or diluent gas, and deposit a ruthenium-containing metal thin film, oxide thin film, or nitride thin film at a wide range of deposition temperatures from room temperature to about 550°C, but it is not limited thereto.

[0115] In one embodiment of the present invention, at least one mixed gas selected from argon (Ar), nitrogen (N2), helium (He) or hydrogen (H2) can preferably be used as a carrier gas or diluent gas, but is not limited thereto.

[0116] In one embodiment of the invention, various methods can be applied as methods for delivering ruthenium precursor components onto a substrate, such as the bubbling method using a carrier gas to forcefully vaporize the precursor, the liquid delivery system (LDS) method using liquid phase supply at room temperature and vaporization via a vaporizer, and the vapor flow control (VFC) method using vapor pressure to directly supply the precursor. If the vapor pressure is too high, the VFC method can be used. If the vapor pressure is too low, a bypass method can be used, in which the container is heated to evaporate the vapor.

[0117] A bubbling method can be used, in which the ruthenium precursor composition is contained in a bubbling container or a VFC container and bubbled with a carrier gas at a temperature range of about room temperature to about 100°C and at a pressure of about 0.1 Torr to about 10 Torr, or a high vapor pressure can be used to deliver it to the reaction chamber. Specifically, the LDS method can be used, in which the ruthenium precursor composition, which is in a liquid phase at room temperature, is supplied and vaporized via a vaporizer, but is not limited to this method.

[0118] In one embodiment of the present invention, in order to vaporize the ruthenium precursor composition, the ruthenium precursor composition can be transported by argon (Ar) or nitrogen (N2), thermal energy or plasma can be used, or a bias voltage can be applied to the substrate.

[0119] In one embodiment of the present invention, a deposition temperature of room temperature to about 550°C or about 200°C to about 500°C widens the process temperature range applicable to memory devices, logic devices, and display devices; therefore, it can be applied to various fields.

[0120] In one embodiment of the present invention, when a ruthenium-containing thin film is deposited as a ruthenium-containing metal thin film or oxide thin film, at least one of water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O plasma), oxygen nitride (N2O2), hydrogen peroxide (H2O2), and ozone (O3) can be used as the reactant gas.

[0121] In one embodiment of the present invention, when a ruthenium-containing thin film is deposited as a ruthenium-containing nitride thin film, at least one of ammonia (NH3), ammonia plasma (NH3 plasma), hydrazine (N2H4), and nitrogen plasma (N2 plasma) can be used as the reaction gas.

[0122] When forming ruthenium-containing thin films using a ruthenium precursor composition according to one embodiment of the present invention, it is possible to prevent changes in the composition of the ruthenium precursor composition during or after its vaporization process and to minimize the formation of byproducts such as thermally decomposed materials. Therefore, it is possible to obtain physically stable and consistent deposition results in semiconductor processes, thereby effectively providing ruthenium-containing thin films with guaranteed reproducibility and reliability. [[] [Ruthenium-containing thin film] []]

[0123] According to one embodiment of the present invention, a ruthenium-containing thin film formed using a ruthenium precursor composition is provided.

[0124] Ruthenium-containing thin films can have thicknesses ranging from about 1 nanometer (nm) to several micrometers (µm) and can be used in different applications depending on the purpose of the application.

[0125] For example, the thickness, aspect ratio, and width of ruthenium-containing films are as described above, and various options are available.

[0126] Because the contents of the compounds represented by Formula 1, Formula 2, and Formula 3 in the ruthenium precursor composition according to one embodiment of the present invention are each controlled within a specific range, it exhibits excellent thermal stability; therefore, ruthenium-containing thin films can be effectively formed over a wide temperature range by CVD and ALD. In particular, even on substrates with finely patterned surfaces (grooves), porous substrates, or plastic substrates with a thickness of several micrometers to tens of nanometers, it is possible to uniformly form ruthenium-containing thin films within a temperature range from room temperature to 550°C.

[0127] The ruthenium-containing thin film may be selected from at least one of the following groups: ruthenium-containing metal thin films, ruthenium-containing oxide thin films, ruthenium-containing carbide thin films, ruthenium-containing sulfide thin films, and ruthenium-containing nitride thin films. [example]

[0128] The invention will be described in detail below with reference to examples. These examples are merely illustrative and the scope of the invention is not limited thereto. [Preparation Example] [1] [:] [[RuCl , 2, ( ] [p-Isopropyltoluene] [)] , 2, ] [Preparation]

[0129] 27 g (0.13 mol) of hydrated ruthenium trichloride (RuCl3·nH2O) was dissolved in 200 ml of ethanol (C2H5OH) in a flame-dried 500-ml Schlenk flask. 35.4 g (0.26 mol, 2 equivalents) of α-terpinene was slowly added to the solution at room temperature, and the mixture was refluxed for 15 hours to complete the reaction.

[0130] After the reaction was complete, a dark brown solid was obtained by filtration, washed three times with 50 ml of n-hexane (C6H14), and dried under vacuum to obtain a reddish-brown solid compound [RuCl2(p-isopropyltoluene)]2. [example] [1] Preparation of Ruthenium Precursor Components

[0131] A suspension was prepared by mixing 30 g (0.048 mol) of [RuCl₂(p-isopropyltoluene)]₂ obtained in Preparation Example 1 and 31.1 g (0.294 mol) of Na₂CO₃ with 400 ml of 2-propanol in a flame-dried 1,000-ml Schlenk flask. 15.8 g (0.192 mol) of 1,5-hexadiene was slowly added to the suspension, and the mixture was refluxed for 40 hours to complete the reaction. After the reaction was complete, the solvent and volatile byproducts were removed under reduced pressure, and the product was then extracted with 500 ml of n-hexane. The n-hexane extract was filtered through a diatomaceous earth pad and glass glue, and the resulting filtrate was subjected to solvent removal under reduced pressure and distilled under reduced pressure to obtain liquid mixtures represented by Formulas 1, 2, and 3, having the compositions shown in Table 1 below. The ratio of the three isomers with the same molecular weight was determined as the relative ratio of the integral values ​​of the NMR peaks appearing at 2.01 ppm (Equation 1), 1.97 ppm (Equation 2), and 1.84 ppm (Equation 3), which is due to the hydrogen bonding of the methyl group (CH3) to the ligand benzene ring in the 1H-NMR (400 MHz, C6D6, 25℃) spectrum. 1H-NMR (400 MHz, C 6D 6, 25℃): Compound represented by Formula 1: (p-isopropyltoluene)(2,4-hexadiene)Ru, [CH 3C 6H 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru δ 4.668 (m, 4H, [CH 3C 6 [H] 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru)、 δ 4.330 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 3CH=C [H]-C [H] =CHCH 3)Ru)、 δ 2.338 (m, 1H, [CH 3C 6H 4C [H] (CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru)、 δ 2.013 (s, 3H, [C [H] 3C 6H 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru)、 δ 1.371 (d, 6H, [CH 3C 6H 4CH(CH 3) 2](C [H] 3CH=CH-CH=CHC [H] 3)Ru)、 δ 1.147 (d, 6H, [CH 3C 6H 4CH(C [H] 3) 2](CH 3CH=CH-CH=CHCH 3)Ru)、 δ 0.739 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 3C [H] =CH-CH=C [H]CH 3)Ru)、 2-dimensional: (1.3-dimensional) Ru、 [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH=CHCH 2CH 3)Ru δ 4.983 (m, 1H, [CH 3C 6 [H] 4CH(CH 3) 2](CH 2=CHCH=CHCH 2CH 3)Ru、 δ 4,835 (m, 2H, [CH3C6 [H]4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 4.727 (m, 1H, [CH3C6 [H]4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 4.603 (m, 1H, [CH3C6H4CH(CH3)2](CH2=C [H] CH=CHCH 2CH 3)Ru、 δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHC [H] =CHCH 2CH 3)Ru、 δ 2,302 (m, 1H, [CH3C6H4C [H](CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 1,969 (s, 3H, [[C [H]3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 1.758 (d, 1H, [CH3C6H4CH(CH3)2](C [H] 2=CHCH=CHCH 2CH 3)Ru、 δ 1,703 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC [H]2CH3)Ru、 δ 1,401 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC [H]2CH3)Ru、 δ 1,120 (t, 3H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2C [H] 3)Ru、 δ 1,098 (m, 6H, [CH3C6H4CH(C). [H] 3) 2](CH 2=CHCH=CHCH 2CH 3)Ru、 δ 0.726 (m, 1H, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH=C [H] CH 2CH 3)Ru、 δ 0.194 (d, 1H, [CH 3C 6H 4CH(CH 3) 2](C [H] 2=CHCH=CHCH 2CH 3)Ru 3-inch square footage: (1.5-square inch) Ruぁ [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH 2-CH 2CH=CH 2)Ru δ 4.505 (m, 4H, [CH 3C 6 [H] 4CH(CH 3) 2](CH 2=CHCH 2-CH 2CH=CH 2)Ru、 δ 3.425 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 2=C [H] CH 2-CH 2C [H] =CH 2)Ru、 δ 2.235 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHC [H] 2-CH 2CH=CH 2)Ru、 δ 2.227 (d, 2H, [CH 3C 6H 4CH(CH 3) 2](C [H] 2=CHCH 2-CH 2CH=CH 2)Ru、 δ 2.133 (m, 1H, [CH 3C 6H 4C [H] (CH 3) 2](CH 2=CHCH 2-CH 2CH=CH 2)Ru、 δ 1.924 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH 2-C [H] 2CH=CH 2)Ru、 δ 1.844 (s, 3H, [C [H] 3C 6H 4CH(CH 3) 2](CH 2=CHCH 2-CH 2CH=CH 2)Ru, δ 1.512 (d, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH 2-CH 2CH=C [H] 2)Ru、 δ 1.118 (d, 6H, [CH 3C 6H 4CH(C [H] 3) 2](CH 2=CHCH 2-CH 2CH=CH 2)Ru [example] [2] [to] [4]

[0132] The ruthenium precursor compositions having the compositions shown in Table 1 below were each prepared in the same manner as in Example 1, except that the temperature and number of vacuum distillations were changed. [example] [5]

[0133] A suspension was prepared by mixing 30 g (0.048 mol) of [RuCl2(p-isopropyltoluene)]2 and 14.2 g (0.192 mol) of Li2CO3 with 400 ml of 2-propanol in a flame-dried 1,000-ml Schlenk flask.

[0134] 23.7 g (0.288 mol) of 1,5-hexadiene was slowly added to the suspension, and the mixture was refluxed for 24 hours (first reflux reaction), followed by cooling to room temperature. 20.4 g (0.192 mol) of Na₂CO₃ was added to the product, and the reaction solution was further refluxed for 48 hours (second reflux reaction) to complete the reaction.

[0135] After the reaction was complete, the solvent and volatile byproducts were removed under reduced pressure, and the product was then extracted with 500 ml of n-hexane. The n-hexane extract was filtered through a diatomaceous earth mat and glass glue, and the resulting filtrate was subjected to solvent removal and vacuum distillation to obtain the ruthenium precursor composition, which comprises the orange liquid mixture (p-isopropyltoluene) (2,4-hexadiene)Ru represented by Formula 1 and the orange liquid mixture (p-isopropyltoluene) (1,3-hexadiene)Ru represented by Formula 2. 1H-NMR (400 MHz, C 6D 6, 25℃): Compound represented by Formula 1: (p-isopropyltoluene)(2,4-hexadiene)Ru, [CH 3C 6H 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru δ 4.668 (m, 4H, [CH 3C 6 [H] 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru), δ 4.330 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 3CH=C [H]-C [H] =CHCH 3)Ru), δ 2.338 (m, 1H, [CH 3C 6H 4C [H] (CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru), δ 2.013 (s, 3H, [C [H] 3C 6H 4CH(CH 3) 2](CH 3CH=CH-CH=CHCH 3)Ru), δ 1.371 (d, 6H, [CH 3C 6H 4CH(CH 3) 2](C [H] 3CH=CH-CH=CHC [H] 3)Ru), δ 1.147 (d, 6H, [CH 3C 6H 4CH(C [H] 3) 2](CH 3CH=CH-CH=CHCH 3)Ru), δ 0.739 (m, 2H, [CH 3C 6H 4CH(CH 3) 2](CH 3C [H] =CH-CH=C [H]CH 3)Ru), Compound represented by Formula 2: (p-isopropyltoluene)(1,3-hexadiene)Ru, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH=CHCH 2CH 3)Ru δ 4,983 (m, 1H, [CH3C6 [H]4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 4,835 (m, 2H, [CH3C6 [H]4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 4.727 (m, 1H, [CH3C6 [H]4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 4.603 (m, 1H, [CH3C6H4CH(CH3)2](CH2=C [H] CH=CHCH 2CH 3)Ru、 δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHC [H] =CHCH 2CH 3)Ru、 δ 2,302 (m, 1H, [CH3C6H4C [H](CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 1,969 (s, 3H, [[C [H]3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru. δ 1.758 (d, 1H, [CH3C6H4CH(CH3)2](C [H] 2=CHCH=CHCH 2CH 3)Ru、 δ 1,703 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC [H]2CH3)Ru、 δ 1,401 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHC [H]2CH3)Ru、 δ 1,120 (t, 3H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2C [H] 3)Ru、 δ 1.098 (m, 6H, [CH 3C 6H 4CH(C [H] 3) 2](CH 2=CHCH=CHCH 2CH 3)Ru, δ 0.726 (m, 1H, [CH 3C 6H 4CH(CH 3) 2](CH 2=CHCH=C [H] CH 2CH 3)Ru、 δ 0.194 (d, 1H, [CH 3C 6H 4CH(CH 3) 2](C [H] 2=CHCH=CHCH 2CH 3)Ru

[0136] Compound represented by Formula 3: Not observed.

[0137] The contents of the compounds represented by Formula 1, Formula 2 and Formula 3 in each ruthenium precursor composition prepared in Examples 1 to 5 are summarized in Table 1 below. [Table 1] Compound represented by Formula 1 (weight%) Compound represented by Formula 2 (weight%) Compound represented by Formula 3 (weight%) Example 1 22.9 22.0 55.1 Example 2 36.0 34.1 29.9 Example 3 43.3 36.4 20.3 Example 4 50.8 39.3 9.9 Example 5 57.9 42.1 0 Unit: Integration ratio of NMR peaks (the sum of the integrated values ​​of NMR peaks is 100%) Here, since the compounds represented by Formulas 1 to 3 are three isomers with the same molecular weight, the integral ratio of the NMR peaks is expressed as weight % [Evaluation Example] [1] [Evaluation of Dynamic Thermal Stability]

[0138] The dynamic thermal stability of the ruthenium precursor composition prepared in Example 1 was evaluated under the conditions shown in Table 2 below. [Table 2] condition MFC value (sccm) 200 Source tank temperature (°C) 120 Cooling temperature of the recovery tank (°C) -76 (dry ice) Can connector circuit temperature (°C) 130 Vaporization time (hours) 0-168 hours (Week 1) 169-336 hours (Week 2) Instrument Name NMR (Varian MR-400)

[0139] Specifically, 50 g of the ruthenium precursor composition was placed in a stainless steel container and heated to 120 °C under vacuum. The composition was vaporized by passing an argon carrier gas at a flow rate of 200 sccm through the stainless steel container containing the ruthenium precursor composition. The vapor was collected in a stainless steel container cooled to -76 °C. The composition vaporized during the first 7 days (0–168 hours) was collected in a first container cooled to -76 °C, and the composition vaporized during days 8–14 (168–336 hours) was collected in a second container cooled to -76 °C. The 1H-NMR spectra (400 MHz, C 6D 6, 25 °C) of the unheated composition (week 0), the vapor collected in the first container (week 1), and the vapor collected in the second container (week 2) were measured. The peak areas were compared relative to 100%, which is the sum of the NMR peak areas at 2.01 ppm (Equation 1), 1.97 ppm (Equation 2), 1.95 ppm (byproduct A), 1.86 ppm (byproduct B), and 1.84 ppm (Equation 3).

[0140] The results are shown in Table 3. [Table 3] temperature (°C) Time (week) Compound represented by Formula 1 Compound represented by Formula 2 Compound represented by Formula 3 Byproduct A Byproduct B Example 1 room temperature (weight%) 0 22.9 twenty two 55.1 ND ND 120 1 30.5 26.5 28.7 9.9 4.4 2 29 25.7 20.6 16.7 8 ND: Not detected Unit: Integration ratio of NMR peaks (the sum of the integrated values ​​of NMR peaks is 100%) Here, since the compounds represented by Formulas 1 to 3 are three isomers with the same molecular weight in the composition at room temperature and do not contain byproducts, the integral ratio of the NMR peaks represents weight. [Evaluation Example] [2] [Evaluation of Static Thermal Stability]

[0141] The static thermal stability of the ruthenium precursor compositions prepared in Examples 1 to 5 was evaluated under the conditions shown in Table 4 below. [Table 4] condition Raw material weight (g) 1 Oven temperature (°C) 110 120 Heating time (hours) 0-168 hours (Week 1) 0-336 hours (Week 2) Instrument type NMR (Varian MR-400)

[0142] Specifically, 1 g of each ruthenium precursor composition from Examples 1 to 5 was placed in a sealed stainless steel container and heated in ovens at 110°C and 120°C for 7 days and 14 days, respectively. The heated ruthenium precursor compositions from Examples 1 to 5 were then cooled to room temperature and measured by 1H-NMR (400 MHz, C 6D 6, 25°C). The peak areas relative to 100% were compared; 100% is the sum of the NMR peak areas at 2.01 ppm (Equation 1), 1.97 ppm (Equation 2), 1.95 ppm (byproduct A), 1.86 ppm (byproduct B), and 1.84 ppm (Equation 3).

[0143] The results are shown in Table 5. [Table 5] temperature (°C) time (week) Compound represented by Formula 1 Compound represented by Formula 2 Compound represented by Formula 3 Byproduct A Byproduct B Example 1 Room temperature (wt%) 0 22.9 22.0 55.1 ND ND 110 1 22.8 20.8 47.5 6.8 2.1 2 23.2 20.7 42.0 9.9 4.1 120 1 25.4 21.8 35.6 11.0 6.2 2 26.0 23.3 21.4 18.3 11.0 Example 2 Room temperature (wt%) 0 36.0 34.1 29.9 ND ND 110 1 37.6 30.5 26.0 3.2 2.7 2 38.6 30.4 23.9 4.4 2.7 120 1 38.6 30.7 12.0 11.6 7.1 2 38.3 31.4 11.3 11.2 7.8 Example 3 Room temperature (wt%) 0 43.3 36.4 20.3 ND ND 110 1 43.6 34.7 17.3 3.6 0.8 2 45.0 33.6 15.9 3.8 1.7 120 1 45.4 33.1 7.5 8.4 5.6 2 45.8 33.0 6.9 8.0 6.3 Example 4 Room temperature (wt%) 0 50.8 39.3 9.9 ND ND 110 1 50.5 38.2 8.6 2.1 0.6 2 51.4 37.5 8.8 1.7 0.6 120 1 51.4 37.6 4.6 4.3 2.1 2 51.7 37.3 4.2 4.3 2.5 Example 5 Room temperature (wt%) 0 57.9 42.1 ND ND ND 110 1 58.1 41.9 ND ND ND 2 58.6 41.4 ND ND ND 120 1 58.3 41.7 ND ND ND 2 58.8 41.2 ND ND ND ND: Not detected Unit: Integration ratio of NMR peaks (the sum of the integrated values ​​of NMR peaks is 100%) Here, since the compounds represented by Formulas 1 to 3 are three isomers with the same molecular weight in the composition at room temperature and do not contain byproducts, the integral ratio of the NMR peaks represents weight.

[0144] As can be seen from Table 5, in this invention, it is possible to control the ruthenium precursor composition of Examples 1 to 5 according to the purpose, so that the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 each have a specific content.

[0145] Furthermore, it has been confirmed that the thermal stability of ruthenium precursor components varies significantly depending on their composition.

[0146] Specifically, in the ruthenium precursor compositions of Examples 1 to 5, the lower the content of the compound represented by Formula 3, the better the thermal stability of the ruthenium precursor composition. Therefore, even at temperatures of 110°C and 120°C, the composition of the compounds represented by Formulas 1 to 3 does not change significantly, and the generation rates of byproducts A and B are low.

[0147] In particular, when compound 3 is absent (0% by weight), it remains very thermally stable even after two weeks at room temperature and at 110°C and 120°C, respectively. Therefore, the composition of compounds 1 and 2 is not significantly altered, and no byproducts are formed.

[0148] Meanwhile, the NMR spectra of the static thermal stability test results of the ruthenium precursor compositions of Examples 1 and 5 are shown in Figures 1 and 2, respectively.

[0149] As can be seen from Figure 1, in the NMR analysis of the ruthenium precursor composition of Example 1, a peak representing the compound of Formula 1 was observed at approximately 2.01 ppm, a peak representing the compound of Formula 2 was observed at approximately 1.97 ppm, and a peak representing the compound of Formula 3 was observed at approximately 1.84 ppm. Furthermore, the peaks corresponding to byproducts A and B in Table 5 appeared at 1.95 ppm and 1.86 ppm, respectively.

[0150] On the other hand, as can be seen from Figure 2, in the NMR analysis of the ruthenium precursor composition of Example 5, a peak representing the compound of Formula 1 was observed at approximately 2.01 ppm, and a peak representing the compound of Formula 2 was observed at approximately 1.97 ppm, while no peak representing the compound of Formula 3 was observed at approximately 1.84 ppm. Furthermore, the peaks corresponding to byproducts A and B in Table 5 did not appear at 1.95 ppm and 1.86 ppm, respectively. Therefore, it is confirmed that the ruthenium precursor composition of Example 5 does not contain the compound represented by Formula 3, nor does it contain the components corresponding to byproducts A and B in Table 5.

[0151] (none)

Claims

1. A ruthenium precursor composition comprising 20% ​​to 60% by weight of a compound represented by Formula 1, 20% to 50% by weight of a compound represented by Formula 2, and 0% to 55% by weight of a compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [Formula 1] [Formula 2] [Formula 3].

2. The ruthenium precursor composition of claim 1, comprising 30% to 60% by weight of the following compounds represented by Formula 1, 30% to 50% by weight of the following compounds represented by Formula 2, and 0% to 25% by weight of the following compounds represented by Formula 3, based on the total weight of the ruthenium precursor composition.

3. The ruthenium precursor composition of claim 1, wherein the ratio (by weight) of the total content of the compound represented by formula 1 and the compound represented by formula 2 to the content of the compound represented by formula 3 is 100:0 to 80:

20.

4. The ruthenium precursor composition of claim 1, comprising 10% by weight or less of the compound represented by formula 3, based on the total weight of the ruthenium precursor composition.

5. The ruthenium precursor composition of claim 1, comprising 5% by weight or less of the compound represented by formula 3, based on the total weight of the ruthenium precursor composition.

6. The ruthenium precursor composition of claim 1 does not contain the compound represented by formula 3.

7. The ruthenium precursor composition of claim 1, wherein the weight ratio of the compound represented by formula 1 to the compound represented by formula 2 is 7:3 to 5:

5.

8. The ruthenium precursor composition of claim 6, wherein the weight ratio of the compound represented by formula 1 to the compound represented by formula 2 is 6:4 to 5:

5.

9. The ruthenium precursor composition of claim 1, wherein when the ruthenium precursor composition is measured by 1H-NMR (400 MHz, C6D6, 25°C) at room temperature, no NMR spikes are observed at 1.95 ppm, 1.86 ppm, or both.

10. A method for preparing a ruthenium precursor composition comprising reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, wherein the ruthenium precursor composition comprises 20% to 60% by weight of the compound represented by Formula 1, 20% to 50% by weight of the compound represented by Formula 2, and 0% to 55% by weight of the compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 5] M2CO3 In the above formula, M is selected from the group consisting of Li, Na and K, and X is selected from the group consisting of Cl, Br and I.

11. The method for preparing a ruthenium precursor composition as claimed in claim 10, wherein the reaction comprises a reflux reaction.

12. The method for preparing a ruthenium precursor composition as claimed in claim 11, wherein the reflux reaction is carried out at 60 to 160°C for 10 to 100 hours.

13. The method for preparing a ruthenium precursor composition as claimed in claim 10 further includes distillation under reduced pressure of 0.1 Torr to 1 Torr and at 50°C to 200°C after the reaction.

14. The method for preparing a ruthenium precursor composition as claimed in claim 10, wherein the reaction comprises a first reflux reaction of the compound represented by formula 4 with a first alkali metal carbonate and 1,5-hexadiene in an organic solvent; and a second reflux reaction of the product with a second alkali metal carbonate.

15. The method for preparing a ruthenium precursor composition as claimed in claim 14, wherein the first reflux reaction is carried out at 60 to 160°C for 10 to 40 hours, and the second reflux reaction is carried out at 60 to 160°C for 10 to 60 hours.

16. The method for preparing a ruthenium precursor composition as claimed in claim 14, wherein the first alkali metal carbonate comprises Li2CO3 and the second alkali metal carbonate comprises Na2CO3.

17. The method for preparing a ruthenium precursor composition as claimed in claim 14, wherein the molar ratio of the first alkali metal carbonate to the second alkali metal carbonate is from 1:0.2 to 3.

0.

18. The method for preparing a ruthenium precursor composition as claimed in claim 14 further includes cooling the product to room temperature prior to the second reflux reaction.

19. The method for preparing a ruthenium precursor composition as claimed in claim 10, wherein the molar ratio of the compound represented by Formula 4, the alkali metal carbonate, and 1,5-hexadiene is from 1:2 to 10:1 to 8.

20. The method for preparing a ruthenium precursor composition as claimed in claim 10, wherein the organic solvent comprises a primary or secondary alcohol having five or fewer carbon atoms.

21. A method for forming a ruthenium-containing thin film, comprising preparing a ruthenium precursor composition; and forming a ruthenium-containing thin film using the ruthenium precursor composition, wherein the ruthenium precursor composition is prepared by reacting a compound represented by Formula 4 with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent, and comprises 20% to 60% by weight of the compound represented by Formula 1, 20% to 50% by weight of the compound represented by Formula 2, and 0% to 55% by weight of the compound represented by Formula 3, based on the total weight of the ruthenium precursor composition: [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 5] M2CO3 In the above formula, M is selected from the group consisting of Li, Na and K, and X is selected from the group consisting of Cl, Br and I.

22. The method for forming a ruthenium-containing thin film as claimed in claim 21, wherein the ruthenium-containing thin film is deposited by chemical vapor deposition or atomic layer deposition (ALD), and the deposition is carried out in a temperature range from room temperature to 550°C.

23. A ruthenium-containing thin film formed using a ruthenium precursor composition as claimed in claim 1.

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