Method for manufacturing a ruthenium-containing thin film and the ruthenium-containing thin film manufactured thereby

Abstract

This invention provides a method for producing a ruthenium-containing thin film and a ruthenium-containing thin film produced thereby. The method for producing a ruthenium-containing thin film according to this invention allows for the easy production of a high-purity thin film in a simple process using a ruthenium compound and a specific reaction gas.

Description

Technical Field

[0001] The present invention relates to a method for producing a ruthenium-containing thin film and a ruthenium-containing thin film produced thereby, and more specifically, to a method for producing a ruthenium-containing thin film by reacting a ruthenium compound as a thin film deposition precursor with a specific gas, and a ruthenium-containing thin film produced thereby.

Background Art

[0002] Ruthenium is excellent in conductivity and the possibility of forming conductive oxides, and has electrical properties such as a relatively high work function (Fbulk=4.71 eV). In addition, due to its characteristics such as excellent etching properties and lattice adhesion to copper, it is one of the materials widely used as a thin film electrode material for semiconductor devices.

[0003] Semiconductor devices adopt high-level miniaturization and three-dimensional design for high storage capacity and responsiveness. Therefore, in order to use ruthenium in semiconductor devices, a technique for uniformly forming a ruthenium-containing thin film with a thickness of several nanometers on a substrate is required, and in particular, it is necessary to ensure that the unique electrical properties of ruthenium as described above, such as high conductivity, are fully exhibited.

[0004] Therefore, methods using molecular beam epitaxy (MBE), chemical vapor deposition (CVD), physical vapor deposition (PVD) and the like have been studied as thin film deposition methods for semiconductor elements. Recently, along with the scaling down of semiconductor elements and the reduction of design rules, thin film formation using atomic layer deposition (ALD) following a self-limiting surface reaction mechanism has been extensively studied as a deposition method that satisfies the requirements of low-temperature processes, precise thickness control, thin film uniformity and step coverage.

[0005] Conventionally, atomic layer deposition methods using ruthenium raw materials such as Ru(OD)3[tris(2,4-octanedionato)Ruthenium(III)] and Ru(EtCP)2[bis(ethylcyclopentadienyl)Ruthenium(II)] have been limited by the fact that the purity of the ruthenium deposited on the reaction substrate is low due to the oxygen contained in Ru(OD)2, and some RuOx is formed. In the case of Ru(EtCP)2, the ruthenium atoms are difficult to exist independently as they break chemical bonds, resulting in a problem of a large amount of impurities remaining in the ruthenium thin film, and requiring an additional step of reduction using O2 plasma during deposition.

[0006] Therefore, in order to fabricate next-generation semiconductor devices that are expected to be highly miniaturized, there is a need to develop ruthenium compounds with low resistance and high purity through simpler processes than conventional methods. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Korean Patent Publication No. 10-2010-0049587 [Overview of the project] [Problems that the invention aims to solve]

[0008] To solve the aforementioned problems, the present invention provides a method for producing a ruthenium-containing thin film using a ruthenium compound as a precursor for ruthenium-containing thin film deposition, and a ruthenium-containing thin film produced thereby, along with a specific reaction gas.

[0009] Furthermore, the present invention provides a ruthenium-containing thin film deposition composition comprising a ruthenium compound and a specific reaction gas. [Means for solving the problem]

[0010] The present invention provides a method for producing a ruthenium-containing thin film, As a precursor for thin film deposition, use the ruthenium compound of the following chemical formula 1: The process may also include the step of producing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof as a reaction gas. [Chemical formula 1] [ka] (In the above chemical formula 1, R, R1, and R2 are, independently, C1-C5 alkyl groups.

[0011] Preferably, in Chemical Formula 1 of the method for producing a ruthenium-containing thin film according to one embodiment of the present invention, R, R1, and R2 may be C1-C3 alkyl groups independently of each other.

[0012] More preferably, the ruthenium compound of chemical formula 1 according to one embodiment of the present invention may be represented by the following chemical formula 2. [Chemical formula 2] [ka]

[0013] As the reaction gas for the method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the halogen-containing silicon compound or halogen-containing tin compound may be represented by the following chemical formula 3. [Chemical formula 3] RmMHnX4-nm (In the above chemical formula 3) M is either Sn or Si. R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, mono-C1-C3 alkylsilyl, di-C1-C3 alkylsilyl, or tri-C1-C3 alkylsilyl. X is F, Cl, Br, or I. n and m are integers between 0 and 3, and both n and m are not simultaneously 0. Preferably, the reaction gas according to one embodiment of the present invention may be I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3, SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I.

[0014] A method for producing a ruthenium-containing thin film according to one embodiment of the present invention comprises: A) maintaining the temperature of a substrate mounted in a chamber at 80 to 500°C; B) injecting a carrier gas and a ruthenium compound; C) injecting a reaction gas which is iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound or a mixture thereof to form a ruthenium-containing thin film.

[0015] A method for producing a ruthenium-containing thin film according to yet another embodiment of the present invention comprises: a) maintaining the temperature of a substrate mounted in a chamber at 80 to 500°C; b) injecting a ruthenium compound and a reaction gas which is iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound or a mixture thereof to form a ruthenium-containing thin film.

[0016] The method for producing a ruthenium-containing thin film according to one embodiment of the present invention may further comprise a step of performing heat treatment after the step of producing the ruthenium-containing thin film.

[0017] Preferably, the heat treatment may be performed at 200 to 700°C.

[0018] Preferably, the heat treatment may be performed under hydrogen gas atmosphere.

[0019] According to one embodiment of the present invention, the composition for depositing a ruthenium-containing thin film is: a ruthenium compound represented by the following Chemical Formula 1, and as a reaction gas, may comprise iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof. [Chemical Formula 1]

Chemical Formula

[0020] The ruthenium-containing thin film according to one embodiment of the present invention is produced using the composition for depositing a ruthenium-containing thin film, and may have a specific resistance of 130 µΩ·cm or less. Effects of the Invention

[0021] The method for producing a ruthenium-containing thin film according to the present invention does not use oxygen as a reaction gas in a process using a ruthenium compound as a precursor for thin film deposition, so that a separate reduction step is not required, thereby providing excellent convenience.

[0022] The ruthenium-containing thin film produced by the above production method minimizes the content of impurities such as carbon, oxygen and hydrogen, has excellent step coverage and gap fill, and has high density and purity.

[0023] In addition, the ruthenium-containing thin film produced by the production method can be deposited with uniform and excellent step coverage for trenches, contacts, or via patterns. [Brief explanation of the drawing]

[0024] [Figure 1] This figure shows the differential scanning calorimetry (DSC) analysis results of the ruthenium compound of Example 1. [Figure 2] This figure shows the thermogravimetric analysis (TGA) results of the ruthenium compound in Example 1. [Figure 3] This figure shows the results of measuring the vapor pressure of the ruthenium compound in Example 1 as it changes with temperature. [Figure 4] This figure shows the growth rate of the ruthenium-containing thin film of Example 2 with respect to substrate temperature. [Figure 5] This figure shows the thickness of the ruthenium-containing thin film of Example 2 as measured by electron scanning microscope (SEM) at the substrate temperature. [Figure 6] This figure shows the ruthenium-containing thin film of Example 4 measured via transmission electron microscopy (TEM). [Modes for carrying out the invention]

[0025] The method for producing a ruthenium-containing thin film, the ruthenium-containing thin film deposition composition, and the ruthenium-containing thin film produced using the present invention will be described in detail below. However, unless otherwise defined, the technical and scientific terms used herein have the meaning that a person with ordinary skill in the art to which the present invention belongs would ordinarily understand, and descriptions of known functions and structures that could obscure the gist of the present invention in the following description will be omitted.

[0026] The "alkyl" and other "alkyl" moieties described herein may be in either a linear or branched chain form and have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 3 carbon atoms.

[0027] Furthermore, the "alkene compounds" described herein are acyclic or cyclic hydrocarbon compounds, and are organic radicals derived from hydrocarbons containing one or more double bonds. The present invention provides a method for producing high-purity ruthenium-containing thin films in a simple process without requiring a separate reduction step, by using a ruthenium compound as a precursor and employing specific reaction gases such as iodine, (C1-C3) alkyl iodide, silane iodide, or mixtures thereof. This enables the production of thin films with uniform surface thickness, high step coverage, and gap filling without voids.

[0028] The ruthenium compound according to one embodiment of the present invention may be a ruthenium(0) compound in which the ruthenium atom is in an oxidation state of ±0.

[0029] A method for producing a ruthenium-containing thin film according to one embodiment of the present invention is: As a precursor for thin film deposition, use the ruthenium compound of the following chemical formula 1: The process may also include a step of producing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodide, halogen-containing silicon compounds, halogen-containing tin compounds, or mixtures thereof as the reaction gas.

[0030] [Chemical formula 1] [ka]

[0031] (In the above chemical formula 1, R, R1, and R2 are, independently, C1-C5 alkyl groups.

[0032] The present invention's method for producing ruthenium-containing thin films does not use oxygen, which is a reaction gas used conventionally. Therefore, it is possible to produce high-purity thin films, and there is no need for a separate reduction step to remove oxygen contained in the thin film. Thus, ruthenium-containing thin films can be produced in a simple process.

[0033] According to one embodiment of the present invention, R, R1, and R2 in chemical formula 1 may be C1-C3 alkyl groups, independently of each other.

[0034] According to one embodiment of the present invention, the ruthenium compound may be a compound represented by the following chemical formula 2.

[0035] [Chemical formula 2] [ka]

[0036] According to one embodiment of the present invention, the halogen-containing silicon compound or halogen-containing tin compound may be represented by the following chemical formula 3.

[0037] [Chemical formula 3] RmMHnX4-nm

[0038] (In the above chemical formula 3) M is either Sn or Si. R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, mono-C1-C3 alkylsilyl, di-C1-C3 alkylsilyl, or tri-C1-C3 alkylsilyl. X is F, Cl, Br, or I. n and m are integers between 0 and 3, and both n and m are not simultaneously 0.

[0039] According to one embodiment of the present invention, the reaction gas is I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3, SiH2Cl2, It may also be SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0040] The present invention provides a method for producing a ruthenium-containing thin film, which is not limited to a method in which a precursor ruthenium compound is reacted with a reaction gas which is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof to produce a ruthenium-containing thin film. Preferably, the method for producing a ruthenium-containing thin film according to one embodiment of the present invention is as follows: A) A step of maintaining the temperature of the substrate mounted in the chamber at 80-500°C, B) The step of injecting a carrier gas and a ruthenium compound, The process may also include the step of injecting a reaction gas which is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film.

[0041] A method for producing a ruthenium-containing thin film according to yet another embodiment of the present invention is: a) A step of maintaining the temperature of the substrate mounted in the chamber at 80 to 500°C, b) The process may include the step of injecting a reaction gas which is a ruthenium compound and iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film.

[0042] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the step of heat treatment may be further included after the step of producing the ruthenium-containing thin film, and more specifically, the heat treatment may be performed at 200 to 700°C, and more specifically at 300 to 600°C.

[0043] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the heat treatment may be performed under hydrogen gas.

[0044] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium compound used as a precursor may be changed to a gaseous state by a method such as heating for thin film deposition and then introduced into the process chamber.

[0045] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the reaction gas may be changed to a gaseous state by a method such as heating and introduced into a process chamber containing a substrate on which a ruthenium compound is adsorbed.

[0046] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium compound and the reaction gas can be supplied to the chamber alternately or independently of each other. Furthermore, the ruthenium compound and the reaction gas can be supplied to the chamber continuously or discontinuously, and the discontinuous supply may include a pulsed state.

[0047] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, it goes without saying that after step B) and / or step C), a further step may be taken to supply an inert gas into the chamber and purge it to remove unreacted ruthenium compound gas, by-product gas, or unreacted reaction gas. The inert gas may be one or more selected from nitrogen (N2), argon, and helium. The amount of purge gas injected is not limited, but may be specifically in the range of 800 to 5,000 sccm, and more specifically in the range of 1,000 to 3,000 sccm.

[0048] In other words, a manufacturing method according to one embodiment of the present invention may include: A) maintaining the temperature of a substrate mounted in a chamber at 80 to 500°C; B) injecting a carrier gas and a ruthenium compound; D1) purging the inside of the chamber using an inert gas; C) injecting a reaction gas which is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film on the substrate; and D2) purging the inside of the chamber using an inert gas.

[0049] Furthermore, in a manufacturing method according to yet another embodiment of the present invention, the purging step described above may be performed after step b). Specifically, this may include a) a step of maintaining the temperature of a substrate mounted in a chamber at 80 to 500°C, b) a step of injecting a reaction gas which is a ruthenium compound and iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film on the substrate, and D2) a purging step of purging the inside of the chamber with an inert gas.

[0050] The substrate according to one embodiment of the present invention can be any usable substrate within the range recognized by those skilled in the art, and the temperature of the substrate is not limited, but preferably 200 to 400°C. This temperature range is due to the decomposition characteristics of the ruthenium compound used as a precursor itself and the reaction characteristics with the reaction gas used as a reaction gas, which is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof.

[0051] In one embodiment of the present invention, the usable substrate may be, but is not limited to, a substrate containing one or more semiconductor materials from among Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, an SOI (Silicon On Insulator) substrate, a quartz substrate, a display glass substrate, a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), or polyester, or a tungsten substrate.

[0052] In addition to using a reaction gas that is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, with a ruthenium compound as a precursor, the thin film deposition conditions can be adjusted according to the structure or thermal properties of the target thin film.

[0053] Evaporation conditions according to one embodiment of the present invention include the flow rate of the precursor ruthenium compound, the flow rate of the carrier gas, pressure, RF power, and substrate temperature. A non-limiting example of such evaporation conditions is that the flow rate of the ruthenium compound can be adjusted within the range of 1 to 1000 cc / min, the carrier gas within the range of 1 to 1000 cc / min, the reaction gas within the range of 1 to 1000 cc / min, the pressure within the range of 0.1 to 100 torr, the RF power within the range of 200 to 1000 W, and the substrate temperature within the range of 80 to 500°C, preferably 200 to 400°C, but is not limited thereto.

[0054] Preferably, the reaction gas according to one embodiment of the present invention can be used in an amount of 0.1 to 200 moles per mole of ruthenium compound, but is not limited thereto, and can be adjusted according to the thin film deposition conditions. For example, in the case of atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD), preferably 1 to 100 moles, more preferably 1 to 50 moles, and even more preferably 2 to 30 moles may be used per mole of ruthenium compound.

[0055] A method for producing a ruthenium-containing thin film according to one embodiment of the present invention may further include a step of heat treatment after the step of producing the ruthenium-containing thin film, and the heat treatment may be performed at 200 to 700°C for 30 minutes to 4 hours, preferably at 300 to 600°C for 1 to 2 hours, and may be performed in a hydrogen atmosphere.

[0056] According to one embodiment of the present invention, the reaction gas is I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3, SiH2Cl2, It may also be SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0057] In a method for producing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium compound may be supplied to the chamber together with a carrier gas. Specifically, the carrier gas may be one or more selected from nitrogen (N2), hydrogen, argon, and helium, and may be one or more inert gases selected from nitrogen (N2), argon, and helium as a preferred combination with the specific reaction gas of the present invention.

[0058] In this art, where ruthenium precursors are supplied in the gas phase to produce ruthenium-containing thin films, any thin film that can be manufactured within the scope recognized by those skilled in the art is acceptable. As a specific and substantial example, a ruthenium-containing thin film may typically be conductive ruthenium, a ruthenium oxide film, or a hybrid film thereof. In addition, various other high-quality thin films containing ruthenium can be manufactured within the scope recognized by those skilled in the art.

[0059] The present invention relates to a ruthenium compound represented by the following chemical formula 1, The present invention provides a ruthenium-containing thin film deposition composition comprising iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof as a reaction gas.

[0060] [Chemical formula 1] [ka]

[0061] (In the above chemical formula 1, R, R1, and R2 are, independently, C1-C5 alkyl groups.

[0062] Preferably, the reaction gas according to one embodiment of the ruthenium-containing thin film deposition composition of the present invention may be used in an amount of 0.1 to 200 moles, preferably 1 to 100 moles, more preferably 1 to 50 moles, and even more preferably 2 to 30 moles, per mole of the ruthenium compound represented by chemical formula 1.

[0063] Preferably, the reaction gas according to one embodiment of the ruthenium-containing thin film deposition composition of the present invention is I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3 It may also be SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0064] Furthermore, the present invention provides a ruthenium-containing thin film manufactured using the ruthenium-containing thin film deposition composition according to one embodiment of the present invention, wherein the manufactured ruthenium-containing thin film may have a resistivity of 130 μΩ·cm or less, preferably 100 μΩ·cm or less.

[0065] The ruthenium-containing thin film of the present invention can be manufactured in a simple process using a ruthenium compound represented by chemical formula 1 and specific reaction gases such as iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, resulting in a ruthenium-containing thin film with high purity, high density, and high durability. Furthermore, by using iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof as the reaction gas instead of oxygen during the manufacturing of the ruthenium-containing thin film, oxidation of the underlying film can be prevented during the deposition process, and oxidation of the underlying film of the ruthenium-containing thin film can also be prevented after formation. This prevents an increase in contact resistance between the ruthenium-containing thin film and the underlying film due to oxides formed at the interface with the underlying film.

[0066] Furthermore, when manufacturing ruthenium-containing thin films, using ruthenium compounds with specific reaction gases such as iodine, (C1-C3) alkyl iodide, halogen-containing silicon compounds, halogen-containing tin compounds, or mixtures thereof can improve crystal quality and reduce the resistivity of the thin film to 130 μΩ·cm or less, preferably 100 μΩ·cm or less.

[0067] The present invention will be described more specifically below with reference to the following embodiments. Before that, however, the terms and words used in this specification and claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather should be interpreted in a manner consistent with the technical idea of ​​the present invention, in accordance with the principle that inventors may define the concepts of terms as appropriate to best describe their invention.

[0068] Therefore, the embodiments described herein and the configurations illustrated in the drawings represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the invention. It should be understood that there are various equivalents and modifications that can be substituted for them at the time of filing.

[0069] Furthermore, all the following examples were performed using a commercially available showerhead-type 200mm single-wafer ALD system (CN1, Atomic Premium) and known atomic layer deposition (ALD) methods. Alternatively, these methods can be performed using a commercially available showerhead-type 200mm single-wafer CVD (PECVD) system (CN1, Atomic Premium) and known plasma chemical vapor deposition methods.

[0070] The resistivity of the deposited ruthenium-containing thin film was measured using a sheet resistance meter (4pointprobe, DASOLENG, ARMS-200C), its thickness was measured using a transmission electron microscope (FEI (Netherlands) Tecnai G2F30S-Twin), and the composition of the thin film was analyzed using Time of Flight-Elastic Recoil Detection (TOF-ERD), NEC.

[0071] [Example 1] Preparation of ruthenium compounds Production of [(Ethylbenzene)RuCl2]2 [ka]

[0072] Ruthenium(III) chloride hydrate (RuCl3·nH2O) (250.5 g, 1.01 mol) was mixed with ethanol solution (2003 ml, 32.94 mol), and then 1-ethyl-1,4-cyclohexadiene (389 ml, 3.03 mol) was added while maintaining an internal temperature of 66°C. The mixture was then stirred under reflux at 90°C for 5 hours. During this time, the internal temperature was maintained at 79°C. After the reaction was complete, the solid obtained by recrystallization was removed under reduced pressure to remove the solvent and volatile by-products, yielding 281.2 g of a brown solid compound. (Yield 100%)

[0073] Production of (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) [ka]

[0074] To the [(Ethylbenzene)RuCl2]2 (277.9 g, 0.5 mol) prepared as described above, sodium carbonate (222.39 g, 2.10 mol) and a solution of 2-propanol (1912.4 ml, 24.98 mol) were added and stirred to the turbidity. 2,3-dimethyl(dimethyl)-1,3-butadiene (226.0 ml, 2.00 mol) was added at room temperature, and the mixture was stirred under reflux at 95°C for 7 hours. After the reaction was complete, the solution was filtered, and the solvent and volatile by-products were removed under reduced pressure. The solution was then extracted with n-hexane. After filtering the n-hexane extract, the solvent was removed from the resulting filtrate under reduced pressure, and the filtrate was distilled under reduced pressure to recover 201.9 g of a yellow liquid compound (yield 69.8%). The compound (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) obtained through the above process was defined as compound 1.

[0075] 1H-NMR (400 MHz, benzene-d6) δ (ppm): 4.93 (m, 2H, C6H5CH2CH3 m-CH), 4.85 (m, 1H, C6H5CH2CH3 p-CH), 4.72,4.70 (d, 2H, C6H5CH2CH3 o-CH), 2.01 (s, 2H, C6H5CH2CH3), 1.99 (s, 6H, CH2=C(CH3)C(CH3)=CH2), 1.91 (s, 2H, CH2=CHC(CH3)=CH2), 0.98 (t, 3H, C6H5CH2CH3), 0.21 (s, 2H, CH2=C(CH3)C(CH3)=CH2).

[0076] To confirm the basic thermal properties of the ruthenium compound (Compound 1) produced in Example 1, differential scanning calorimeter analysis (DSC) and thermogravimetric analysis (TGA) were performed, and the results are shown in Figures 1 and 2.

[0077] Figure 1 shows the differential scanning calorimetry (DSC) results of compound 1 (3.7 mg) measured in an argon atmosphere at a heating rate of 10°C / min up to 500°C. It can be seen that no thermal decomposition peak was observed up to approximately 200°C, and thermal decomposition occurred at approximately 290°C.

[0078] Figure 2 shows the thermogravimetric analysis results of 29.5 mg of compound 1 measured in an argon atmosphere at a heating rate of 10°C / min up to 500°C. The vertical axis represents the percentage of weight loss with increasing temperature. Compound 1 exhibits a single evaporation step at around 210°C and almost no residue at 300°C, demonstrating rapid vaporization characteristics. These results confirm that compound 1 has excellent thermal stability.

[0079] Furthermore, the vapor pressure of compound 1 was measured with respect to temperature changes and is shown in Figure 3. According to Figure 3, a vapor pressure of approximately 1 Torr level can be confirmed under conditions of 120°C.

[0080] [Example 2] Fabrication of a ruthenium-containing thin film A ruthenium-containing thin film was formed by atomic layer deposition using a Ru-containing precursor (EthylbenzeneRu(2,3-dimethyl(dimethyl)-1,3-butadiene)) and an iodine-containing precursor (Diiodomethane, CH2I2) as the reaction gas.

[0081] The silicon oxide substrate was maintained at 200-300°C, and compound 1 was filled into a stainless steel bubbler container and maintained at the specified temperature. The vaporized compound in the stainless steel bubbler container was supplied with argon gas as a carrier gas for 5 seconds (0.0084 g) to be transferred to the silicon oxide substrate and adsorbed onto the silicon oxide substrate. Next, unreacted compound was removed using argon gas (2000 sccm) for 5 seconds. Then, diiodomethane (CH2I2) heated at 90°C was supplied for 1.5 seconds (0.018 g) to form a ruthenium-containing thin film. Finally, reaction by-products and residual reaction gases were removed using argon gas (2000 sccm) for 10 seconds. 2.3 moles of reaction gas (diiodomethane) were used for 1 mole of compound 1. The above process constituted one cycle, and the ruthenium-containing thin film was formed by repeating 300 cycles. Detailed thin film manufacturing conditions are shown in Table 1 below.

[0082] [Table 1]

[0083] Figure 4 shows the growth rate of the ruthenium-containing thin film manufactured according to Example 2, with respect to substrate temperature. Figure 4 shows that the ruthenium-containing thin film of Example 2 has a predetermined saturated deposition rate in the range of 220 to 270°C. This indicates that the ruthenium-containing thin film can have a safe deposition margin during mass production.

[0084] The thickness of the ruthenium-containing thin film formed according to the substrate temperature was analyzed via an electron scanning microscope (SEM), and the results are shown in Figure 5. This shows that a uniform surface thin film with a thickness of 2 nm or less can be manufactured using the ruthenium-containing thin film in the temperature range of 220 to 270°C.

[0085] [Example 3] Fabrication of a ruthenium-containing thin film In Example 2, a ruthenium-containing thin film was heat-treated in a hydrogen atmosphere at 450°C for 30 minutes, with the deposition temperature of the silicon oxide film substrate being 260°C.

[0086] Table 2 below shows the resistivity values ​​of the ruthenium-containing thin films produced in Example 2 at deposition temperatures of 220°C, 250°C, 260°C, and 270°C, as well as the ruthenium-containing thin film produced according to Example 3. According to Table 2, it can be seen that the resistivity value of Example 2, which was not heat-treated, was around 100 μΩ·cm, while in Example 3, which was heat-treated, the resistivity improved significantly to 25 μΩ·cm.

[0087] [Table 2]

[0088] Furthermore, the composition of the ruthenium-containing thin film in Example 2, when the deposition temperature was 260°C, and the ruthenium-containing thin film in Example 3 were analyzed using a secondary ion mass spectrometer and are shown in Table 3 below.

[0089] In Example 3, the heat treatment resulted in a significant decrease in the elements carbon (C), iodine (I), and hydrogen (H), which improved the resistivity.

[0090] [Table 3]

[0091] [Example 4] Fabrication of a ruthenium thin film A ruthenium thin film was deposited on a pattern with an aspect ratio of 27 under the conditions of Example 2. Figure 6 shows the deposition pattern measured using a transmission electron microscope. It was confirmed that the deposition aspect ratio (step coverage) of the ruthenium thin film was 100%.

[0092] Specifically, the ruthenium-containing thin film fabricated in the trench structure in Example 2 (substrate temperature: 260°C) was measured using a transmission electron microscope (TEM) and is shown in Figure 6. This demonstrates that the ruthenium-containing thin film can be deposited uniformly and with excellent step coverage.

[0093] As described above, the present invention is explained by specific matters and limited examples and comparative examples, which are provided to aid in a more general understanding of the present invention. The present invention is not limited to the above examples, and various modifications and variations can be made from such descriptions by those who have ordinary skill in the art to which the present invention belongs.

[0094] Therefore, the concept of the present invention should not be limited to the embodiments described above. Not only the claims described later, but also all modifications that are equivalent or comparable to the claims described herein can be said to fall within the scope of the concept of the present invention.

Claims

1. As a precursor for thin film deposition, use the ruthenium compound of the following chemical formula 1: A method for producing a ruthenium-containing thin film, comprising the step of producing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof as a reaction gas. [Chemical formula 1] 【Chemistry 1】 (In the above chemical formula 1, R, R1, and R2 are independently C1-C5 alkyl groups.

2. A method for producing a ruthenium-containing thin film according to claim 1, wherein in the chemical formula 1, R, R1, and R2 are independently C1-C3 alkyl groups.

3. The ruthenium compound is represented by the following chemical formula 2, as described in claim 1, for the method of producing a ruthenium-containing thin film. [Chemical formula 2] 【Chemistry 2】

4. The method for producing a ruthenium-containing thin film according to claim 1, wherein the halogen-containing silicon compound or halogen-containing tin compound is represented by the following chemical formula 3. [Chemical formula 3] RmMHnX4-n-m (In the above chemical formula 3) M is either Sn or Si. R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, mono-C1-C3 alkylsilyl, di-C1-C3 alkylsilyl, or tri-C1-C3 alkylsilyl. X is F, Cl, Br, or I. n and m are integers between 0 and 3, and both n and m are not simultaneously zero.

5. The reaction gases are I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2HCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3, SiH2Cl2, SiH3Cl A method for producing a ruthenium-containing thin film according to claim 1, wherein the thin film is SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3, or ICHCHCH2I.

6. A) A step of maintaining the temperature of the substrate mounted in the chamber at 80 to 500°C, B) Steps of injecting a carrier gas and a ruthenium compound, A method for producing a ruthenium-containing thin film according to claim 1, comprising the step of injecting a reaction gas which is iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film.

7. a) A step of maintaining the temperature of the substrate mounted in the chamber at 80 to 500°C, b) A method for producing a ruthenium-containing thin film according to claim 1, comprising the step of injecting a reaction gas which is a ruthenium compound and iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof, to produce a ruthenium-containing thin film.

8. A method for producing a ruthenium-containing thin film according to claim 6 or 7, further comprising the step of heat treatment after the step of producing the ruthenium-containing thin film.

9. The method for producing a ruthenium-containing thin film according to claim 8, wherein the heat treatment is performed at 200 to 700°C.

10. The method for producing a ruthenium-containing thin film according to claim 8, wherein the heat treatment is performed under hydrogen gas.

11. A ruthenium compound represented by the following chemical formula 1, A ruthenium-containing thin film deposition composition comprising iodine, (C1-C3) alkyl iodide, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof as a reaction gas. [Chemical formula 1] 【Transformation 3】 (In the above chemical formula 1, R, R1, and R2 are independently C1-C5 alkyl groups.

12. A ruthenium-containing thin film manufactured using the ruthenium-containing thin film deposition composition described in claim 11, having a resistivity of 130 μΩ·cm or less.

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