Method for producing ruthenium-containing thin film and ruthenium-containing thin film produced thereby

Abstract

Provided are: a method for producing a ruthenium-containing thin film, which is capable of easily producing a high-purity thin film by a simple process by using a ruthenium compound and a specific reaction gas; and a ruthenium-containing thin film produced thereby.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for manufacturing a ruthenium-containing thin film and a ruthenium-containing thin film manufactured thereby, and more particularly, to a method for manufacturing 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 manufactured thereby. BACKGROUND

[0002] Ruthenium has excellent electrical conductivity and excellent possibility of forming a conductive oxide, and has electrical characteristics such as a relatively high work function (Fbulk=4.71 eV). Furthermore, due to excellent etching characteristics and lattice matching with copper, it is one of materials widely used as a thin film electrode material for semiconductor devices.

[0003] Semiconductor devices employ highly miniaturized and three-dimensional structure designs for high storage capacity or responsiveness, and thus, in order to use ruthenium in semiconductor devices, a technology for uniformly forming a ruthenium-containing thin film having a thickness of several nanometers on a substrate is required, and in particular, the special electrical characteristics of ruthenium, i.e., high electrical conductivity, etc., as described above, need to be well exhibited.

[0004] Therefore, as a thin film deposition method for semiconductor devices, methods using molecular beam epitaxy (MBE), chemical vapor deposition (CVD), and physical vapor deposition (PVD) are being studied. Recently, with the miniaturization of semiconductor devices, as the design rule is reduced, as a deposition method satisfying low-temperature processing, precise thickness control, thin film uniformity, and coatability, thin film formation using atomic layer deposition (ALD) based on a self-limiting surface reaction mechanism is being widely studied.

[0005] Conventionally, atomic layer deposition methods using Ru(OD)3 [tris(2,4-octanedionato) ruthenium(III)] and Ru(EtCP)2 [bis(ethylcyclopentadienyl) ruthenium(II)] as a ruthenium raw material substance have a problem in that the purity of ruthenium deposited on a reaction substrate is low due to the inclusion of oxygen in Ru(OD)3 in the raw material substance, and a part of RuO xthe limitations of the conventional method. In addition, in the case of Ru(EtCP)2, since the Ru atom is difficult to break the chemical bond and exist independently, there is a problem that a large amount of impurities remain in the Ru thin film, and there is a problem that an additional process of reducing using O2 plasma is required in the deposition.

[0006] Therefore, in order to manufacture a new generation of semiconductor devices of a desired high degree of miniaturization, it is required to develop a ruthenium compound having a low resistance value and a high purity by a simpler process than ever before. SUMMARY

[0007] The present application provides a method for manufacturing a ruthenium-containing thin film using a ruthenium compound as a precursor for deposition of the ruthenium-containing thin film, and a ruthenium-containing thin film manufactured thereby, in order to solve the problems as described above.

[0008] In addition, the present application provides a composition for deposition of a ruthenium-containing thin film including a ruthenium compound and a specific reaction gas.

[0009] The method for manufacturing a ruthenium-containing thin film according to the present application can include the following steps:

[0010] A ruthenium compound of the following Chemical Formula 1 is used as a precursor for thin film deposition,

[0011] The ruthenium-containing thin film is manufactured using iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas.

[0012] [Chemical Formula 1]

[0013]

[0014] (In the above Chemical Formula 1,

[0015] R, R1, and R2 are each independently a C1-C5 alkyl group.)

[0016] Preferably, in the Chemical Formula 1 of the method for manufacturing a ruthenium-containing thin film according to an embodiment of the present application, R, R1, and R2 can each independently be a C1-C3 alkyl group.

[0017] More preferably, the ruthenium compound of Chemical Formula 1 according to an embodiment of the present application can be represented by the following Chemical Formula 2.

[0018] [Chemical Formula 2]

[0019]

[0020] In the reaction gas of the method for manufacturing a ruthenium-containing thin film according to an embodiment of the present application, the halogen-containing silicon compound or the halogen-containing tin compound can be represented by the following Chemical Formula 3.

[0021] [Chemical Formula 3]

[0022] R m MH n X 4-n-m

[0023] (In the above Chemical Formula 3,

[0024] M is Sn or Si;

[0025] R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, mono C1-C3 alkylsilyl, di C1-C3 alkylsilyl, or tri C1-C3 alkylsilyl,

[0026] X is F, Cl, Br, or I,

[0027] n and m are integers of 0 to 3, and n and m are not simultaneously 0.)

[0028] Preferably, the reaction gas according to an embodiment of the present application can 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.

[0029] The method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application can include the steps of:

[0030] A) a step of maintaining the temperature of a substrate installed in a chamber at 80 to 500°C;

[0031] B) a step of injecting a carrier gas and a ruthenium compound; and

[0032] C) a step of injecting iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas to manufacture a ruthenium-containing thin film.

[0033] The method of manufacturing a ruthenium-containing thin film according to another embodiment of the present application can include the steps of:

[0034] a) a step of maintaining the temperature of a substrate installed in a chamber at 80 to 500°C;

[0035] b) a step of injecting a ruthenium compound and iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas to produce a ruthenium-containing thin film.

[0036] The method of producing a ruthenium-containing thin film according to an embodiment of the present application can further include a step of performing a heat treatment after the step of producing a ruthenium-containing thin film.

[0037] Preferably, the heat treatment can be performed at 200 to 700°C.

[0038] Preferably, the heat treatment can be performed in hydrogen gas.

[0039] The composition for ruthenium-containing thin film deposition according to an embodiment of the present application can include:

[0040] a ruthenium compound represented by the following Chemical Formula 1; and

[0041] iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas.

[0042] [Chemical Formula 1]

[0043]

[0044] (In the above Chemical Formula 1,

[0045] R, R1, and R2 are each independently C1-C5 alkyl.)

[0046] The ruthenium-containing thin film according to an embodiment of the present application can be produced using the composition for ruthenium-containing thin film deposition, and can have a resistivity of 130 μΩ·cm or less.

[0047] The method of producing a ruthenium-containing thin film of the present application has excellent simplicity because, in the process of using a ruthenium compound as a thin film deposition precursor, no oxygen gas is used as a reaction gas, and no additional reduction process is required.

[0048] The ruthenium-containing thin film produced by the above production method has a minimized content of impurities such as carbon, oxygen, and hydrogen, and thus has excellent step coverage and gap fill properties, and high density and purity.

[0049] In addition, the ruthenium-containing thin film produced by the above production method can be uniformly and excellently deposited with respect to a trench, a contact hole, or a via hole pattern. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 A graph showing the results of differential scanning calorimeter analysis (DSC) of the ruthenium compound of Example 1.

[0051] Figure 2 A graph showing the results of thermogravimetric analysis (TGA) of the ruthenium compound of Example 1.

[0052] Figure 3 A graph showing the results of measuring the vapor pressure of the ruthenium compound according to Example 1 with respect to the temperature change.

[0053] Figure 4 A graph showing the growth rate of the substrate temperature of the ruthenium-containing thin film according to Example 2.

[0054] Figure 5 A graph showing the thickness of the ruthenium-containing thin film of Example 2 according to the substrate temperature, measured by a scanning electron microscope (SEM).

[0055] Figure 6 A graph showing the ruthenium-containing thin film of Example 4, measured by a transmission electron microscope (TEM). DETAILED DESCRIPTION

[0056] The manufacturing method of the ruthenium-containing thin film, the composition for deposition of the ruthenium-containing thin film, and the ruthenium-containing thin film manufactured using the same according to the present application will be described in detail hereinafter, in which the technical and scientific terms used have the same meanings as those generally understood by those skilled in the art to which the present application pertains, unless otherwise defined, and the description of the well-known functions and configurations that can unnecessarily obscure the gist of the present application is omitted.

[0057] The "alkyl group" described in the present specification, and the substituent group including other "alkyl group" moieties, include both linear and branched forms, and have 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0058] In addition, the "olefin compound" described in the present specification is a hydrocarbon compound that is acyclic or cyclic, and is an organic radical derived from a hydrocarbon including one or more double bonds.

[0059] The present application provides a method of manufacturing a ruthenium-containing thin film having high purity by using a ruthenium compound as a precursor, and using iodine, (C1-C3) alkyl iodide, a silane iodide, or a mixture thereof as a specific reaction gas, without the need for an additional reduction process, with a simple process, and also enables the manufacture of a thin film having a thin film thickness and a uniform surface, enabling high step coverage and gap filling without voids.

[0060] The ruthenium compound according to an embodiment of the present application can be a ruthenium (0) compound in which the oxidation state of a ruthenium atom is +0.

[0061] The method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application can include the following steps.

[0062] A ruthenium compound of the following Chemical Formula 1 is used as a precursor for thin film deposition,

[0063] A ruthenium-containing thin film is manufactured using iodine, a (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas.

[0064] [Chemical Formula 1]

[0065]

[0066] (In the above Chemical Formula 1,

[0067] R, R1, and R2 are each independently a C1-C5 alkyl group.)

[0068] The method of manufacturing a ruthenium-containing thin film according to the present application does not use oxygen, which has been used as a reaction gas in the past, and thus can manufacture a thin film with high purity, and does not require an additional reduction process for removing oxygen contained in the thin film, and thus can manufacture a ruthenium-containing thin film through a simple process.

[0069] According to an embodiment of the present application, R, R1, and R2 of the above Chemical Formula 1 can each independently be a C1-C3 alkyl group.

[0070] According to an embodiment of the present application, the ruthenium compound can be a compound represented by the following Chemical Formula 2.

[0071] [Chemical Formula 2]

[0072]

[0073] According to an embodiment of the present application, the halogen-containing silicon compound or the halogen-containing tin compound can be represented by the following Chemical Formula 3.

[0074] [Chemical Formula 3]

[0075] R m MH n X 4-n-m

[0076] (In the above Chemical Formula 3,

[0077] M is Sn or Si;

[0078] R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, mono C1-C3 alkylsilyl, di C1-C3 alkylsilyl or tri C1-C3 alkylsilyl,

[0079] X is F, Cl, Br or I,

[0080] n and m are integers from 0 to 3, n and m are not 0 at the same time.

[0081] According to an embodiment of the present application, the above reaction gas can 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, more preferably, can be CH2I2.

[0082] The method for manufacturing a ruthenium-containing thin film of the present application is not limited as long as it is a method for manufacturing a ruthenium-containing thin film by reacting a ruthenium compound as a precursor with iodine, a (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound or a mixture thereof as a reaction gas, but preferably, the method for manufacturing a ruthenium-containing thin film according to an embodiment of the present application can include the following steps:

[0083] A) a step of maintaining the temperature of a substrate installed in a chamber at 80 to 500°C;

[0084] B) a step of injecting a carrier gas and a ruthenium compound; and

[0085] C) a step of injecting iodine, a (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound or a mixture thereof as a reaction gas to manufacture a ruthenium-containing thin film on the above substrate.

[0086] The method for manufacturing a ruthenium-containing thin film according to another embodiment of the present application can include the following steps:

[0087] a) a step of maintaining the temperature of a substrate installed in a chamber at 80 to 500°C;

[0088] b) a step of injecting a ruthenium compound and iodine, (C1-C3) alkyl iodide, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas to manufacture a ruthenium-containing thin film on the substrate.

[0089] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, after the step of manufacturing the ruthenium-containing thin film, a step of performing a heat treatment can be further included, and specifically, the heat treatment can be performed at 200 to 700°C, more specifically, at 300 to 600°C.

[0090] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, the heat treatment can be performed in hydrogen gas.

[0091] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, for thin film deposition, the ruthenium compound used as a precursor can be introduced into a process chamber in a gaseous state by heating or the like.

[0092] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, the reaction gas can be introduced into a process chamber in which the substrate on which the ruthenium compound is adsorbed is present in a gaseous state by heating or the like.

[0093] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, the ruthenium compound and the reaction gas can be supplied to the chamber in cooperation with each other or independently of each other. In addition, the ruthenium compound and the reaction gas can be supplied to the chamber continuously or intermittently, and the intermittent supply can include a pulse form.

[0094] In the method of manufacturing a ruthenium-containing thin film according to an embodiment of the present application, after the B) step and / or the C) step, for the purpose of exhausting unreacted ruthenium compound gas or byproduct gas or unreacted reaction gas, a step of supplying a non-reactive gas into the chamber to perform purging can be further performed. The non-reactive gas can be any one or two or more selected from nitrogen (N2), argon, and helium. The injection amount of the purging gas is not limited, but specifically, it can be supplied at an injection amount in the range of 800 to 5000 seem, and more specifically, it can be supplied at an injection amount in the range of 1000 to 3000 seem, of course.

[0095] That is, the manufacturing method according to an embodiment of the present invention may include the following steps: A) maintaining the temperature of the substrate mounted in the chamber at 80 to 500°C; B) injecting a carrier gas and a ruthenium compound; D1) purging the chamber with an inactive gas; C) injecting iodine, (C1-C3) alkyl iodine, halogenated silicon compound, halogenated tin compound or a mixture thereof as a reactant gas to manufacture a ruthenium-containing thin film on the substrate; and D2) purging the chamber with an inactive gas.

[0096] In addition, in another embodiment of the manufacturing method according to the present invention, after step b), a purging step as described above may be further performed. Specifically, a) maintaining the temperature of the substrate mounted in the chamber at 80 to 500°C; b) injecting a ruthenium compound and iodine, (C1-C3) alkyl iodine, halogenated silicon compound, halogenated tin compound, or a mixture thereof as a reactant gas to form a ruthenium-containing thin film on the substrate; D2) purging step of purging the interior of the chamber with an inactive gas.

[0097] According to an embodiment of the present invention, any substrate that can be used within the scope of knowledge of those skilled in the art is acceptable. The temperature of the substrate is not limited, but it is preferably 200 to 400°C. The above temperature range is set based on the decomposition characteristics of the ruthenium compound used as a precursor and the reaction characteristics with other substances such as iodine, (C1-C3) alkyl iodine, halogenated silicon compounds, halogenated tin compounds or mixtures thereof used as reaction gases.

[0098] In one embodiment of the present invention, the substrate that can be used may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; an SOI (Silicon On Insulator) substrate; a quartz substrate; or a glass substrate for a display; 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, but is not limited thereto.

[0099] According to an embodiment of the present invention, a method for manufacturing a ruthenium-containing thin film uses a ruthenium compound as a precursor and iodine, (C1-C3) alkyl iodine, halogenated silicon compound, halogenated tin compound, or a mixture thereof as a reaction gas. In addition, the corresponding thin film deposition conditions can be adjusted according to the structure or thermal properties of the target thin film.

[0100] As an example of deposition conditions according to an embodiment of the present invention, examples include the feed flow rate of the ruthenium compound as a precursor, the feed flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. As a non-limiting example of such deposition conditions, the feed flow rate of the ruthenium compound is 1 to 1000 cc / min, the carrier gas is 1 to 1000 cc / min, the flow rate of the reactant gas is 1 to 1000 cc / min, the pressure is 0.1 to 100 Torr, the RF power is 200 to 1000 W, and the substrate temperature is 80 to 500°C. Preferably, the temperature can be adjusted in the range of 200 to 400°C, but it is not limited thereto.

[0101] Preferably, the reactant gas according to an embodiment of the invention can be used in amounts from 0.1 to 200 moles relative to 1 mole of ruthenium compound, but is not limited thereto and can be adjusted according to the thin film deposition conditions. As an 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, relative to 1 mole of ruthenium compound, can be used.

[0102] According to an embodiment of the present invention, the method for manufacturing a ruthenium-containing thin film may further include a heat treatment step after the step of manufacturing the ruthenium-containing thin film. The heat treatment may be carried out at 200 to 700°C for 30 minutes to 4 hours, preferably at 300 to 600°C for 1 hour to 2 hours, and may be carried out in a hydrogen atmosphere.

[0103] According to one embodiment of the present invention, the above-mentioned reactant gas 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, S iH2Cl2, 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, more preferably CH2I2.

[0104] In a method for manufacturing a ruthenium-containing thin film according to an embodiment of the present invention, the ruthenium compound may be supplied to the chamber along with a carrier gas. Specifically, the carrier gas may be any one or more selected from nitrogen (N2), hydrogen, argon, and helium. As a preferred combination with the specific reactive gases of the present invention, it may be any one or more inactive gases selected from nitrogen (N2), argon, and helium.

[0105] Any ruthenium-containing thin film can be manufactured within the scope of knowledge of those skilled in the art, specifically those who manufacture ruthenium-containing thin films by supplying ruthenium precursors in the gas phase. As a specific and substantial example, a ruthenium-containing thin film can be a generally conductive ruthenium film, a ruthenium oxide film, or a mixture thereof. In addition, within the scope of knowledge of those skilled in the art, various high-quality ruthenium-containing thin films can be manufactured.

[0106] This invention provides a composition for ruthenium-containing thin film deposition, comprising: a ruthenium compound represented by the following chemical formula 1; and

[0107] Iodine, (C1-C3) alkyl iodine, halogenated silicon compounds, halogenated tin compounds, or mixtures thereof, may be used as reactant gases.

[0108] [Chemical Formula 1]

[0109]

[0110] (In the above chemical formula 1,

[0111] R, R1, and R2 are independently C1-C5 alkyl groups.

[0112] Preferably, in one embodiment of the composition for ruthenium thin film deposition according to the present invention, the reactant gas relative to 1 mole of the ruthenium compound represented by the above chemical formula 1 can be 0.1 to 200 moles, preferably 1 to 100 moles, more preferably 1 to 50 moles, and even more preferably 2 to 30 moles.

[0113] Preferably, the reaction gas in one embodiment of the ruthenium-containing thin film deposition composition according to the present invention can be I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, Si HCl3, 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, more preferably, CH2I2.

[0114] Furthermore, the present invention provides a ruthenium-containing thin film manufactured using the above-described composition for ruthenium thin film deposition according to an embodiment of the present invention, wherein the resistivity of the manufactured ruthenium-containing thin film is 130 μΩ·cm or less, preferably 100 μΩ·cm or less.

[0115] The ruthenium-containing thin film of the present invention can be manufactured with a simple process by using a ruthenium compound represented by the above-described chemical formula 1 and iodine, (C1-C3)alkyl iodine, halogenated silicon compound, halogenated tin compound, or mixtures thereof as a specific reactant gas. Furthermore, when manufacturing the ruthenium-containing thin film, since non-oxygen iodine, (C1-C3)alkyl iodine, halogenated silicon compound, halogenated tin compound, or mixtures thereof are used as the reactant gas, oxidation of the underlying film is prevented during the deposition process, and oxidation of the underlying film of the ruthenium-containing thin film is also prevented after formation. This prevents an increase in the contact resistance between the ruthenium-containing thin film and the underlying film caused by oxides formed at the interface with the underlying film.

[0116] In addition, when manufacturing ruthenium-containing thin films, by using ruthenium compounds and iodine, (C1-C3) alkyl iodine, halogenated silicon compounds, halogenated tin compounds, or mixtures thereof as specific reaction gases, the crystal quality can be improved, and the resistivity of the thin film can be reduced to below 130 μΩ·cm, preferably below 100 μΩ·cm.

[0117] The invention will now be described in more detail through the following embodiments. Prior to this, the terms or words used in this specification and claims should not be limited to their ordinary or dictionary meanings. Based on the principle that the inventor can appropriately define the concepts of terms in order to best describe their own invention, they should be interpreted in terms of meaning and concept that conform to the technical idea of ​​the invention.

[0118] Therefore, the embodiments described in this specification and the configurations illustrated in the accompanying drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, it should be understood that there are various equivalents and modifications that can be substituted in this application.

[0119] Furthermore, all the embodiments below use a commercially available 200mm single-wafer-type ALD apparatus (CN1, Atomic Premium) with a nozzle configuration and employ a known atomic layer deposition (ALD) method. Alternatively, a commercially available 200mm single-wafer-type CVD (PECVD) apparatus (CN1, Atomic Premium) with a nozzle configuration can be used and employ a known plasma chemical deposition method.

[0120] The resistivity of the deposited ruthenium-containing thin film was measured using a thin film resistivity meter (4-point probe, DASOLENG, ARMS-200C), the thickness was measured using a transmission electron microscope (FEI (Netherlands) Tecnai G²F30S-Twin), and the composition of the film was analyzed using time-of-flight-elastic recoil detection (TOF-ERD, NEC).

[0121] [Example 1] Preparation of Ruthenium Compounds

[0122] Manufacturing of [(Ethylbenzene)RuCl2]2 ([(Ethylbenzene)RuCl2]2)

[0123]

[0124] Ruthenium(III) chloride hydrate (RuCl) 3•n After adding ethanol (2003 ml, 32.94 mol) solution to H₂O (250.5 g, 1.01 mol), the internal temperature was maintained at 66 °C. Then, 1-ethyl-1,4-cyclohexadiene (389 ml, 3.03 mol) was added, and the mixture was refluxed and stirred at 90 °C for 5 hours. The internal temperature was then maintained at 79 °C. After the reaction was complete, recrystallization was performed, and the obtained solid was subjected to reduced pressure to remove the solvent and volatile byproducts, yielding 281.2 g of a brown solid compound (100% yield).

[0125] Manufacturing of (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene)

[0126]

[0127] Sodium carbonate (222.39 g, 2.10 mol) and a 2-propanol solution (1912.4 mL, 24.98 mol) were added to the [(ethylbenzene)RuCl2]2 ([(Ethylbenzene)RuCl2]2) (277.9 g, 0.5 mol) prepared above. At room temperature, 2,3-dimethyl-1,3-butadiene (226.0 mL, 2.00 mol) was added to the stirred suspension, and the mixture was refluxed and stirred at 95 °C for 7 hours. After the reaction was complete, the mixture was filtered. The obtained solution was then subjected to reduced pressure to remove the solvent and volatile byproducts, followed by extraction with n-hexane. After filtering the n-hexane extract, the obtained filtrate was subjected to reduced pressure to remove the solvent, followed by distillation under reduced pressure to obtain 201.9 g of a yellow liquid compound. (Yield 69.8%) The (ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) obtained by the above process is defined as compound 1.

[0128] 1H-NMR (400MHz, 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, C H2=CHC(CH3)=CH2); 0.98 (t, 3H, C6H5CH2CH3); 0.21 (s, 2H, CH2=C(CH3)C(CH3)=CH2).

[0129] To confirm the fundamental thermal properties of the ruthenium compound (compound 1) produced in Example 1 above, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were performed, and the results are presented below. Figure 1 and Figure 2 .

[0130] Figure 1 The results of differential scanning calorimetry (DSC) analysis of 3.7 mg of compound 1 under argon atmosphere at a heating rate of 10 °C / min up to 500 °C are presented. No thermal decomposition peak was observed up to approximately 200 °C, indicating that thermal decomposition occurred at approximately 290 °C.

[0131] Figure 2 The results of thermogravimetric analysis (TGA) of 29.5 mg of Compound 1 measured up to 500 °C under an argon atmosphere at a heating rate of 10 °C / min are shown. The vertical axis represents the percentage weight loss due to temperature increase. It can be seen that Compound 1 exhibits a single evaporation phase around 210 °C and displays rapid vaporization characteristics at 300 °C, with almost no residue. These results confirm that Compound 1 has excellent thermal stability.

[0132] In addition, the vapor pressure was measured according to the temperature change of compound 1 and is shown in... Figure 3 .according to Figure 3 It can be confirmed that the vapor pressure is approximately 1 Torr at 120°C.

[0133] [Example 2] Manufacturing of Ruthenium-containing thin film

[0134] Ruthenium-containing thin films were formed by atomic layer deposition using (ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) as a Ru-containing precursor, as a reaction gas, and diiodomethane (CH2I2) as an iodine-containing precursor.

[0135] The silicon oxide substrate was maintained at 200-300°C. Compound 1 was filled into a stainless steel foam container and maintained at a certain temperature. The compound vaporized in the stainless steel foam container was supplied to the silicon substrate for 5 seconds (0.0084 g) using argon gas as a carrier, causing it to adsorb onto the silicon substrate. Next, unreacted compound was removed using argon gas (2000 sccm) for 5 seconds. Then, diiodomethane (CH2I2) heated to 90°C was supplied for 1.5 seconds (0.018 g), thereby forming a ruthenium-containing thin film. Finally, reaction byproducts and residual reaction gases were removed using argon gas (2000 sccm) for 10 seconds. 2.3 moles of reaction gas (diiodomethane) were used relative to 1 mole of compound 1. The above-described process was repeated for 300 cycles, thereby forming a ruthenium-containing thin film. Detailed thin film manufacturing conditions are shown in Table 1 below.

[0136]

[0137] The growth rate based on the substrate temperature of the ruthenium-containing thin film manufactured according to Example 2 is shown in the figure. Figure 4 .according to Figure 4 It can be seen that the deposition rate of the ruthenium-containing thin film in Example 1 has a certain saturation deposition rate in the temperature range of 220~270℃. This indicates that the above-mentioned ruthenium-containing thin film has a stable deposition process window during mass production.

[0138] The thickness of the ruthenium-containing thin film formed at the substrate temperature was analyzed using scanning electron microscopy (SEM), and the results are shown below. Figure 5 Therefore, it can be concluded that ruthenium-containing films with a uniform surface thickness of less than 2 nm can be manufactured in the temperature range of 220~270℃.

[0139] [Example 3] Manufacturing of Ruthenium-containing thin film

[0140] In Example 2, a ruthenium-containing thin film deposited at a silicon oxide substrate at a deposition temperature of 260°C was heat-treated at 450°C for 30 minutes in a hydrogen atmosphere.

[0141] In Example 2 above, the resistivity of the ruthenium-containing thin films deposited at temperatures of 220°C, 250°C, 260°C, and 270°C, and the ruthenium-containing thin film prepared in Example 3, are shown in Table 2 below. According to Table 2, the resistivity in Example 2 without heat treatment is approximately 100 μΩ·cm, while the resistivity in Example 3 after heat treatment is 25 μΩ·cm, confirming a significant improvement.

[0142]

[0143] In addition, the compositions of the ruthenium-containing thin film at a deposition temperature of 260°C in Example 2 and the ruthenium-containing thin film in Example 3 were analyzed by secondary ion mass spectrometry and are shown in Table 3 below.

[0144] As can be seen from the heat treatment, in Example 3, the carbon (C), iodine (I), and hydrogen (H) elements were significantly reduced, which shows that the resistivity was improved.

[0145]

[0146] [Example 4] Fabrication of Ruthenium Thin Film

[0147] A ruthenium film was deposited in a pattern with an aspect ratio of 27, under the conditions of Example 2. The deposition pattern was determined using transmission electron microscopy and is shown below. Figure 6 It can be confirmed that the ruthenium thin film has a deposition step coverage of 100%.

[0148] Specifically, the appearance of the ruthenium-containing thin film in the trench structure manufactured in Example 2 (substrate temperature: 260°C) was measured by transmission electron microscopy (TEM) and shown. Figure 6 Therefore, it can be seen that ruthenium-containing thin films can be deposited to achieve uniform and excellent step coverage.

[0149] As described above, the present invention has been illustrated by specific details and limited embodiments and comparative examples, but this is only provided to help to understand the invention more completely. The present invention is not limited to the embodiments described above, and those skilled in the art to which this invention pertains can make various revisions and modifications based on such description.

[0150] Therefore, the concept of the present invention is not limited to the illustrated embodiments. Not only the scope of protection claimed by the present invention, but also all forms that are equivalent to or have equivalent variations of the scope of protection claimed by the present invention are within the scope of the present invention.

Claims

1. A method for manufacturing a ruthenium-containing thin film, wherein, Includes the following steps: Ruthenium-containing thin films are fabricated using ruthenium compounds of chemical formula 1 as precursors for thin film deposition, and iodine, (C1-C3) alkyl iodine, halogenated silicon compounds, halogenated tin compounds, or mixtures thereof as reactant gases. [Chemical Formula 1] In the chemical formula 1, R, R1, and R2 are independently C1-C5 alkyl groups.

2. The method for manufacturing 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 method for manufacturing a ruthenium-containing thin film according to claim 1, wherein, The ruthenium compound is a compound represented by the following chemical formula 2. [Chemical Formula 2] 。 4. The method for manufacturing 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] R m MH n X 4-n-m In the chemical formula 3, M is either Sn or Si; R can be 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 from 0 to 3, and n and m cannot both be 0.

5. The method for manufacturing a ruthenium-containing thin film according to claim 1, wherein, The reacting gases are I2, CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, CHBr3, CH2Br2, CH3CHBr2, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiHCl3, S iH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3 Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I.

6. The method for manufacturing a ruthenium-containing thin film according to claim 1, wherein, The manufacturing method includes the following steps: A) The step of maintaining the temperature of the substrate installed in the cavity at 80 to 500°C; B) The steps of injecting the carrier gas and ruthenium compound; and C) The step of producing a ruthenium-containing thin film by injecting iodine, (C1-C3) alkyl iodine, halogenated silicon compound, halogenated tin compound or mixture thereof as a reactant gas.

7. The method for manufacturing a ruthenium-containing thin film according to claim 1, wherein, The manufacturing method includes the following steps: a) The step of maintaining the temperature of the substrate installed in the cavity at 80 to 500°C; b) The step of producing a ruthenium-containing thin film by injecting a ruthenium compound and iodine, (C1-C3) alkyl iodine, halogenated silicon compound, halogenated tin compound or a mixture thereof as a reactant gas.

8. The method for manufacturing a ruthenium-containing thin film according to claim 6 or 7, wherein, Following the step of manufacturing the ruthenium-containing thin film, a heat treatment step is also included.

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

10. The method for manufacturing a ruthenium-containing thin film according to claim 8, wherein, The heat treatment is carried out in hydrogen gas.

11. A composition for ruthenium-containing thin film deposition, wherein, Include: Ruthenium compounds represented by the following chemical formula 1; and Iodine, (C1-C3) alkyl iodine, halogenated silicon compounds, halogenated tin compounds, or mixtures thereof, can be used as reactant gases. [Chemical Formula 1] In the chemical formula 1, R, R1, and R2 are independently C1-C5 alkyl groups.

12. A ruthenium-containing thin film, wherein, It is manufactured using the ruthenium-containing thin film deposition composition according to claim 11, and has a resistivity of 130 μΩ·cm or less.

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