Ruthenium precursor compositions, methods for preparing ruthenium precursor compositions, and methods for forming ruthenium-containing films using the ruthenium precursor compositions

Abstract

The present invention relates to a ruthenium precursor composition, a method for preparing the ruthenium precursor composition, and a method for forming a ruthenium-containing film using the ruthenium precursor composition. According to an embodiment of the present invention, the method includes 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 content of the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 2, and the compound represented by Chemical Formula 3 within a specific range, a thermally highly stable ruthenium precursor composition can be provided in an economical and efficient manner.

Description

[Technical field]

[0001] The present invention relates to ruthenium precursor compositions, methods for preparing ruthenium precursor compositions, and methods for forming ruthenium-containing films using the ruthenium precursor compositions. [Background technology]

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

[0003] In general, as the integration of semiconductor devices progresses and the width of metal wiring becomes narrower, the resistance of the metal wiring may increase. However, if ruthenium metal is used for wiring of semiconductor devices having an extremely narrow metal wiring width (a wiring width of about 40 nm or less), ruthenium (Ru) metal can be advantageously used as a next-generation wiring material because the increase in resistance is smaller than that of copper or cobalt.

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

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

[0006] However, when such ruthenium precursor compositions are applied to semiconductor devices, the ruthenium precursor compositions may change during the vaporization process or over time, become thermally unstable, and result in the formation of by-products such as thermal decomposition materials, etc. As a result, serious problems will arise in that stable and consistent deposition results cannot be obtained in semiconductor processes, and reproducibility cannot be guaranteed.

[0007] Therefore, there is a need to develop ruthenium precursor compositions that are thermally stable, such that their composition does not change readily even at vaporization temperatures, and that can minimize the formation of by-products. [Prior art documents] [Non-patent literature]

[0008] [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. [Non-Patent Document 2] YM Wuu et al., Inorganic Chemistry 1988, 27(17), 3039-3044, doi:10.1021 / ic00290a028. DISCLOSURE OF THEINVENTION technical challenges

[0009] It is an object of the present invention to provide a ruthenium precursor composition which is thermally stable, such that its composition does not readily change even at vaporization temperatures, and which minimizes the formation of by-products such as thermal decomposition materials.

[0010] Another object of the present invention is to provide a method for preparing, in an economical and efficient manner, a ruthenium precursor composition that is thermally stable, such that its composition does not readily change even at vaporization temperatures, and that minimizes the formation of by-products such as thermal decomposition materials.

[0011] It is yet another object of the present invention to provide a method for forming a ruthenium-containing film, wherein the ruthenium-containing film is formed in a stable and efficient manner using a ruthenium precursor composition.

[0012] It is yet another object of the present invention to provide ruthenium-containing films formed using the ruthenium precursor compositions having uniform thickness and excellent quality even on a variety of substrates.

[0013] However, the problems to be solved by the present invention are not limited to those mentioned above, and a person skilled in the art will clearly understand other problems not mentioned from the following description.

[0014] The present invention provides 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:

[0015] [ka]

[0016] The present invention provides a method for preparing a ruthenium precursor composition, 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 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.

[0017] [ka]

[0018] 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.

[0019] In addition, the present invention provides a method for forming a ruthenium-containing film, comprising preparing a ruthenium precursor composition, and forming a ruthenium-containing film using the ruthenium precursor composition, 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 in an organic solvent of 1,5-hexadiene, and contains 20 wt % to 60 wt % of the compound represented by the above formula 1, 20 wt % to 50 wt % of the compound represented by the above formula 2, and 0 wt % to 55 wt % of the compound represented by the above formula 3, based on the total weight of the ruthenium precursor composition.

[0020] Additionally, the present invention provides ruthenium-containing films formed using the ruthenium precursor compositions.

[0021] According to an 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 specific ranges, a thermally extremely stable ruthenium precursor composition can be provided in an economical and efficient manner.

[0022] 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 kept constant during or after vaporization of the ruthenium precursor composition, and the formation of by-products such as thermal decomposition materials can be minimized. As a result, deposition results having stable and consistent physical properties can be obtained in semiconductor processing, thereby providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0023] Furthermore, according to another embodiment of the present invention, a ruthenium-containing film having a thickness of several nanometers to several micrometers can be uniformly formed over a variety of temperature ranges even on a substrate having a pattern (groove) on its surface, a porous substrate, or a plastic substrate, thereby making it possible to realize a high-quality ruthenium-containing film. [Brief description of the drawings]

[0024] [Figure 1] 1 is a graph of static thermal stability test results measured using NMR at 120° C. for the ruthenium precursor composition of Example 1 of the present invention. [Diagram 2] 1 is a graph of static thermal stability test results measured using NMR at 120° C. for the ruthenium precursor composition of Example 5 of the present invention. BEST MODE FOR CARRYING OUT THEINVENTION

[0025] The present invention will now be described in detail.

[0026] The advantages and features of the present invention, as well as the methods for realizing them, will become apparent from the following description of the embodiments. However, the present invention is not limited to the following embodiments, and can be embodied in various different forms. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. The present invention is defined solely by the claims.

[0027] Additionally, when an element is referred to as being formed "on" another element, this specification means not only that one element is formed directly "on" the other element, but also that there is another element(s) interposed therebetween.

[0028] In this specification, when a part is described as "comprising" certain elements, it should be understood that the part does not exclude other elements, but may include other elements as well, unless otherwise specified.

[0029] All numbers and expressions relating to quantities of ingredients, reaction conditions, and the like used herein are understood to be modified by the term "about," unless otherwise indicated.

[0030] [Ruthenium precursor composition] A ruthenium precursor composition according to an embodiment of the present invention comprises, 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.

[0031] [ka]

[0032] The contents of the compound represented by formula 1, the compound represented by formula 2, and the compound represented by formula 3 are each controlled within a specific range, so that the thermal stability of the ruthenium precursor composition can be greatly enhanced.

[0033] When a ruthenium-containing film is formed using the ruthenium precursor composition of the present invention having excellent thermal stability, it is possible to minimize changes in the composition of the ruthenium precursor composition at high temperatures of 100° C. or higher over time during and after vaporization of the ruthenium precursor composition, as well as the formation of by-products such as thermal decomposition materials.

[0034] Therefore, the present invention provides a ruthenium precursor composition having the above-mentioned properties, and therefore has great technical significance in that it is possible to obtain deposition results having more stable and consistent physical properties in semiconductor processes, thereby providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0035] According to certain embodiments of the present invention, in order to achieve the above properties, it is extremely important to control the content range and content ratio of each compound.

[0036] The ruthenium precursor composition may contain the compound represented by formula 1 in an amount of, for example, 22% by weight to 60% by weight, for example, 25% by weight to 60% by weight, for example, 28% by weight to 60% by weight, for example, 30% by weight to 60% by weight, for example, 35% by weight to 60% by weight, for example, 40% by weight to 60% by weight, for example, 45% by weight to 60% by weight, for example, 50% by weight to 60% by weight, or for example, 55% by weight to 60% by weight, 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 by-products such as thermal decomposition materials can be minimized.

[0037] In addition, the ruthenium precursor composition may contain the compound represented by formula 2 in an amount of, 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 satisfies the above content range, the thermal stability can be further enhanced and the formation of by-products such as thermal decomposition materials can be minimized.

[0038] In addition, the ruthenium precursor composition may include 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.

[0039] The ruthenium precursor composition may include 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.

[0040] If the content of the compound represented by formula 3 satisfies the above range, the ruthenium precursor composition is extremely thermally stable and can minimize the formation of by-products such as thermal decomposition materials at temperatures of 100°C or higher.

[0041] 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.

[0042] The content of each of the compound represented by formula 1, the compound represented by formula 2, and the compound represented by formula 3 is, for example, 1It is a value calculated by obtaining the integral ratio of the NMR peak to the sum of the integral values ​​of the NMR peaks, which is 100%, when measured by H-NMR (400 MHz, C6D6, 25°C). Since the ruthenium precursor composition contains a mixture of the compound represented by formula 1, the compound represented by formula 2, and the compound represented by formula 3 as a mixture of three isomers having the same molecular weight, their respective contents can be expressed as weight %.

[0043] In particular, according to certain embodiments of the present invention, it is extremely important to control the content of the compound represented by formula 3.

[0044] That is, when the compound represented by formula 3 meets a certain content range or less, it has excellent thermal stability, so that the composition change during the vaporization process is small, and thermal decomposition is minimized, so that by-products are not formed. However, if the compound represented by formula 3 does not meet the certain content range and is used in excess, the composition changes easily during the vaporization process, so that the composition changes easily over time above a certain temperature, and the formation of by-products increases, making it difficult to obtain deposition results with stable and consistent properties, and thus making it difficult to achieve reproducibility and reliability.

[0045] In addition, the ruthenium precursor composition may be free of a compound represented by Formula 3.

[0046] In such a case, the ruthenium precursor composition may be more advantageous in achieving this objective since it is extremely thermally stable.

[0047] 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 is, by weight, 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.

[0048] 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 extremely thermally stable, which may be more advantageous in achieving the present object.

[0049] 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 highly thermally stable, which may be more advantageous in achieving the present object.

[0050] According to another embodiment of the present invention, the ruthenium precursor composition may include more compounds represented by formula 1 than compounds represented by formula 2. In such a case, it may be more advantageous to further enhance thermal stability and minimize the formation of by-products due to thermal decomposition.

[0051] 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, 20-60:20-50:0-50, for example, 30-60:25-50:0-30, for example, 35-60:30-50:0-20, or for example, 40-60:30-50:0-10. 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, the ruthenium precursor composition is extremely thermally stable, which may be more advantageous in achieving the object of the present invention.

[0052] On the other hand, the ruthenium precursor composition may include by-products, which may include unreacted materials formed during the process for preparing the ruthenium precursor composition, impurities formed by thermal decomposition, etc.

[0053] The content 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.

[0054] In particular, the ruthenium precursor composition may include one or more by-products. For example, the by-products may include a first by-product, or a second by-product having a different constituent component, or a combination thereof.

[0055] Additionally, according to certain embodiments of the present invention, no by-products may be included.

[0056] In particular, the ruthenium precursor composition is placed in a sealed stainless steel canister, heated, cooled to room temperature, 1 When measured by H-NMR (400 MHz, C6D6, 25° C.), when the sum of the integral values ​​of the NMR peaks at about 2.01 ppm (Formula 1), about 1.97 ppm (Formula 2), about 1.95 ppm (by-product A), about 1.86 ppm (by-product B), and about 1.84 ppm (Formula 3) is 100%, the sum of the integral values ​​of the two integral peaks at 1.95 ppm (by-product A) and 1.86 ppm (by-product A) that do 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 peaks are measured at 1.95 ppm, 1.86 ppm, or both, and more particularly, no NMR peaks are measured at 1.95 ppm and 1.86 ppm.

[0057] The substances with NMR peaks at 1.95 ppm and 1.86 ppm are impurities formed by pyrolysis upon prolonged heating. The thermal stability of the ruthenium precursor composition according to the present invention is significantly enhanced, so that the above NMR peaks are preferably not observed.

[0058] NMR spectroscopy is used to analyze thermal stability. For example, a ruthenium precursor composition is vaporized by heating to about 120° C. under vacuum and flowing argon carrier gas at a flow rate of about 200 sccm, and then cooled to about −76° C. and recovered. The compositions recovered from the first 7 days (first week) of vaporization and the compositions recovered from the 8th to 14th days (second week) of vaporization were 1 H-NMR (400 MHz, C6D6, 25° C.), respectively.

[0059] Thus, the ruthenium precursor composition according to the present invention can provide stable and consistent deposition results in semiconductor processes, and thus can be advantageous in terms of reliability and reproducibility.

[0060] Methods for preparing ruthenium precursor compositions A 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 contains 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.

[0061] [ka]

[0062] 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.

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

[0064] In particular, as shown in Reaction Scheme 1 below, a method for preparing a ruthenium precursor composition according to an embodiment of the present invention may include reacting a compound represented by Formula 4 above with an alkali metal carbonate represented by Formula 5 above and 1,5-hexadiene in an organic solvent.

[0065] [ka]

[0066] In Reaction Scheme 1, X is as defined above.

[0067] In the method for preparing a ruthenium precursor composition according to certain embodiments of the present invention, the reaction may be, but is not limited to, a reflux reaction.

[0068] In detail, the reaction may include a reflux reaction carried out 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.

[0069] In certain embodiments of the present invention, the organic solvent may include, but is not limited to, primary or secondary alcohols having 5 or fewer carbon atoms.

[0070] A primary or secondary alcohol having 5 or less carbon atoms can act as a solvent and a reducing agent at the same time, so that the ruthenium compounds according to the present invention can be produced by an economical and simple process that does not require a separate reducing agent.

[0071] The primary or secondary alcohol may be selected from the group consisting of, but is not limited to, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, iso-butanol, n-pentanol, iso-pentanol, and combinations thereof.

[0072] The alkali metal carbonate may include at least one selected from the group consisting of Na2CO3, Li2CO3, and K2CO3.

[0073] Additionally, in the method for preparing a ruthenium precursor composition, 1,5-hexadiene may be used as the material to react with the compound represented by Formula 4 and the alkali metal carbonate represented by Formula 5. 1,5-hexadiene can be highly advantageous for commercial applications because it is cost-effective and can be purchased in bulk compared to, for example, 2,4-hexadiene or 1,3-hexadiene.

[0074] In particular, it is not easy to purchase 2,4-hexadiene or 1,3-hexadiene commercially, and the purchase and purchase amount thereof are very limited (e.g., limited to a few grams or tens of grams). Therefore, there may be limitations in mass-producing the desired ruthenium precursor composition using 2,4-hexadiene or 1,3-hexadiene. In contrast, it is easy to purchase 1,5-hexadiene in large quantities at a low price. Furthermore, when 1,5-hexadiene is used to prepare a ruthenium precursor composition, especially when it is used to prepare a ruthenium precursor composition that does not contain a compound represented by formula 3, it can easily and efficiently produce the desired effect. That is, the use of 1,5-hexadiene can be extremely advantageous in terms of cost, productivity, efficiency, and quality in the preparation process of the ruthenium precursor composition and the semiconductor process.

[0075] 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, 1:2-10:1-8, for example, 1:2-10:2-8, or for example, 1:4-10:3-7.

[0076] 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 advantageous to realize the desired effects in the present invention.

[0077] Alternatively, in certain embodiments of the present invention, compounds of formula 4 may be prepared as shown in Reaction Scheme 2 below.

[0078] [ka]

[0079] In Reaction Scheme 2, X is as defined above, and n is an integer of 0 or less than 10.

[0080] In particular, the compound represented by formula 4, [RuX2(p-cymene)]2, may be prepared by the reaction of 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 an alcohol.

[0081] In such cases, β-terpinene, δ-terpinene, α-phellandrene, β-phellandrene, or isomers thereof may be used in place of α-terpinene or γ-terpinene. In some embodiments of the present invention, the reaction for preparing the compound represented by formula 4 may be, but is not limited to, a reflux reaction.

[0082] In the method for preparing a ruthenium precursor composition according to certain embodiments of the present invention, the reflux reaction may be carried out once or at least twice.

[0083] In particular, the method 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.

[0084] In addition, after subjecting the compound represented by Formula 4 to a reaction, such as 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 a ruthenium precursor composition may further include performing a distillation 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 at 50°C to 200°C, 70°C to 150°C, 70°C to 140°C, or 80°C to 120°C.

[0085] In addition, the composition of the ruthenium precursor composition may be adjusted by changing the distillation conditions. In particular, the compound represented by formula 3 can be adjusted to be contained in an amount of, for example, about 10% by weight or less by changing the distillation conditions to 0.2 Torr to 0.4 Torr and 100°C to 120°C.

[0086] Meanwhile, in a method for preparing a ruthenium precursor composition according to another embodiment of the present invention, the reflux reaction may be carried out at least twice, for example, twice.

[0087] In detail, as shown in the following Reaction Scheme 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 reaction product obtained by the first reflux reaction with a second alkali metal carbonate.

[0088] [ka]

[0089] In Reaction Scheme 3, X is as defined above.

[0090] In Reaction Scheme 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.

[0091] In Reaction Scheme 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.

[0092] The first alkali metal carbonate may include Li2CO3. If Li2CO3 is used as the first alkali metal carbonate, it can be confirmed that the NMR peak corresponding to 1,5-hexadiene decreases and then completely disappears when analyzed by NMR during the first reflux reaction. An isomerization reaction in which hydrogen bonded to a double bond carbon coordinated to a Ru central metal is transferred to another carbon is known [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 converted to 2,4-hexadiene and 1,3-hexadiene through such an isomerization reaction. For this reason, it may be more advantageous to control the ruthenium precursor composition within a specific range as desired in the present invention.

[0093] 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 high yield can be achieved, and thus it may be more advantageous to control the ruthenium precursor composition within a specific range as desired in the present invention.

[0094] The molar ratio of the first alkali metal carbonate to the second alkali metal carbonate may be, for example, 1:0.2-3.0, for example, 1:0.5-2.5, for example, 1:0.5-2.0, or for example, 1:0.5-2.0. 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 desired in the present invention.

[0095] Meanwhile, the method for preparing a ruthenium precursor composition according to certain embodiments of the present invention may further include cooling the reaction product to room temperature before carrying out the second reflux reaction.

[0096] In particular, the method 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 a reaction product obtained from the first reflux reaction to room temperature, and a second reflux reaction of the reaction product with a second alkali metal carbonate.

[0097] Additionally, according to certain embodiments of the present invention, the method for preparing a ruthenium precursor composition may further comprise distillation and / or filtration after the second reflux reaction.

[0098] Distillation and / or filtration are as described above.

[0099] According to an embodiment of the present invention, by 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.

[0100] In addition, according to certain embodiments of the present invention, the method for preparing the ruthenium precursor composition can be controlled so that the compound represented by formula 3 is not present.

[0101] In such a case, it is possible to provide a ruthenium precursor composition that is extremely thermally stable. When a ruthenium-containing film is formed using the ruthenium precursor composition, it is possible to ensure that the composition of the ruthenium precursor composition does not change during or after vaporization of the ruthenium precursor composition, and to minimize the formation of by-products such as thermal decomposition materials. As a result, deposition results having stable and consistent physical properties can be obtained in semiconductor processing, thereby providing a ruthenium-containing film with guaranteed reproducibility and reliability.

[0102] Methods for forming ruthenium-containing films According to certain embodiments of the present invention, the ruthenium precursor compositions prepared by the above methods can be used to form ruthenium-containing films.

[0103] In detail, a method for forming a ruthenium-containing film includes preparing a ruthenium precursor composition (a first step) and forming a ruthenium-containing film using the ruthenium precursor composition (a second step). 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 contains 20% by weight to 60% by weight of a compound represented by the following Formula 1, 20% by weight to 50% by weight of a compound represented by the following Formula 2, and 0% by weight to 55% by weight of a compound represented by the following Formula 3, based on the total weight of the ruthenium precursor composition.

[0104] In the method for forming a ruthenium-containing film, the step (first step) of preparing a ruthenium precursor composition is as described above.

[0105] A method for forming a ruthenium-containing film can include forming a ruthenium-containing film using a ruthenium precursor composition (second step).

[0106] In particular, the second step is depositing a ruthenium-containing film on the substrate using a ruthenium precursor composition. The depositing step may include forming a ruthenium-containing film on the substrate by providing a gaseous ruthenium precursor composition.

[0107] In some embodiments of the present invention, the ruthenium-containing film may be formed on one or more substrates selected from, but not limited to, conventional semiconductor wafers, compound semiconductor wafers, and plastic substrates (PI, PET, PES, and PEN). In addition, substrates with holes or grooves may be used, and porous substrates with large surface areas may be used, but are not limited to these. In addition, the ruthenium-containing film may be formed simultaneously or sequentially on all or a portion of a substrate where two or more different types of substrates are in contact with or connected to each other, but are not limited to these.

[0108] According to certain embodiments of the present invention, in a method for depositing a ruthenium-containing film, a substrate may be placed in a reaction chamber and then a carrier gas or diluent gas may be used to transport a ruthenium precursor composition onto the substrate to deposit the ruthenium-containing film.

[0109] In detail, the deposition may be performed at a temperature of 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 500°C, about 150°C to about 45 The film may be formed in a temperature range of, but is not limited to, 0°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. In certain embodiments of the present invention, the ruthenium-containing film may be formed at a temperature range of about 200°C to about 500°C, or about 300°C to about 500°C.

[0110] In certain embodiments of the present invention, the ruthenium-containing film may be deposited by chemical vapor deposition (CVD), particularly, but not limited to, metal-organic chemical vapor deposition (MOCVD), or atomic layer deposition (ALD). In certain embodiments of the present invention, the 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 reactive gases known in the art, but may not be limited to such.

[0111] In some embodiments of the present invention, hydrogen (H2), ammonia (NH3), oxygen (O2), or ozone (O3) gases used in semiconductor processes may be used as reactant gases for ALD and CVD methods to form ruthenium-containing films, but may not be limited thereto.

[0112] For example, if hydrogen gas and / or ammonia gas is used to form the film in the ALD and CVD methods, a ruthenium-containing film containing fewer impurities can be formed. For example, if oxygen gas or ozone gas is used to form the film in the ALD and CVD methods, a ruthenium metal film or a ruthenium oxide film can be formed, but is not limited thereto.

[0113] In certain embodiments of the present invention, a method for forming a ruthenium-containing film may include, but is not limited to, delivering a gaseous ruthenium precursor composition onto a substrate disposed within a growth chamber to form a ruthenium-containing film on a surface of the substrate.

[0114] In an embodiment of the present invention, the ruthenium-containing film can be applied in various ways according to the application purpose, and may be formed in a thickness range of about 1 nm to about 500 nm, but is not limited thereto. For example, the ruthenium-containing film may be formed in a thickness range of 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 200 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 5 ...500 nm, about 10 nm to about 500 nm, about 10 nm to about 200 nm, about 10 nm to about 300 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 300 nm, about 10 nm to about 300 nm, about 10 nm to about 2 About 100nm, about 10nm to about 50nm, about 10nm to about 40nm, about 10nm to about 30nm, about 10nm to about 20nm, about 20nm to about 500nm, about 20nm to about 400nm, about 20nm to about 300nm, Approximately 20nm to approximately 200nm, approximately 20nm to approximately 100nm, approximately 20nm to approximately 50nm, approximately 20nm to approximately 40nm, approximately 20nm to approximately 30nm, approximately 30nm to approximately 500nm, approximately 30nm to approximately 400nm, approximately 30nm to approximately Approximately 300nm, approximately 30nm ~ approximately 200nm, approximately 30nm ~ approximately 100nm, approximately 30nm ~ approximately 50nm, approximately 30nm ~ approximately 40nm, approximately 40nm ~ approximately 500nm, approximately 40nm ~ approximately 400nm, approximately 40nm ~ approximately 300 nm, approximately 40 nm to approximately 200 nm, approximately 40 nm to approximately 100 nm, approximately 40 nm to approximately 50 nm, approximately 50 nm to approximately 500 nm, approximately 50 nm to approximately 400 nm, approximately 50 nm to approximately 300 nm, approximately 50 nm to approximately 200 nm, approximately The ruthenium-containing film may be formed to a thickness range of 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, 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 the thickness range is not limited to these. In some embodiments of the present invention, the ruthenium-containing film may be formed to a thickness range of about 1 nm to about 50 nm.

[0115] In certain embodiments of the present invention, the ruthenium-containing film may be formed on a substrate that includes features (grooves) having an aspect ratio of about 1 to about 100 and a width of about 10 nm to about 1 μm, but is not limited thereto. The features (grooves) may be in the form of holes or trenches. For example, the aspect ratio may 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 about 30, about 30 to about 10 It may be, but is not limited to, 0, about 30 to about 90, about 30 to about 80, about 30 to about 70, about 30 to about 60, about 30 to about 50, about 30 to about 40, about 40 to about 100, about 40 to about 90, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 40 to about 50, about 50 to about 100, about 50 to about 90, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 100, about 60 to about 90, about 60 to about 80, about 60 to about 70, about 70 to about 100, about 70 to about 90, about 70 to about 80, about 80 to about 100, about 80 to about 90, or about 90 to about 100. In addition, for example, the width may be from about 10 nm to about 1 μm, from about 10 nm to about 900 nm, from about 10 nm to about 800 nm, from about 10 nm to about 700 nm, from about 10 nm to about 600 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, from about 10 nm to about 100 nm, from about 10 nm to about 90 nm, from about 10 nm to about 80 nm, from about 10 nm to about 70 nm, from about 10 nm to about 60 nm, from about 10 nm to about 50nm, about 10nm to about 40nm, about 10nm to about 30nm, about 10nm to about 20nm, about 20nm to about 1μm, about 20nm to about 900nm, about 20nm to about 800nm, about 20nm to about 700nm, about 20nm ~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 20nm to about 40nm, about 20nm to about 30nm, about 30nm to about 1μm, about 30nm to about 900nm, about 30nm to about 800nm, about 30nm to about 700nm, about 30nm to about 600nm, about 30nm to about 500nm, about 30nm to about 400nm, about 30nm to about 300nm, about 30nm to about 200nm, about 30nm to about 100nm, about 30nm to about 90nm, about 30nm to about 80nm, about 30nm to about 70nm, about 30nm to about 60nm, about 30 to about 50nm, about 30nm to about 40nm, about 40nm to about 1μm, about 40nm to about 900nm, about 40nm 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 1μm, 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 m, 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 1μm, 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 1μm, about 400nm to about 900nm, about 400nm to about 800nm,It may be, but is not limited to, 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 to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, or about 900 nm to about 1 μm.

[0116] In one 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 due to its low density and high thermal stability. In particular, a ruthenium-containing film having a thickness of several micrometers to several nanometers can be uniformly formed in a temperature range of room temperature to 550°C even on a substrate having a pattern (groove) on the surface, a porous substrate, or a plastic substrate.

[0117] In one embodiment of the present invention, a method for forming a ruthenium-containing film includes housing a substrate in a reaction chamber, delivering a ruthenium precursor composition onto the substrate using a carrier gas or diluent gas, and depositing a ruthenium-containing metal thin film, oxide thin film, or nitride thin film at a wide range of deposition temperatures, preferably, but not limited to, room temperature to about 550° C.

[0118] In some embodiments 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 dilution gas, but may not be limited thereto.

[0119] In some embodiments of the present invention, various methods may be applied to deliver the ruthenium precursor composition onto the substrate, such as a bubbling method using a carrier gas to forcibly vaporize the precursor, a liquid delivery system (LDS) method supplying the precursor in liquid phase at room temperature and vaporizing it through a vaporizer, and a vapor flow control (VFC) method using the vapor pressure of the precursor to directly supply the precursor. If the vapor pressure is high, the VFC method may be used. If the vapor pressure is low, a bypass method may be used to heat the container and evaporate it.

[0120] A bubbling method in which the ruthenium precursor composition is placed in a bubbler vessel or a VFC vessel and subjected to bubbling with a carrier gas at a temperature range of room temperature to about 100° C. and about 0.1 Torr to about 10 Torr, or the use of high vapor pressure may be used for delivery to the chamber. In particular, an LDS method in which a ruthenium precursor composition in a liquid phase at room temperature is supplied and vaporized through a vaporizer may be used, but is not limited thereto.

[0121] In some embodiments of the invention, the ruthenium precursor composition may be delivered with argon (Ar) or nitrogen (N2) gas, thermal energy or plasma may be used, or a bias may be applied to the substrate to vaporize the ruthenium precursor composition.

[0122] In some embodiments of the present invention, the deposition temperature is from room temperature to about 550° C., or from about 200° C. to about 500° C., which broadens the applicable process temperature range for memory devices, logic devices, and display devices, thereby allowing the ruthenium precursor composition to be applied in various fields.

[0123] In some embodiments of the present invention, when a ruthenium-containing film is deposited as a ruthenium-containing metal or oxide film, at least one selected from water vapor (HO), oxygen (O), oxygen plasma (O plasma), nitrogen oxides (NO, NO), nitrogen oxide plasma (NO plasma), oxygen nitride (NO), hydrogen peroxide (HO), and ozone (O) may be used as a reactive gas.

[0124] In some embodiments of the present invention, when a ruthenium-containing film is deposited as a ruthenium-containing nitride film, at least one selected from ammonia (NH), ammonia plasma (NH plasma), hydrazine (N2H4), and nitrogen plasma (N2 plasma) may be used as the reactive gas.

[0125] 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 kept unchanged during or after vaporization of the ruthenium precursor composition, and the formation of by-products such as thermal decomposition materials can be minimized. As a result, deposition results with stable and consistent physical properties can be obtained in semiconductor processing, thereby efficiently providing ruthenium-containing films with guaranteed reproducibility and reliability.

[0126] [Ruthenium-containing film] According to certain embodiments of the present invention, there is provided a ruthenium-containing film formed using a ruthenium precursor composition.

[0127] The ruthenium-containing film may have a thickness of about 1 nanometer (nm) to several micrometers (μm) and may be applied in a variety of ways depending on the intended application.

[0128] For example, the thickness, aspect ratio, and width of the ruthenium-containing film are described above and may be selected in various ways.

[0129] Since the contents of the compound represented by formula 1, the compound represented by formula 2, and the compound represented by formula 3 are each controlled within a specific range in the ruthenium precursor composition according to an embodiment of the present invention, the ruthenium precursor composition has excellent thermal stability, and therefore a ruthenium-containing film can be efficiently formed by CVD and ALD in a wide temperature range. In particular, even on a substrate having a fine pattern (groove) on the surface, a porous substrate, or a plastic substrate having a thickness of several micrometers to several tens of nanometers, it is possible to form a ruthenium-containing film uniformly in a temperature range of room temperature to 550°C.

[0130] The ruthenium-containing film may be at least one selected from the group consisting of 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.

[0131] The present invention will be described in detail below with reference to examples. The following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to these examples.

[0132] Preparation Example 1: Preparation of [RuCl2(p-cymene)]2 27 g (0.13 mol) of ruthenium trichloride hydrate (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 equiv.) of α-terpinene was slowly added to the solution at room temperature and the mixture was refluxed for 15 h to complete the reaction.

[0133] Upon completion of the reaction, the dark brown solid obtained by filtration was dissolved in 50 ml of n-hexane (CH 14 ) and dried under vacuum to give [RuCl2(p-cymene)]2 as a reddish brown solid compound.

[0134] Example 1: Preparation of a Ruthenium Precursor Composition [ka]

[0135] 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 flame-dried 1,000 ml Schlenk flask to prepare a suspension. 15.8 g (0.192 mole) of 1,5-hexadiene was slowly added to the suspension, and the mixture was refluxed for 40 hours to complete the reaction. Upon completion of the reaction, the solvent and volatile by-products were removed under reduced pressure, and then 500 ml of n-hexane was used to extract the reaction product. The n-hexane extract was filtered through a Celite pad and a glass frit, and the filtrate thus obtained was subjected to solvent removal under reduced pressure and vacuum distillation to obtain a liquid mixture represented by Formula 1, Formula 2, and Formula 3 having the composition shown in Table 1 below. The ratio of the three isomers having the same molecular weight is: 1 In the H-NMR (400 MHz, C6D6, 25 °C) spectrum, it was determined as the relative ratio of the integral values ​​of the NMR peaks at 2.01 ppm (Formula 1), 1.97 ppm (Formula 2), and 1.84 ppm (Formula 3) appearing due to the hydrogen of the methyl (CH3) bonded to the benzene ring of the ligand.

[0136] 1 H-NMR (400MHz, C6D6, 25°C): Compounds represented by formula 1: (p-cymene)(2,4-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru δ 4.668(m, 4H, [CH3C6H * 4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 4.330(m, 2H, [CH3C6H4CH(CH3)2](CH3CH=CH * -CH * =CHCH3)Ru), δ 2.338(m, 1H, [CH3C6H4CH * (CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 2.013 (s, 3H, [CH * 3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 1.371 (d, 6H, [CH3C6H4CH(CH3)2](CH * 3CH=CH-CH=CHCH * 3)Ru), δ 1.147 (d, 6H, [CH3C6H4CH(CH * 3)2](CH3CH=CH-CH=CHCH3)Ru), δ 0.739 (m, 2H, [CH3C6H4CH(CH3)2](CH3CH * =CH-CH=CH * CH3)Ru), The compound represented by Formula 2: (p-cymene)(1,3-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.983 (m, 1H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru, δ 4.835 (m, 2H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru, δ 4.727 (m, 1H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru, δ 4.603 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CH * CH=CHCH2CH3)Ru, δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH * =CHCH2CH3)Ru, δ 2.302 (m, 1H, [CH3C6H4CH * (CH3)2](CH2=CHCH=CHCH2CH3)Ru, δ 1.969 (s, 3H, [[CH * 3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru, δ 1.758 (d, 1H, [CH3C6H4CH(CH3)2](CH * 2=CHCH=CHCH2CH3)Ru, δ 1.703 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH * 2CH3)Ru, δ 1.401 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH * 2CH3)Ru, δ 1.120 (t, 3H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH * 3)Ru, δ 1.098 (m, 6H, [CH3C6H4CH(CH * 3)2](CH2=CHCH=CHCH2CH3)Ru, δ 0.726 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CH * CH2CH3)Ru, δ 0.194 (d, 1H, [CH3C6H4CH(CH3)2](CH * 2=CHCH=CHCH2CH3)Ru The compound represented by Formula 3: (p-cymene)(1,5-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ru δ 4.505 (m, 4H, [CH3C6H * 4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ 3.425 (m, 2H, [CH3C6H4CH(CH3)2](CH2=CH * CH2-CH2CH * =CH2)Ru, δ 2.235 (m, 2H, [CH3C6H4CH(CH3)2](CH2=CHCH * 2-CH2CH=CH2)Ru, δ 2.227 (d, 2H, [CH3C6H4CH(CH3)2](CH * 2=CHCH2-CH2CH=CH2)Ru, δ 2.133(m, 1H, [CH3C6H4CH * (CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ 1.924(m, 2H, [CH3C6H4CH(CH3)2](CH2=CHCH2-CH * 2CH=CH2)Ru, δ 1.844(s, 3H, [CH * 3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=CH2)Ru, δ 1.512(d, 2H, [CH3C6H4CH(CH3)2](CH2=CHCH2-CH2CH=CH * 2) Ru, δ 1.118(d, 6H, [CH3C6H4CH(CH * 3)2](CH2=CHCH2-CH2CH=CH2)Ru

[0137] Examples 2 to 4 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 times of vacuum distillation were changed.

[0138] Example 5 A suspension was prepared by mixing 30 g (0.048 mol) of [RuCl2(p-cymene)]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.

[0139] 23.7g (0.288mol) of 1,5-hexadiene was slowly added to the suspension, and the mixture was refluxed for 24 hours (first reflux reaction), and then cooled to room temperature. 20.4g (0.192mol) of Na2CO3 was added to the reaction product, and the reaction was further refluxed for 48 hours (second reflux reaction) to complete the reaction.

[0140] Upon completion of the reaction, the solvent and volatile by-products were removed under reduced pressure, and then 500 ml of n-hexane was used to extract the reaction product. The n-hexane extract was filtered through a celite pad and a glass frit, and the filtrate thus obtained was subjected to solvent removal and distillation under reduced pressure to obtain a ruthenium precursor composition comprising 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.

[0141] 1 H-NMR (400MHz, C6D6, 25°C): Compounds represented by formula 1: (p-cymene)(2,4-hexadiene)Ru, [CH3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru δ 4.668(m, 4H, [CH3C6H * 4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 4.330(m, 2H, [CH3C6H4CH(CH3)2](CH3CH=CH * -CH * =CHCH3)Ru), δ 2.338(m, 1H, [CH3C6H4CH * (CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 2.013(s, 3H, [CH * 3C6H4CH(CH3)2](CH3CH=CH-CH=CHCH3)Ru), δ 1.371(d, 6H, [CH3C6H4CH(CH3)2](CH * 3CH=CH-CH=CHCH * 3) Ru), δ 1.147(d, 6H, [CH3C6H4CH(CH * 3)2](CHCH=CH-CH=CHCH3)Ru), δ 0.739(m, 2H, [CH3C6H4CH(CH3)2](CH3CH * =CH-CH=CH * CH3)Ru), Compound represented by formula 2: (p-cymene)(1,3-hexadiene)Ru [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.983 (m, 1H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.835 (m, 2H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.727 (m, 1H, [CH3C6H * 4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 4.603 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CH * CH=CHCH2CH3)Ru δ 4.418 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH * =CHCH2CH3)Ru δ 2.302 (m, 1H, [CH3C6H4CH * (CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 1.969 (s, 3H, [[CH * 3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH3)Ru δ 1.758 (d, 1H, [CH3C6H4CH(CH3)2](CH * 2=CHCH=CHCH2CH3)Ru δ 1.703 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH * 2CH3)Ru δ 1.401 (m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH * 2CH3)Ru δ 1.120 (t, 3H, [CH3C6H4CH(CH3)2](CH2=CHCH=CHCH2CH * 3)Ru δ 1.098 (m, 6H, [CH3C6H4CH(CH *3) 2](CH2=CHCH=CHCH2CH3)Ru, δ 0.726(m, 1H, [CH3C6H4CH(CH3)2](CH2=CHCH=CH * CH2CH3)Ru, δ 0.194(d, 1H, [CH3C6H4CH(CH3)2](CH * 2=CHCH=CHCH2CH3)Ru Compound represented by formula 3: Not observed.

[0142] The contents of the compound represented by formula 1, the compound represented by formula 2, and 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.

[0143] [Table 1]

[0144] Evaluation Example 1: Evaluation of Dynamic Thermal Stability The ruthenium precursor composition prepared in Example 1 was evaluated for dynamic thermal stability under the conditions shown in Table 2 below.

[0145] [Table 2]

[0146] In detail, 50 g of the ruthenium precursor composition was placed in a stainless steel canister and heated to a temperature of 120° C. under vacuum. The ruthenium precursor composition contained in the stainless steel canister was vaporized by flowing argon carrier gas at a flow rate of 200 sccm. The vapor was collected in a stainless steel canister cooled to −76° C. The composition vaporized during the first 7 days (0-168 hours) was collected in a first canister cooled to −76° C., and the composition vaporized during the 8th to 14th days (168-336 hours) was collected in a second canister cooled to −76° C. The unheated composition (week 0), the vapor collected in the first canister (week 1), and the vapor collected in the second canister (week 2) were collected in a second canister cooled to −76° C. 1 H-NMR (400 MHz, C6D6, 25°C) spectra were measured for each. The peak areas were compared to 100% as the sum of the NMR peak areas at 2.01 ppm (Formula 1), 1.97 ppm (Formula 2), 1.95 ppm (By-product A), 1.86 ppm (By-product B), and 1.84 ppm (Formula 3). The results are shown in Table 3.

[0147] [Table 3]

[0148] Evaluation Example 2: Evaluation of static thermal stability The ruthenium precursor compositions prepared in Examples 1-5 were evaluated for static thermal stability under the conditions shown in Table 4 below.

[0149] [Table 4]

[0150] Specifically, 1 g of each of the ruthenium precursor compositions of Examples 1 to 5 was placed in a sealed stainless steel canister and heated for 7 days and 14 days in an oven heated to 110° C. and 120° C., respectively. The heated ruthenium precursor compositions of Examples 1 to 5 were each cooled to room temperature, 1H-NMR (400 MHz, C6D6, 25° C.) was used to measure the peak areas relative to 100% as 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). The results are shown in Table 5.

[0151] [Table 5]

[0152] As can be seen from Table 5, in the present invention, it was possible to control the ruthenium precursor compositions of Examples 1 to 5 so that the compound represented by formula 1, the compound represented by formula 2, and the compound represented by formula 3 each had a specific content depending on the purpose.

[0153] In addition, it has been determined that the thermal stability of the ruthenium precursor compositions varies significantly depending on their composition.

[0154] Specifically, in the ruthenium precursor compositions of Examples 1 to 5, the lower the content of the compound represented by formula 3, the more thermally stable the ruthenium precursor composition becomes. Thus, the composition of the compounds represented by formulas 1 to 3 hardly changed even at temperatures of 110°C and 120°C, and the production rates of by-products A and B were low.

[0155] In particular, when the compound of formula 3 was absent (0 wt%), the ruthenium precursor composition was extremely thermally stable even after two weeks at room temperature and at 110° C. and 120° C., respectively. Thus, the composition of the compounds of formulas 1 and 2 changed little, and no by-products were formed.

[0156] Meanwhile, the NMR spectra of the results of the static thermal stability test of the ruthenium precursor compositions of Examples 1 and 5 are shown in Figures 1 and 2, respectively.

[0157] 1, in the NMR analysis of the ruthenium precursor composition of Example 1, peaks were observed for the compound represented by Formula 1 at about 2.01 ppm, the compound represented by Formula 2 at about 1.97 ppm, and the compound represented by Formula 3 at about 1.84 ppm. In addition, peaks for components corresponding to by-products A and B in Table 5 appeared at both 1.95 ppm and 1.86 ppm.

[0158] On the other hand, as can be seen from Figure 2, in the NMR analysis of the ruthenium precursor composition of Example 5, the peaks of the compound represented by formula 1 at about 2.01 ppm and the compound represented by formula 2 at about 1.97 ppm were observed, but the peak of the compound represented by formula 3 at about 1.84 ppm was not observed. In addition, the peaks of the components corresponding to by-products A and B in Table 5 did not appear at both 1.95 ppm and 1.86 ppm. As a result, it was confirmed that the ruthenium precursor composition of Example 5 did not contain the compound represented by formula 3 and did not 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% to 60% by weight of a compound represented by the following formula 1, 20% to 50% by weight of a compound represented by the following formula 2, and 0% to 55% by weight of a compound represented by the following formula 3: 【Chemistry 1】

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

3. 2. The ruthenium precursor composition according to claim 1, wherein 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 is 100:0 to 80:20 on a weight basis.

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

5. 2. The ruthenium precursor composition of 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. 2. The ruthenium precursor composition of claim 1, which is free of a compound represented by formula 3.

7. 2. 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 from 7:3 to 5:

5.

8. The ruthenium precursor composition １ H-NMR (400MHz, C ６ D ６ 2. The ruthenium precursor composition of claim 1, wherein no NMR peaks appear at 1.95 ppm, 1.86 ppm, or both, when measured at room temperature by NMR spectroscopy (NMR spectroscopy, 25° C.).

9. 1. A method for preparing a ruthenium precursor composition, comprising the step of 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:

1. A method for preparing a ruthenium precursor composition, wherein the ruthenium precursor composition comprises, based on a total weight of the ruthenium precursor composition, 20% to 60% by weight of a compound represented by the following formula 1, 20% to 50% by weight of a compound represented by the following formula 2, and 0% to 55% by weight of a compound represented by the following formula 3. 【Chemistry 2】 [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.]

10. 10. The method for preparing a ruthenium precursor composition of claim 9, wherein the reaction comprises a reflux reaction.

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

12. 10. The method for preparing a ruthenium precursor composition according to claim 9, further comprising the step of carrying out distillation after said reaction at a reduced pressure of 0.1 Torr to 1 Torr and at 50°C to 200°C.

13. 10. The method for preparing a ruthenium precursor composition of claim 9, wherein the reacting comprises a first reflux reaction of the compound represented by formula 4 with a first alkali metal carbonate and 1,5-hexadiene in the organic solvent, and a second reflux reaction of the reaction product with a second alkali metal carbonate.

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

15. The first alkali metal carbonate is Li ２ CO ３ and the second alkali metal carbonate is Na ２ CO ３ 14. A method for preparing the ruthenium precursor composition of claim 13 comprising:

16. 14. 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 1:0.2-3.

0.

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

18. 10. 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 1:2-10:1-8.

19. 10. The method for preparing a ruthenium precursor composition of claim 9, wherein the organic solvent comprises a primary or secondary alcohol having 5 or fewer carbon atoms.

20. 1. A method for forming a ruthenium-containing film, comprising: preparing a ruthenium precursor composition; and forming a ruthenium-containing film using the ruthenium precursor composition, 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 in an organic solvent of 1,5-hexadiene, and contains, based on the total weight of the ruthenium precursor composition, 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. 【Chemistry 3】 [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.]

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

22. 13. A ruthenium-containing film formed using the ruthenium precursor composition of claim 1.

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