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

Abstract

The present invention relates to a ruthenium precursor composition, a method for preparing the same, and a method for forming a ruthenium-containing film using the same. According to an embodiment of the present invention, the method comprises a step of reacting a compound represented by chemical formula 4 with an alkali metal carbonate represented by chemical formula 5 and 1, 5-hexadiene in an organic solvent, and by controlling the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 2, and the compound represented by Chemical Formula 3 within specific content ranges, a highly thermally stable ruthenium precursor composition can be provided in an economical and efficient manner. Furthermore, in the case of forming a ruthenium-containing film using the ruthenium precursor composition, a change in the composition of the ruthenium precursor composition can be prevented during or even after the vaporization of the ruthenium precursor composition, the generation of by-products such as pyrolysis substances can be minimized, and the yield of the ruthenium-containing film can be improved. Therefore, deposition results with stable and constant properties can be obtained in a semiconductor process. In this regard, it is possible to provide a ruthenium-containing film with guaranteed reproducibility and reliability.

Description

Technical Field

[0001] The present invention relates to a ruthenium precursor composition, a preparation method thereof and a method for forming a ruthenium-containing film using the same. Background Art

[0002] Since metal ruthenium (Ru) has a low resistivity (ρ 体 =7.6μΩ·cm) and large work function (Φ 体 =4.71eV), so it can be used as a gate electrode of a transistor; or as a capacitor electrode material for a dynamic random access memory (DRAM) or a ferroelectric random access memory (FeRAM). In particular, since metal ruthenium (Ru) has good conductivity like copper (Cu), tungsten (W) and cobalt (Co), it can be used as a wiring material for semiconductor devices.

[0003] Generally, as the integration of semiconductor devices increases, the width of metal wiring becomes narrower, and the resistance of metal wiring may increase. However, if metal ruthenium is used for wiring of semiconductor devices with extremely narrow metal wiring width (wiring width of about 40nm or less), metal ruthenium (Ru) increases resistance less than copper or cobalt; therefore, it can be advantageously used as a next-generation wiring material.

[0004] Meanwhile, in order to fill the narrow grooves required for wiring of next-generation semiconductor devices with metallic ruthenium, it is advantageous to provide a gaseous ruthenium compound to the substrate surface to form a ruthenium-containing film by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0005] To this end, various ruthenium precursor compositions that can be used for CVD or ALD have recently been developed.

[0006] However, when such a ruthenium precursor composition is applied to a semiconductor device, the ruthenium precursor composition may change during vaporization or change over time, and may be thermally unstable, resulting in the formation of byproducts such as thermal decomposition products. Therefore, there is a serious problem that a stable and constant deposition result cannot be obtained in a semiconductor process, and reproducibility cannot be guaranteed.

[0007] Therefore, it is necessary to develop a thermally stable ruthenium precursor composition that is not prone to change its composition even at vaporization temperature and that can minimize the formation of by-products.

[0008] [Prior art literature]

[0009] [Non-patent literature]

[0010] (Non-patent document 1) LGWen 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] Technical issues

[0013] An object of the present invention is to provide a thermally stable ruthenium precursor composition which is not prone to change in composition even at vaporization temperature and which minimizes the formation of by-products such as thermal decomposition products.

[0014] Another object of the present invention is to provide a method for preparing a thermally stable ruthenium precursor composition which is not susceptible to changes in composition even at vaporization temperatures and which minimizes the formation of by-products such as thermal decomposition products in a cost-effective manner.

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

[0016] Still another object of the present invention is to provide a ruthenium-containing film having uniform thickness and excellent quality even on various substrates formed using the ruthenium precursor composition.

[0017] However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and those skilled in the art can clearly understand other unmentioned problems through the following description.

[0018] Solution to the problem

[0019] The present invention provides a ruthenium precursor composition, which comprises 20 wt % to 60 wt % of a compound represented by the following formula 1, 20 wt % to 50 wt % of a compound represented by the following formula 2, and 0 wt % to 55 wt % of a compound represented by the following formula 3, based on the total weight of the ruthenium precursor composition:

[0020] [Formula 1]

[0021]

[0022] [Formula 2]

[0023]

[0024] [Formula 3]

[0025]

[0026] The present invention provides a method for preparing a ruthenium precursor composition, the method comprising: reacting a compound represented by the following formula 4 with an alkali metal carbonate represented by the following formula 5 and 1,5-hexadiene in an organic solvent, wherein, based on the total weight of the ruthenium precursor composition, the ruthenium precursor composition comprises 20 wt % to 60 wt % of the compound represented by the following formula 1, 20 wt % to 50 wt % of the compound represented by the following formula 2, and 0 wt % to 55 wt % of the compound represented by the following formula 3.

[0027] [Formula 1]

[0028]

[0029] [Formula 2]

[0030]

[0031] [Formula 3]

[0032]

[0033] [Formula 4]

[0034]

[0035] [Formula 5]

[0036] M2CO3

[0037] In the above formula, M is selected from Li, Na and K, and X is selected from Cl, Br and I.

[0038] In addition, the present invention provides a method for forming a ruthenium-containing film, the method comprising: preparing a ruthenium precursor composition; and using the ruthenium precursor composition to form a ruthenium-containing film, wherein the ruthenium precursor composition is prepared by reacting a compound represented by the above formula 4 with an alkali metal carbonate represented by the above formula 5 and 1,5-hexadiene in an organic solvent, and based on the total weight of the ruthenium precursor composition, the ruthenium precursor composition contains 20 weight % to 60 weight % of the compound represented by the above formula 1, 20 weight % to 50 weight % of the compound represented by the above formula 2, and 0 weight % to 55 weight % of the compound represented by the above formula 3.

[0039] In addition, the present invention also provides a ruthenium-containing film formed using the ruthenium precursor composition.

[0040] Advantageous Effects of the Invention

[0041] According to an embodiment of the present invention, a very thermally stable ruthenium precursor composition can be provided in an economical and effective manner by controlling the content of the compound represented by Formula 1, the content of the compound represented by Formula 2, and the content of the compound represented by Formula 3 within specific ranges, respectively.

[0042] When a ruthenium precursor composition according to an embodiment of the present invention is used to form a ruthenium-containing film, the composition of the ruthenium precursor composition can be prevented from changing during or after its vaporization, and the formation of byproducts such as thermal decomposition products can be minimized. Therefore, a deposition result with stable and consistent physical properties can be obtained in a semiconductor process, thereby providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0043] In addition, according to another embodiment of the present invention, even on a substrate having a pattern (groove) on the surface, a porous substrate or a plastic substrate, a ruthenium-containing film with a thickness of several nanometers to several microns can be uniformly formed within various temperature ranges, thereby obtaining a high-quality ruthenium-containing film. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 4 is a graph showing the static thermal stability test results of the ruthenium precursor composition of Example 1 of the present invention measured at 120° C. using NMR.

[0045] Figure 2 4 is a graph showing the static thermal stability test results of the ruthenium precursor composition of Example 5 of the present invention measured at 120° C. using NMR. DETAILED DESCRIPTION

[0046] Best Mode for Carrying Out the Invention

[0047] The present invention will be described in detail below.

[0048] The advantages and features of the present invention and methods for achieving these advantages and features will become apparent in the embodiments described below. However, the present invention is not limited to the embodiments described below, but can be embodied in various different forms. These embodiments are provided to make the disclosure of the present invention comprehensive and complete and to fully convey the scope of the present invention to those skilled in the art. The present invention is limited only by the scope of the claims.

[0049] Furthermore, in the present specification, when it is mentioned that one element is formed “on” another element, it not only means that the one element is formed directly “on” the other element but also means that other elements are interposed therebetween.

[0050] In this specification, when a component is referred to as “comprising” an element, unless otherwise specified, it should be understood that the component may also include other elements, rather than excluding other elements.

[0051] Unless otherwise indicated, all numbers and expressions relating to amounts of components, reaction conditions, and so forth used herein are to be understood as modified by the term "about."

[0052] [Ruthenium precursor composition]

[0053] The ruthenium precursor composition according to an embodiment of the present invention includes 20 wt % to 60 wt % of a compound represented by the following formula 1, 20 wt % to 50 wt % of a compound represented by the following formula 2, and 0 wt % to 55 wt % of a compound represented by the following formula 3, based on the total weight of the ruthenium precursor composition:

[0054] [Formula 1]

[0055]

[0056] [Formula 2]

[0057]

[0058] [Formula 3]

[0059]

[0060] Since the content of the compound represented by Formula 1, the content of the compound represented by Formula 2, and the content of the compound represented by Formula 3 are all controlled within specific ranges, the thermal stability of the ruthenium precursor composition can be greatly improved.

[0061] When a ruthenium-containing film is formed using the ruthenium precursor composition of the present invention having excellent thermal stability, composition changes over time during and after the ruthenium precursor composition's vaporization at high temperatures of 100°C or higher and the formation of by-products such as thermal decomposition products can be minimized.

[0062] Therefore, the present invention has important technical significance because the present invention provides a ruthenium precursor composition with the above-mentioned characteristics, which can obtain deposition results with more stable and consistent physical properties in semiconductor processes, thereby providing ruthenium-containing films with guaranteed reproducibility and reliability.

[0063] According to an embodiment of the present invention, controlling the content range and content ratio of each compound is very important to achieve the above characteristics.

[0064] The ruthenium precursor composition may include, for example, 22 to 60 wt %, for example, 25 to 60 wt %, for example, 28 to 60 wt %, for example, 30 to 60 wt %, for example, 35 to 60 wt %, for example, 40 to 60 wt %, for example, 45 to 60 wt %, for example, 50 to 60 wt %, or for example, 55 to 60 wt % of the compound represented by Formula 1, based on the total weight of the ruthenium precursor composition. If the compound represented by Formula 1 satisfies the above content range, thermal stability can be further improved, and the formation of byproducts such as thermal decomposition products can be minimized.

[0065] In addition, the ruthenium precursor composition may include, 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 % of the compound represented by Formula 2, based on the total weight of the ruthenium precursor composition. If the compound represented by Formula 2 satisfies the above content range, thermal stability can be further improved, and the formation of byproducts such as thermal decomposition products can be minimized.

[0066] In addition, the ruthenium precursor composition may contain the compound represented by Formula 3 in an amount of, 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.

[0067] The ruthenium precursor composition may contain the compound represented by Formula 3 in an amount of 10 wt % or less, 9 wt % or less, 8 wt % or less, 5 wt % or less, 3 wt % or less, 2 wt % or less, or 1 wt % or less, based on the total weight of the ruthenium precursor composition.

[0068] If the compound represented by Formula 3 satisfies the above content range, the ruthenium precursor composition is very thermally stable, and the formation of by-products such as thermal decomposition products can be minimized at 100° C. or higher.

[0069] The compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 may be isomers having the same molecular weight.

[0070] For example, the respective contents of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 are in the range of1 When H-NMR (400MHz, C6D6, 25°C) is measured, the value calculated by the integral ratio of the obtained NMR peak relative to the sum of the NMR peak integral values ​​(100%). Since the ruthenium precursor composition contains a mixture of a compound represented by Formula 1, a compound represented by Formula 2, and a compound represented by Formula 3 in the form of a mixture of three isomers having the same molecular weight, their respective contents can be expressed as weight %.

[0071] Particularly, according to an embodiment of the present invention, controlling the content of the compound represented by Formula 3 is very important.

[0072] That is, when the compound represented by Formula 3 satisfies a specific content range or less, the thermal stability is excellent, so that the composition changes less during the vaporization process, the thermal decomposition is minimal, and the formation of by-products is prevented. However, if the compound represented by Formula 3 does not meet the specific content range and is used excessively, the composition is prone to change during the vaporization process, so that at a certain temperature or higher, the composition is prone to change over time, the formation of by-products increases, and it is difficult to obtain a deposition result with stable and consistent characteristics, resulting in difficulty in achieving reproducibility and reliability.

[0073] In addition, the ruthenium precursor composition may not include the compound represented by Formula 3.

[0074] In this case, since the ruthenium precursor composition is very thermally stable, it can be more advantageous to achieve the goal.

[0075] 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, for example, 100:0 to 85:15, for example, 100:0 to 90:10, for example, 100:0 to 95:5, or for example, 100:0 to 97:3.

[0076] 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 satisfies the above range, the ruthenium precursor composition is very thermally stable and thus can more advantageously achieve the goal.

[0077] In addition, 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, for example, 7:3 to 5.5:4.5, for example, 6.5:3.5 to 5.5:4.5, for example, 6:4 to 5:5, or for example, 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 satisfies the above range, the ruthenium precursor composition is very thermally stable, and thus it can be more conducive to achieving the goal.

[0078] According to another embodiment of the present invention, the ruthenium precursor composition may contain more of the compound represented by Formula 1 than the compound represented by Formula 2. In this case, it may be more advantageous to further improve thermal stability and minimize byproducts formed due to thermal decomposition.

[0079] 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 may 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 range, since the ruthenium precursor composition is very thermally stable, it can be more conducive to achieving the objectives of the present invention.

[0080] Meanwhile, the ruthenium precursor composition may contain by-products. The by-products may include unreacted materials formed in the process for preparing the ruthenium precursor composition, impurities formed by thermal decomposition, and the like.

[0081] The amount of by-products in the ruthenium precursor composition may be 30 wt % or less, 25 wt % or less, 20 wt % or less, 15 wt % or less, 10 wt % or less, 9 wt % or less, 8 wt % or less, 7 wt % or less, 6 wt % or less, 5 wt % or less, 4 wt % or less, 3 wt % or less, 2 wt % or less, 1 wt % or less, 0.5 wt % or less, 0.2 wt % or less, or 0 wt %, based on the total weight of the ruthenium precursor composition.

[0082] Specifically, the ruthenium precursor composition may include one or more byproducts. For example, the byproduct may include a first byproduct or a second byproduct having different components, or a combination thereof.

[0083] Furthermore, according to an embodiment of the present invention, by-products may not be included.

[0084] Specifically, the ruthenium precursor composition is placed in a sealed stainless steel tank, heated, cooled to room temperature, and 1H-NMR (400MHz, C6D6, 25°C) is measured, and the sum of the integral values ​​of the NMR peaks at about 2.01ppm (Formula 1), about 1.97ppm (Formula 2), about 1.95ppm (by-product A), about 1.86ppm (by-product B), and about 1.84ppm (Formula 3) is 100%, and the sum of the integral values ​​of the two integral peaks at 1.95ppm (by-product A) and 1.86ppm (by-product A) that do not appear in the NMR spectrum before heating is 30% or less, or NMR peaks do not appear at 1.95ppm, 1.86ppm or two positions. Preferably, NMR peaks are not detected at 1.95ppm, 1.86ppm or two positions, and more specifically, NMR peaks are not detected at 1.95ppm and 1.86ppm positions.

[0085] The substances having NMR peaks at 1.95 ppm and 1.86 ppm are impurities formed by thermal decomposition after long-term heating. Since the thermal stability of the ruthenium precursor composition according to the present invention is greatly improved, it is preferred that the above NMR peaks are not observed.

[0086] NMR spectroscopy is used to analyze thermal stability. For example, a ruthenium precursor composition vaporized by heating to about 120° C. under vacuum and flowing an argon carrier gas at a flow rate of about 200 sccm is recovered by cooling to about −76° C. 1 H-NMR (400 MHz, C6D6, 25°C) can measure the composition recovered by vaporization in the first 7 days (first week) and the composition recovered by vaporization from the 8th to 14th day (second week), respectively.

[0087] Therefore, since the ruthenium precursor composition according to the present invention can achieve stable and consistent deposition results in a semiconductor process, it can have advantages in terms of reliability and reproducibility.

[0088] [Method for preparing ruthenium precursor composition]

[0089] The method for preparing a ruthenium precursor composition according to an embodiment of the present invention includes: reacting a compound represented by the following formula 4 with an alkali metal carbonate represented by the following formula 5 and 1,5-hexadiene in an organic solvent, wherein the ruthenium precursor composition comprises 20 wt % to 60 wt % of the compound represented by the following formula 1, 20 wt % to 50 wt % of the compound represented by the following formula 2, and 0 wt % to 55 wt % of the compound represented by the following formula 3, based on the total weight of the ruthenium precursor composition:

[0090] [Formula 1]

[0091]

[0092] [Formula 2]

[0093]

[0094] [Formula 3]

[0095]

[0096] [Formula 4]

[0097]

[0098] [Formula 5]

[0099] M2CO3

[0100] In the above formula, M is selected from Li, Na and K, and X is selected from Cl, Br and I.

[0101] According to an embodiment of the present invention, since the method includes reacting the compound represented by the above formula 4 with the alkali metal carbonate represented by the above 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.

[0102] Specifically, as shown in the following reaction scheme 1, the method for preparing a ruthenium precursor composition according to an embodiment of the present invention may include reacting a compound represented by the above formula 4 with an alkali metal carbonate represented by the above formula 5 and 1,5-hexadiene in an organic solvent:

[0103] [Reaction Scheme 1]

[0104]

[0105] In Reaction Scheme 1, X is as defined above.

[0106] In the method for preparing a ruthenium precursor composition according to an embodiment of the present invention, the reaction may be a reflux reaction, but may not be limited thereto.

[0107] Specifically, the reaction may include a reflux reaction at, for example, 60 to 160°C, for example, 70 to 150°C, or for example, 80 to 140°C for about 10 to 100 hours, about 20 to 100 hours, or about 20 to 80 hours.

[0108] In an embodiment of the present invention, the organic solvent may include a primary alcohol or a secondary alcohol having 5 or less carbon atoms, but may not be limited thereto.

[0109] A primary alcohol or secondary alcohol having 5 or less carbon atoms can serve as both a solvent and a reducing agent. Therefore, the ruthenium compound according to the present invention can be produced by an economical and simple process because a separate reducing agent is not required.

[0110] The primary or secondary alcohol may be selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, and combinations thereof, but may not be limited thereto.

[0111] The alkali metal carbonate may include at least one selected from the group consisting of Na2CO3, Li2CO3, and K2CO3.

[0112] Furthermore, in the method for preparing a ruthenium precursor composition, 1,5-hexadiene may be used as a substance to react with the compound represented by Formula 4 and the alkali metal carbonate represented by Formula 5. Since 1,5-hexadiene is cost-effective and can be purchased in large quantities compared to, for example, 2,4-hexadiene or 1,3-hexadiene, 1,5-hexadiene may be very advantageous for commercial applications.

[0113] Specifically, 2,4-hexadiene or 1,3-hexadiene is not easily available on the market, and their purchase amount is very limited (for example, limited to a few grams or tens of grams). Therefore, there may be limitations when using 2,4-hexadiene or 1,3-hexadiene to mass-produce the required ruthenium precursor composition. On the contrary, it is easy to buy 1,5-hexadiene in large quantities at a low price. In addition, when it is used to prepare a ruthenium precursor composition, especially when it is used to prepare a ruthenium precursor composition that does not include a compound represented by Formula 3, the desired effect can be easily and effectively produced. That is, in the preparation process of the ruthenium precursor composition and the semiconductor process, the use of 1,5-hexadiene can be very advantageous in terms of cost, productivity, efficiency and quality.

[0114] Meanwhile, in the method for preparing a ruthenium precursor composition according to an 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.

[0115] If the molar ratio of the compound represented by Formula 4, the alkali metal carbonate and 1,5-hexadiene satisfies the above range, the desired effects of the present invention may be more advantageously achieved.

[0116] Meanwhile, in an embodiment of the present invention, the compound of Formula 4 can be prepared according to the following reaction scheme 2.

[0117] [Reaction Scheme 2]

[0118]

[0119] In Reaction Scheme 2, X is as defined above, and n is 0 or an integer of 10 or less.

[0120] Specifically, the compound [RuX2(p-cymene)]2 represented by Formula 4 can be prepared by reacting α-terpinene represented by Formula 6 or γ-terpinene represented by Formula 7 with ruthenium trichloride hydrate (RuX3·nH2O) in an organic solvent such as alcohol.

[0121] In this case, β-terpinene, δ-terpinene, α-phellandrene, β-phellandrene or isomers thereof may be used instead of α-terpinene or γ-terpinene. In an embodiment of the present invention, the reaction for preparing the compound represented by Formula 4 may be a reflux reaction, but is not limited thereto.

[0122] In the method for preparing a ruthenium precursor composition according to an embodiment of the present invention, the reflux reaction may be performed once or at least twice.

[0123] Specifically, it may include subjecting the compound represented by Formula 4 to a first reflux reaction with an alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent.

[0124] In addition, after reacting the compound represented by Formula 4 with the alkali metal carbonate represented by Formula 5 and 1,5-hexadiene in an organic solvent (e.g., a first reflux reaction), the method for preparing a ruthenium precursor composition may further include distilling at a 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 50°C to 200°C, 70°C to 150°C, 70°C to 140°C, or 80°C to 120°C.

[0125] In addition, the composition of the ruthenium precursor composition can also be adjusted by changing the distillation conditions. Specifically, the content of the compound represented by Formula 3 can be adjusted to, for example, about 10 wt % or less by changing the distillation conditions to 100° C. to 120° C., 0.2 torr to 0.4 torr.

[0126] Meanwhile, in the method for preparing a ruthenium precursor composition according to another embodiment of the present invention, the reflux reaction may be performed at least twice, for example, twice.

[0127] Specifically, as shown in the following reaction scheme 3, the reaction may include: a first reflux reaction of a 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 a product obtained by the first reflux reaction with a second alkali metal carbonate.

[0128] [Reaction Scheme 3]

[0129]

[0130] In Reaction Scheme 3, X is as defined above.

[0131] In Reaction Scheme 3, the first reflux reaction can be carried out at 60°C to 160°C, for example, 70°C to 140°C, or for example, 90°C to 120°C for about 10 hours to 40 hours, about 15 hours to 35 hours, or about 20 hours to 25 hours.

[0132] In Reaction Scheme 3, the second reflux reaction can be carried out at 60°C to 160°C, for example, 70°C to 140°C, or for example, 90°C to 120°C, for about 10 hours to 60 hours, about 15 hours to 55 hours, or about 20 hours to 50 hours.

[0133] The first alkali carbonate may include Li2CO3. If Li2CO3 is used as the first alkali carbonate, it can be confirmed that when NMR analysis is performed during the first reflux reaction, the NMR peak corresponding to 1,5-hexadiene decreases and then disappears completely. In the known isomerization reaction, the hydrogen bonded to the double-bonded carbon coordinated with the Ru central metal is transferred to another carbon [YMWuu et al., Inorganic Chemistry 1988, 27 (17), 3039-3044, doi: 10.1021 / ic00290a028]. It is speculated that 1,5-hexadiene used as a raw material becomes 2,4-hexadiene and 1,3-hexadiene through this isomerization reaction. Therefore, it is more conducive to controlling the ruthenium precursor composition within the specific range required by the present invention.

[0134] In addition, the second alkali metal carbonate may include Na2CO3, K2CO3 or a combination thereof, preferably Na2CO3. If Na2CO3 is used as the second alkali metal carbonate, a higher yield can be obtained; therefore, it is more conducive to controlling the ruthenium precursor composition within the specific range required by the present invention.

[0135] For example, 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, for example, 1:0.5 to 2.5, for example, 1:0.5 to 2.0, or for example, 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 conducive to obtaining the ruthenium precursor composition required by the present invention.

[0136] Meanwhile, the method for preparing a ruthenium precursor composition according to an embodiment of the present invention may further include cooling the product to room temperature before performing the second reflux reaction.

[0137] Specifically, it may include subjecting the compound represented by Formula 4 to a first reflux reaction with a first alkali metal carbonate and 1,5-hexadiene in an organic solvent; cooling a product obtained by the first reflux reaction to room temperature; and subjecting the product to a second reflux reaction with a second alkali metal carbonate.

[0138] In addition, according to an embodiment of the present invention, the method for preparing a ruthenium precursor composition may further include performing distillation and / or filtration after the second reflux reaction.

[0139] Distillation and / or filtration are as described above.

[0140] According to an embodiment of the present invention, when using the method for preparing a ruthenium precursor composition, the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 can be adjusted to have a specific content range, respectively. In particular, the content of the compound represented by Formula 3 can be adjusted to 10 wt % or less.

[0141] In addition, according to an embodiment of the present invention, when the method for preparing a ruthenium precursor composition is used, it may be controlled so that the compound represented by Formula 3 is not included.

[0142] In this case, a very thermally stable ruthenium precursor composition can be provided. When a ruthenium-containing film is formed using the ruthenium precursor composition, the composition of the ruthenium precursor composition can be prevented from changing during or after its vaporization, and the formation of byproducts such as thermal decomposition products can be minimized. Therefore, a deposition result with stable and consistent physical properties can be obtained in a semiconductor process, thereby providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0143] [Method for forming a ruthenium-containing film]

[0144] According to an embodiment of the present invention, a ruthenium-containing film may be formed using the ruthenium precursor composition prepared by the above method.

[0145] Specifically, the method for forming a ruthenium-containing film includes: preparing a ruthenium precursor composition (first step); and using the ruthenium precursor composition to form a ruthenium-containing 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 the ruthenium precursor composition contains 20 weight % to 60 weight % of the compound represented by the following Formula 1, 20 weight % to 50 weight % of the compound represented by the following Formula 2, and 0 weight % to 55 weight % of the compound represented by the following Formula 3, based on the total weight of the ruthenium precursor composition.

[0146] In the method for forming a ruthenium-containing film, the step of preparing a ruthenium precursor composition (first step) is as described above.

[0147] The method for forming a ruthenium-containing film may include forming the ruthenium-containing film using a ruthenium precursor composition (second step).

[0148] Specifically, the second step is a step of depositing a ruthenium-containing film on a substrate using a ruthenium precursor composition. It may include providing a gaseous ruthenium precursor composition to form a ruthenium-containing film on a substrate.

[0149] In an embodiment of the present invention, the ruthenium-containing 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 may not be limited thereto. In addition, a substrate having holes or grooves may be used, and a porous substrate having a large surface area may be used, but may not be limited thereto. In addition, the ruthenium-containing film may be formed simultaneously or sequentially on all or part of a substrate (where two or more different types of substrates are in contact or interconnected with each other), but may not be limited thereto.

[0150] According to an embodiment of the present invention, in a method for depositing a ruthenium-containing film, a substrate is placed in a reaction chamber, and then a ruthenium precursor composition is transferred to the substrate using a carrier gas or a diluent gas to deposit the ruthenium-containing film.

[0151] Specifically, the deposit may be formed in the following temperature range: 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 15 ...5 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 may not be limited thereto. In an embodiment of the present invention, the ruthenium-containing film may be formed at a temperature ranging from about 200°C to about 500°C or from about 300°C to about 500°C.

[0152] In an embodiment of the present invention, the ruthenium-containing film may be deposited by chemical vapor deposition (CVD), specifically, metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but may not be limited thereto. In an embodiment of the present invention, chemical vapor deposition or atomic layer deposition of the ruthenium-containing film may be performed using deposition equipment, deposition conditions, and one or more additional reaction gases known in the art, but may not be limited thereto.

[0153] In an embodiment of the present invention, hydrogen (H2) gas, ammonia (NH3) gas, oxygen (O2) gas or ozone (O3) gas used in semiconductor processes can be used as reaction gases for ALD and CVD methods to form a ruthenium-containing film, but is not limited thereto.

[0154] For example, if hydrogen and / or ammonia are used to form a film in the ALD and CVD methods, a ruthenium-containing film containing less impurities can be formed. For example, if oxygen or ozone gas is used to form a film in the ALD and CVD methods, a ruthenium metal film or a ruthenium oxide film can be formed, but it may not be limited thereto.

[0155] In an embodiment of the present invention, a method for forming a ruthenium-containing film includes providing a gaseous ruthenium precursor composition on a substrate located in a deposition chamber to form the ruthenium-containing film on a surface of the substrate, but may not be limited thereto.

[0156] In an embodiment of the present invention, the thickness of the formed ruthenium-containing film may range from about 1 nm to about 500 nm, and may be applied in various ways according to the application purpose, but may not be limited thereto. For example, the thickness of the formed ruthenium-containing film may range from about 1 nm to about 500 nm, from about 1 nm to about 400 nm, from about 1 nm to about 300 nm, from about 1 nm to about 200 nm, from about 1 nm to about 100 nm, from about 1 nm to about 50 nm, from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 20 nm, from about 1 nm to about 10 nm, from about 10 nm to about 500 nm, from about 10 nm to about 400 nm, from about 10 nm to about 300 nm, from about 10 nm to about 200 nm. 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 50 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 400nm, about 30nm to about 300nm, about 30nm to about 200nm, about 30nm to about 100nm, about 30nm to about 50nm, about 30nm to about 40nm, about 40nm to about 500nm, about 40nm to about 400nm, about 40nm to about 300nm, about 40nm to about 200nm, about 40nm to about 100nm, about 40nm to about 50nm, about 50nm to about 500nm, about 50nm to about 400nm, about 50nm To about 300nm, about 50nm to about 200nm, about 50nm to about 100nm, about 100nm to about 500nm, about 100nm to about 400nm, about 100nm to about 300nm, about 100nm to about 200nm, about 200nm to about 500nm, about 200nm to about 400nm, about 200nm to about 300nm, about 300nm to about 500nm, about 300nm to about 400nm, or about 400nm to about 500nm, but may not be limited thereto. In embodiments of the present invention, the thickness range of the ruthenium-containing film formed may be about 1nm to about 50nm.

[0157] In an embodiment of the present invention, a ruthenium-containing film may be formed on a substrate including an uneven structure (groove) having an aspect ratio of about 1 to about 100 and a width of about 10 nm to about 1 μm, but may not be limited thereto. The uneven structure (groove) may be in the form of a hole or a groove. For example, the aspect 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 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 The invention relates to an embodiment of the present invention in an embodiment of the present invention. The invention relates to an embodiment of the present invention in an embodiment of the present invention in an embodiment of the present invention. In addition, for example, the width may be about 10 nm to about 1 μm, about 10 nm to about 900 nm, about 10 nm to about 800 nm, about 10 nm to about 700 nm, about 10 nm to about 600 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 90 nm, about 10 nm to about 80 nm, about 10 nm to about 70 nm, about 10 nm to about 60 nm, about 10 nm to about 50 nm, about 10 nm to about 40 nm, about 10 nm to about 50 nm, about 10 nm to about 60 nm, about 10 nm to about 80 nm, about 10 nm to about 90 nm, about 10 nm to about 10 ... 10nm to about 30nm, about 10nm to about 20nm, about 20nm to about 1 μm, about 20nm to about 900nm, about 20nm to about 800nm, about 20nm to about 700nm, about 20nm to about 600nm, about 20nm to about 500nm, about 20nm to about 400nm, about 20nm to about 300nm, about 20nm to about 200nm, about 20nm to about 100nm, about 20nm to about 90nm, about 20nm to about 80nm, about 20nm to about 70nm, about 20nm to about 60nm, about 20nm to about 50nm,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 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 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 nm to about 800nm, about 40nm to about 700nm, about 40nm to about 600nm, about 40nm to about 500nm, about 40nm to about 400nm, about 40nm to about 300nm, about 40nm to about 200nm, about 40nm to about 100nm, about 40nm to about 90nm, about 40nm to about 80nm, about 40nm to about 70nm, about 40nm to about 60nm, about 40 to about 50nm, about 50nm to about 1 μm, about 50nm to about 900nm, about 50nm to about 800nm, about 50nm to about 700nm, about 50nm to about 600nm, about 50nm to about 500nm, about 50nm to about 400nm, about 50nm to about 300nm, about 50nm to about 200nm, about 50nm to about 100nm, about 50nm to about 90nm, about 50nm to about 80nm, about 50nm to about 70nm, about 50nm to about 60nm, about 100nm to about 1μm, about 100nm to about 900nm, about 100nm to about 800nm, about 100nm to about 700nm, about 100nm to about 600nm, about 100nm to about 500nm, about 100nm to about 400nm, about 100nm to about 300nm, about 100nm to about 200nm, about 200nm to about 1μm, about 200nm to about 900nm, about 200nm to about 800nm , about 200nm to about 700nm, about 200nm to about 600nm, about 200nm to about 500nm, about 200nm to about 400nm, about 200nm to about 300nm, about 300nm to about 1 μm, about 300nm to about 900nm, about 300nm to about 800nm, about 300nm to about 700nm, about 300nm to about 600nm, about 300nm to about 500nm, about 300nm to about 400nm, about 400nm to about 1 μm, about 400nm to about 900nm, about 400nm to about 800nm, about 400nm to about 700nm, about 400nm to about 600nm, about 400nm to about 500nm,About 500nm to about 1μm, about 500nm to about 900nm, about 500nm to about 800nm, about 500nm to about 700nm, about 500nm to about 600nm, about 600nm to about 1μm, about 600nm to about 900nm, about 600nm to about 800nm, about 600nm to about 700nm, about 700nm to about 1μm, about 700nm to about 900nm, about 700nm to about 800nm, about 800nm ​​to about 1μm, about 800nm ​​to about 900nm, or about 900nm to about 1μm, but may not be limited thereto.

[0158] In an embodiment of the present invention, the ruthenium precursor composition of the present invention contained in the ruthenium-containing film can be used as a precursor for atomic layer deposition or chemical vapor deposition to form a ruthenium-containing film by virtue of its low density and high thermal stability. In particular, even on a substrate with a pattern (groove) on the surface, a porous substrate or a plastic substrate, a ruthenium-containing film with a thickness of several micrometers to several nanometers can be uniformly formed in a temperature range of room temperature to 550°C.

[0159] In an embodiment of the present invention, in a method for forming a ruthenium-containing film, a substrate is preferably placed in a reaction chamber, a ruthenium precursor composition is transported to the substrate using a carrier gas or a dilution gas, and a ruthenium-containing metal film, oxide film or nitride film is deposited within a wide deposition temperature range from room temperature to about 550°C, but may not be limited thereto.

[0160] In an embodiment of the present invention, at least one mixed gas selected from argon (Ar), nitrogen (N2), helium (He) or hydrogen (H2) may be preferably used as a carrier gas or a dilution gas, but it may not be limited thereto.

[0161] In an embodiment of the present invention, various methods can be used as a method for delivering the ruthenium precursor composition to the substrate, such as a bubbling method, in which a carrier gas is used to force vaporization of the precursor; a liquid delivery system (LDS) method for supplying the ruthenium precursor composition in a liquid phase at room temperature so that it is vaporized by a vaporizer; and a vapor flow control (VFC) method of directly supplying the precursor using the vapor pressure of the precursor. If the vapor pressure is high, the VFC method can be used. If the vapor pressure is low, a bypass method can be used, in which the container is heated for evaporation.

[0162] A bubbling method may be used, in which the ruthenium precursor composition is loaded into a bubbling container or a VFC container and transported into the chamber by bubbling with a carrier gas at a temperature range of room temperature to about 100° C. and at about 0.1 torr to about 10 torr, or using a high vapor pressure. Specifically, an LDS method may be used, in which a ruthenium precursor composition in a liquid phase is provided at room temperature and vaporized by a vaporizer, but may not be limited thereto.

[0163] In an embodiment of the present invention, in order to vaporize the ruthenium precursor composition, the ruthenium precursor composition may be delivered using argon (Ar) or nitrogen (N2), thermal energy or plasma may be used, or a bias may be applied to the substrate.

[0164] In an embodiment of the present invention, the deposition temperature is from room temperature to about 550°C, or from about 200°C to about 500°C, so that the process temperature range is wider and is suitable for memory devices, logic devices and display devices; therefore, it can be applied to various fields.

[0165] In an embodiment of the present invention, when a ruthenium-containing film is deposited as a ruthenium-containing metal film or an oxide film, at least one selected from water vapor (H2O), oxygen (O2), oxygen plasma (O2 plasma), nitrogen oxides (NO, N2O), nitrogen oxide plasma (N2O plasma), nitride oxide (N2O2), hydrogen peroxide (H2O2), and ozone (O3) can be used as a reaction gas.

[0166] In an embodiment of the present invention, when a ruthenium-containing film is deposited as a ruthenium-containing nitride film, at least one selected from ammonia (NH3), ammonia plasma (NH3 plasma), hydrazine (N2H4) and nitrogen plasma (N2 plasma) can be used as a reaction gas.

[0167] When a ruthenium-containing film is formed using a ruthenium precursor composition according to an embodiment of the present invention, the composition of the ruthenium precursor composition can be prevented from changing during or after its vaporization, and the formation of byproducts such as thermal decomposition products can be minimized. Therefore, a deposition result with stable and consistent physical properties can be obtained in a semiconductor process, thereby effectively providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0168] [Ruthenium-containing film]

[0169] According to an embodiment of the present invention, there is provided a ruthenium-containing film formed using a ruthenium precursor composition.

[0170] The ruthenium-containing film may have a thickness of about 1 nanometer (nm) to several micrometers (μm), and may be used in various ways depending on the purpose of application.

[0171] For example, the thickness, aspect ratio, and width of the ruthenium-containing film are as described above and may be selected differently.

[0172] Since the content of the compound represented by Formula 1, the content of the compound represented by Formula 2, and the content of the compound represented by Formula 3 are respectively controlled to specific ranges in the ruthenium precursor composition according to an embodiment of the present invention, it has excellent thermal stability; therefore, a ruthenium-containing film can be effectively formed in a wide temperature range by CVD and ALD. In particular, in the temperature range of room temperature to 550°C, even on a substrate with fine patterns (grooves) on the surface, a porous substrate, or a plastic substrate with a thickness of several micrometers to tens of nanometers, a ruthenium-containing film can be uniformly formed.

[0173] The ruthenium-containing film may be at least one selected from a ruthenium-containing metal film, a ruthenium-containing oxide film, a ruthenium-containing carbide film, a ruthenium-containing sulfide film, and a ruthenium-containing nitride film.

[0174] Mode for the Invention

[0175] Hereinafter, the present invention will be described in detail with reference to Examples. The following Examples merely illustrate the present invention, and the scope of the present invention is not limited thereto.

[0176] Preparation Example 1: Preparation of [RuCl2(p-cymene)]2

[0177] 27 g (0.13 mol) of ruthenium trichloride hydrate (RuCl 3· nH2O) was dissolved in 200 ml of ethanol (C2H5OH) in a 500 ml flame-dried Schlenk flask. 35.4 g (0.26 mol, 2 equivalents) of α-terpinene were slowly added to the solution at room temperature, and then the mixture was refluxed for 15 hours to complete the reaction.

[0178] After the reaction was completed, the dark brown solid obtained by filtration was diluted with 50 ml of n-hexane (C6H 14 ) was washed three times and then dried under vacuum to obtain a reddish brown solid compound [RuCl2(p-cymene)]2.

[0179] Example 1: Preparation of ruthenium precursor composition

[0180]

[0181] 30 g (0.048 mole) of [RuCl2 (p-cymene)]2 obtained in Preparation Example 1 and 31.1 g (0.294 mole) of Na2CO3 were mixed with 400 ml of 2-propanol in a 1000 ml flame-dried Schlenk flask to prepare a suspension. 15.8 g (0.192 mole) of 1,5-hexadiene was slowly added to the suspension, and then the mixture was refluxed for 40 hours to complete the reaction. After the reaction was completed, the solvent and volatile by-products were removed under reduced pressure, and then the product was extracted with 500 ml of n-hexane. The n-hexane extract was filtered through a Celite pad and a glass filter, and the filtrate obtained was freed of the solvent under reduced pressure and distilled under reduced pressure to obtain a liquid mixture represented by Formula 1, Formula 2 and Formula 3, the composition of which is shown in Table 1 below. The ratio of the three isomers with the same molecular weight is based on 1 It is determined by the relative proportion of the NMR peak integral values ​​of the hydrogen of the methyl group (CH3) bound to the benzene ring of the ligand appearing at 2.01ppm (Formula 1), 1.97ppm (Formula 2) and 1.84ppm (Formula 3) in the H-NMR (400MHz, C6D6, 25℃) spectrum.

[0182] 1 H-NMR (400MHz, C6D6, 25℃):

[0183] The compound represented by Formula 1: (p-cymene)(2,4-hexadiene)Ru,

[0184] [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru

[0185] δ4.668(m,4H,[CH3C6 H 4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru),

[0186] δ4.330(m,2H,[CH3C6H4CH(CH3)2](CH3CH=C H -C H =CHCH3)Ru),

[0187] δ2.338(m,1H,[CH3C6H4C H (CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ2.013(s,3H,[C H 3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ1.371(d,6H,[CH3C6H4CH(CH3)2](C H 3CH=CH-CH=CHC H3)Ru), δ 1.147 (d, 6H, [CH3C6H4CH(C H 3)2](CH3CH=CH-CH=CHCH3)Ru), δ 0.739 (m, 2H, [CH3C6H4CH(CH3)2](CH3C H =CH-CH=C H CH3)Ru), the compound represented by Formula 2: (p-cymene)(1,3 - hexadiene)Ru,

[0188] [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)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=CHCH2CH3)Ru, δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHC H =CHCH2CH3)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=CHCH2CH3)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 H3)2](CH2=CHCH=CHCH2CH3)Ru, δ0.726(m,1H,[CH3C6H4CH(CH3)2](CH2=CHCH=C H CH2CH3)Ru, δ0.194(d,1H,[CH3C6H4CH(CH3)2](C H 2=CHCH=CHCH2CH3)Ru The compound represented by Formula 3: (p-cymene)(1,5-hexadiene)Ru,

[0189] [CH3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ruδ4.505(m,4H,[CH3C6 H 4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ3.425(m,2H,[CH3C6H4CH(CH3)2](CH2=C H CH2-CH2C H =CH2)Ru, δ2.235(m,2H,[CH3C6H4CH(CH3)2](CH2=CHC H 2-CH2CH=CH2)Ru,δ2.227(d,2H,[CH3C6H4CH(CH3)2](C H 2=CHCH2-CH2CH=CH2)Ru,δ2.133(m,1H,[CH3C6H4C H (CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ1.924(m,2H,[CH3C6H4CH(CH3)2](CH2=CHCH2-C H 2CH=CH2)Ru, δ1.844(s,3H,[C H 3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ1.512(d,2H,[CH3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=C H 2)Ru, δ1.118(d,6H,[CH3C6H4CH(C H 3) 2] (CH2 = CHCH2-CH2CH = CH2) Ru Example 2 to Example 4

[0190] Ruthenium precursor compositions having the compositions shown in Table 1 below were prepared in the same manner as in Example 1, except that the temperature and the number of distillations under reduced pressure were changed.

[0191] Example 5

[0192] 30 g (0.048 mol) of [RuCl2(p-cymene)]2 and 14.2 g (0.192 mol) of Li2CO3 were mixed with 400 ml of 2-propanol in a 1000 ml flame-dried Schlenk flask to prepare a suspension.

[0193] 23.7 g (0.288 mol) of 1,5-hexadiene was slowly added to the suspension, and the mixture was refluxed (first reflux reaction) for 24 hours and then cooled to room temperature. 20.4 g (0.192 mol) of Na2CO3 was added to the product, and the reaction solution was further refluxed (second reflux reaction) for 48 hours to complete the reaction.

[0194] After the reaction is completed, the solvent and volatile by-products are removed under reduced pressure, and then the product is extracted with 500 ml of n-hexane. The n-hexane extract is filtered through a Celite pad and a glass filter, and the filtrate obtained is desolventized and distilled under reduced pressure to obtain a ruthenium precursor composition, which contains an orange liquid mixture represented by Formula 1 (p-cymene) (2,4-hexadiene) Ru and an orange liquid mixture represented by Formula 2 (p-cymene) (1,3-hexadiene) Ru.

[0195] 1 H-NMR (400MHz, C6D6, 25℃):

[0196] The compound represented by Formula 1: (p-cymene)(2,4-hexadiene)Ru,

[0197] [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru

[0198] δ4.668(m,4H,[CH3C6 H 4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru),

[0199] δ4.330(m,2H,[CH3C6H4CH(CH3)2](CH3CH=C H -C H =CHCH3)Ru),

[0200] δ2.338(m,1H,[CH3C6H4C H (CH3)2](CH3CH=CH-CH=CHCH3)Ru),

[0201] δ2.013(s,3H,[C H 3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru),

[0202] δ1.371(d,6H,[CH3C6H4CH(CH3)2](C H 3CH=CH-CH=CHC H 3) Ru),

[0203] δ1.147(d,6H,[CH3C6H4CH(C H 3)2](CH3CH=CH-CH=CHCH3)Ru), δ0.739(m,2H,[CH3C6H4CH(CH3)2](CH3C H =CH-CH=C H CH3)Ru),

[0204] The compound represented by Formula 2: (p-cymene)(1,3-hexadiene)Ru,

[0205] [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru

[0206] δ4.983(m,1H,[CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru,

[0207] δ4.835(m,2H,[CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru,

[0208] δ4.727(m,1H,[CH3C6 H 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru,

[0209] δ4.603(m,1H,[CH3C6H4CH(CH3)2](CH2=C H CH=CHCH2CH3)Ru,

[0210] δ4.418(m,1H,[CH3C6H4CH(CH3)2](CH2=CHC H =CHCH2CH3)Ru,

[0211] δ2.302(m,1H,[CH3C6H4C H (CH3)2](CH2=CHCH=CHCH2CH3)Ru,

[0212] δ1.969(s,3H,[[C H 3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru,

[0213] δ1.758(d,1H,[CH3C6H4CH(CH3)2](C H 2=CHCH=CHCH2CH3)Ru,

[0214] δ1.703(m,1H,[CH3C6H4CH(CH3)2](CH2=CHCH=CHC H 2CH3)Ru,

[0215] δ1.401(m,1H,[CH3C6H4CH(CH3)2](CH2=CHCH=CHC H 2CH3)Ru,

[0216] δ1.120(t,3H,[CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2C H 3) For example,

[0217] δ1.098(m,6H,[CH3C6H4CH(C H 3)2](CH2=CHCH=CHCH2CH3)Ru,

[0218] δ0.726(m,1H,[CH3C6H4CH(CH3)2](CH2=CHCH=C H CH2CH3)Ru, δ0.194(d,1H,[CH3C6H4CH(CH3)2](C H 2=CHCH=CHCH2CH3)Ru

[0219] Compound represented by Formula 3: Not observed.

[0220] The content of the compound represented by Formula 1, the content of the compound represented by Formula 2, and the content of the compound represented by Formula 3 contained in each of the ruthenium precursor compositions prepared in Examples 1 to 5 are summarized in Table 1 below.

[0221] [Table 1]

[0222]

[0223] Evaluation Example 1: Evaluation of dynamic thermal stability

[0224] Under the conditions shown in Table 2 below, the dynamic thermal stability of the ruthenium precursor composition prepared in Example 1 was evaluated.

[0225] [Table 2]

[0226]

[0227]

[0228] Specifically, 50 g of the ruthenium precursor composition was placed in a stainless steel tank and heated to 120° C. under vacuum. The stainless steel tank containing the ruthenium precursor composition was vaporized by flowing an argon carrier gas at a flow rate of 200 sccm. The vapor was collected in a stainless steel tank cooled to -76° C. The composition vaporized in the first 7 days (0-168 hours) was collected in a first tank cooled to -76° C., and the composition vaporized in the 8th to 14th days (168-336 hours) was collected in a second tank cooled to -76° C. The unheated composition (week 0), the vapor collected in the first tank (week 1), and the vapor collected in the second tank (week 2) were respectively subjected to the following steps: 1 H-NMR (400 MHz, C6D6, 25°C) spectrum measurement. The peak areas were compared with the sum of 100% of the NMR peak areas at 2.01 ppm (Formula 1), 1.97 ppm (Formula 2), 1.95 ppm (byproduct A), 1.86 ppm (byproduct B) and 1.84 ppm (Formula 3).

[0229] The results are shown in Table 3.

[0230] [Table 3]

[0231]

[0232] Evaluation Example 2: Evaluation of static thermal stability

[0233] Under the conditions shown in Table 4 below, the static thermal stability of the ruthenium precursor compositions prepared in Examples 1 to 5 was evaluated.

[0234] [Table 4]

[0235]

[0236] Specifically, 1 g of the ruthenium precursor compositions of Examples 1 to 5 were placed in sealed stainless steel cans and heated in ovens heated to 110° C. and 120° C. for 7 days and 14 days, respectively. The heated ruthenium precursor compositions of Examples 1 to 5 were cooled to room temperature and heated to 100° C. and 100° C. respectively. 1 H-NMR (400 MHz, C6D6, 25° C.) was used for the measurement. The peak areas were compared with the sum of the NMR peaks at 2.01 ppm (Formula 1), 1.97 ppm (Formula 2), 1.95 ppm (byproduct A), 1.86 ppm (byproduct B), and 1.84 ppm (Formula 3) as 100%.

[0237] The results are shown in Table 5.

[0238] [Table 5]

[0239]

[0240]

[0241] As can be seen from Table 5, in the present invention, the ruthenium precursor compositions of Examples 1 to 5 can be controlled 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.

[0242] Furthermore, it was demonstrated that the thermal stability of the ruthenium precursor composition varies significantly depending on its composition.

[0243] Specifically, in the ruthenium precursor compositions of Examples 1 to 5, the lower the content of the compound represented by Formula 3, the higher 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 much, and the yields of by-products A and B are low.

[0244] In particular, when the compound of Formula 3 is absent (0 wt%), it is very thermally stable even after 2 weeks at room temperature and 110° C. and 120° C., respectively. Therefore, the compositions of the compounds of Formula 1 and Formula 2 do not change much, and no by-products are formed.

[0245] Meanwhile, the NMR spectra of the static thermal stability test results of the ruthenium precursor compositions of Example 1 and Example 5 are as follows: Figure 1 and Figure 2 shown.

[0246] from Figure 1 It can be seen that in the NMR analysis of the ruthenium precursor composition of Example 1, a peak of the compound represented by Formula 1 was observed at about 2.01 ppm, a peak of the compound represented by Formula 2 was observed at about 1.97 ppm, and a peak of the compound represented by Formula 3 was observed at about 1.84 ppm. In addition, the peaks of the components corresponding to by-products A and B in Table 5 appeared at 1.95 ppm and 1.86 ppm, respectively.

[0247] On the other hand, from Figure 2 It can be seen that in the NMR analysis of the ruthenium precursor composition of Example 5, the peak of the compound represented by Formula 1 was observed at about 2.01ppm, the peak of the compound represented by Formula 2 was observed at about 1.97ppm, and the peak of the compound represented by Formula 3 was not observed at about 1.84ppm. In addition, the peaks of the components corresponding to by-products A and B in Table 5 did not appear at 1.95ppm and 1.86ppm. The results confirm 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 by-products A and B in Table 5.

Claims

1. A ruthenium precursor composition, comprising, based on the total weight of the ruthenium precursor composition, 20 wt % to 60 wt % of a compound represented by the following formula 1, 20 wt % to 50 wt % of a compound represented by the following formula 2, and 0 wt % to 55 wt % of a compound represented by the following formula 3: [Formula 1] [Formula 2] [Formula 3] 2. The ruthenium precursor composition according to claim 1, comprising 30 wt % to 60 wt % of a compound represented by the following formula 1, 30 wt % to 50 wt % of a compound represented by the following formula 2, and 0 wt % to 25 wt % of a compound represented by the following formula 3, based on the total weight of the ruthenium precursor composition.

3. The ruthenium precursor composition according to claim 1, wherein The total content of the compound represented by Formula 1 and the compound represented by Formula 2 and the content of the compound represented by Formula 3 are in a ratio of 100:0 to 80:20 by weight.

4. The ruthenium precursor composition according to claim 1, comprising the compound represented by Formula 3 in an amount of 10 wt% or less, based on the total weight of the ruthenium precursor composition.

5. The ruthenium precursor composition according to claim 1, comprising the compound represented by Formula 3 in an amount of 5 wt% or less based on the total weight of the ruthenium precursor composition. 6 . The ruthenium precursor composition according to claim 1 , which does not contain a compound represented by Formula 3.

7. The ruthenium precursor composition according to claim 1, wherein A 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 according to claim 1, wherein Use at room temperature 1 When the ruthenium precursor composition was measured by H-NMR (400 MHz, C6D6, 25°C), no NMR peaks appeared at 1.95 ppm, 1.86 ppm, or both positions.

9. A method for preparing a ruthenium precursor composition, the method comprising reacting a compound represented by the following formula 4 with an alkali metal carbonate represented by the following formula 5 and 1,5-hexadiene in an organic solvent, in, The ruthenium precursor composition comprises 20 wt % to 60 wt % of a compound represented by the following formula 1, 20 wt % to 50 wt % of a compound represented by the following formula 2, and 0 wt % to 55 wt % of a compound represented by the following 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 Li, Na and K, and X is selected from Cl, Br and I.

10. The method for preparing a ruthenium precursor composition according to claim 9, wherein: The reaction includes a reflux reaction.

11. The method for preparing a ruthenium precursor composition according to claim 10, wherein: The reflux reaction is carried out at 60°C to 160°C for 10 hours to 100 hours. 12 . The method for preparing a ruthenium precursor composition according to claim 9 , further comprising distilling under a reduced pressure of 0.1 torr to 1 torr and at 50° C. to 200° C. after the reaction.

13. The method for preparing a ruthenium precursor composition according to claim 9, wherein: The reaction includes: a first reflux reaction of a 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.

14. The method for preparing a ruthenium precursor composition according to claim 13, wherein: The first reflux reaction is carried out at 60°C to 160°C for 10 hours to 40 hours, and the second reflux reaction is carried out at 60°C to 160°C for 10 hours to 60 hours.

15. The method for preparing a ruthenium precursor composition according to claim 13, wherein: The first alkali metal carbonate includes Li2CO3, and the second alkali metal carbonate includes Na2CO3.

16. The method for preparing a ruthenium precursor composition according to claim 13, wherein: The molar ratio of the first alkali metal carbonate to the second alkali metal carbonate is 1:0.2 to 3.

0.

17. The method for preparing a ruthenium precursor composition according to claim 13, further comprising cooling the product to room temperature before the second reflux reaction.

18. The method for preparing a ruthenium precursor composition according to claim 9, wherein: The molar ratio of the compound represented by Formula 4, the alkali metal carbonate and 1,5-hexadiene is 1:2 to 10:1 to 8.

19. The method for preparing a ruthenium precursor composition according to claim 9, wherein: The organic solvent includes a primary or secondary alcohol having 5 or less carbon atoms.

20. A method for forming a ruthenium-containing film, the method comprising preparing a ruthenium precursor composition; and using the ruthenium precursor composition to form a ruthenium-containing film, in, The ruthenium precursor composition is prepared by reacting a compound represented by the following formula 4 with an alkali metal carbonate represented by the following formula 5 and 1,5-hexadiene in an organic solvent, and the ruthenium precursor composition comprises 20 wt % to 60 wt % of the compound represented by the following formula 1, 20 wt % to 50 wt % of the compound represented by the following formula 2, and 0 wt % to 55 wt % of the compound represented by the following 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 Li, Na and K, and X is selected from Cl, Br and I.

21. The method for forming a ruthenium-containing film according to claim 20, wherein: The ruthenium-containing film is deposited by chemical vapor deposition or atomic layer deposition (ALD), and the deposition is performed at a temperature ranging from room temperature to 550°C.

22. A ruthenium-containing film formed using the ruthenium precursor composition according to claim 1.

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