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

Abstract

The present invention provides a method for manufacturing a ruthenium-containing thin film and a ruthenium-containing thin film manufactured thereby. The method for manufacturing a ruthenium-containing thin film of the present invention can easily produce a high-purity thin film through a simple process by using a ruthenium compound and a specific reaction gas.

Description

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

[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.

[0002] Ruthenium possesses excellent electrical properties, including excellent electrical conductivity and the potential to form conductive oxides, and a relatively high work function (Fbulk = 4.71 eV). Furthermore, it is widely used as a thin-film electrode material for semiconductor devices due to its excellent etching properties and lattice adhesion to copper.

[0003] Since semiconductor devices employ highly detailed and three-dimensional designs for high memory capacity and responsiveness, a technology is needed to uniformly form a ruthenium-containing thin film with a thickness of several nanometers on a substrate in order to use ruthenium in semiconductor devices, and in particular, it is necessary to ensure that the unique electrical properties of ruthenium, such as high conductivity, are well utilized.

[0004] Accordingly, methods using molecular beam epitaxy (MBE), chemical vapor deposition (CVD), and physical vapor deposition (PVD) are being studied as thin film deposition methods for semiconductor devices. Recently, as the design rules are reduced due to the miniaturization of semiconductor devices, thin film formation using atomic layer deposition (ALD) that follows a self-limiting surface reaction mechanism is being widely studied as a deposition method that satisfies low-temperature process, precise thickness control, and thin film uniformity and coating property.

[0005] Conventionally, the atomic layer deposition method using Ru(OD)3[tris(2,4-octanedionato)Ruthenium(Ⅲ)], Ru(EtCP)2[bis(ethylcyclopentadienyl)Ruthenium(Ⅱ)], etc. as ruthenium raw materials has low purity of ruthenium deposited on the reaction substrate due to oxygen contained in Ru(OD)3 among the raw materials, and some of them are RuO x There was a limit to the formation. In addition, in the case of Ru(EtCP)2, there is a problem that many impurities remain in the ruthenium thin film because it is difficult for the ruthenium atoms to break the chemical bond and exist independently, and it has the inconvenience of requiring an additional reduction process using O2 plasma for deposition.

[0006] Accordingly, in order to manufacture next-generation semiconductor devices with high precision, it is necessary to develop ruthenium compounds with low resistance and high purity through simpler processes than before.

[0007] The present invention aims to solve the above problems and provides a method for manufacturing a ruthenium-containing thin film using a ruthenium compound as a precursor for ruthenium-containing thin film deposition and a specific reaction gas, and a ruthenium-containing thin film manufactured thereby.

[0008] The present invention also provides a composition for deposition of a ruthenium-containing thin film comprising a ruthenium compound and a specific reaction gas.

[0009] The method for manufacturing a ruthenium-containing thin film of the present invention is as follows:

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

[0011] It may include a step of manufacturing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, 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 independently C1-C5 alkyl.)

[0016] Preferably, in the chemical formula 1 of the method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, R, R1 and R2 may independently be C1-C3 alkyl.

[0017] More preferably, the ruthenium compound of chemical formula 1 according to one embodiment of the present invention 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 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.

[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, monoC1-C3 alkylsilyl, diC1-C3 alkylsilyl or triC1-C3 alkylsilyl,

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

[0027] n and m are integers from 0 to 3, and neither n nor m is 0 at the same time.)

[0028] Preferably, the reaction gas according to one embodiment 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, SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br 2, , CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3, or ICHCHCH2I.

[0029] A method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention

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

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

[0032] C) A step of manufacturing a ruthenium-containing thin film by injecting a reaction gas that is iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound or a mixture thereof; may be included.

[0033] A method for manufacturing a ruthenium-containing thin film according to another embodiment of the present invention is

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

[0035] b) a step of manufacturing a ruthenium-containing thin film by injecting a reaction gas which is a ruthenium compound and iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof; may be included.

[0036] A method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention may further include a heat treatment step after the step of manufacturing the ruthenium-containing thin film.

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

[0038] Preferably, the above heat treatment may be performed under hydrogen gas.

[0039] A composition for thin film deposition containing ruthenium according to one embodiment of the present invention

[0040] A ruthenium compound represented by the following chemical formula 1; and

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

[0042] [Chemical Formula 1]

[0043]

[0044] (In the above chemical formula 1,

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

[0046] A ruthenium-containing thin film according to one embodiment of the present invention is manufactured using a composition for deposition of a ruthenium-containing thin film, and may have a resistivity of 130 μΩ·cm or less.

[0047] The method for manufacturing a ruthenium-containing thin film of the present invention does not use oxygen as a reaction gas in the process of using a ruthenium compound as a precursor for thin film deposition, so a separate reduction process is not required, and thus has excellent convenience.

[0048] The ruthenium-containing thin film manufactured through the above manufacturing method has excellent step coverage and gap fill properties due to the content of impurities such as carbon, oxygen, and hydrogen being minimized, and has high density and purity.

[0049] In addition, the ruthenium-containing thin film manufactured through the above manufacturing method can be deposited uniformly with excellent step coverage for trench, contact, or via patterns.

[0050] Figure 1 is a diagram showing the results of differential scanning calorimetry analysis (DSC) of the ruthenium compound of Example 1.

[0051] Figure 2 is a diagram showing the results of thermal gravimetric analysis (GTA) of the ruthenium compound of Example 1.

[0052] Figure 3 is a drawing showing the results of measuring the vapor pressure according to the temperature change of the ruthenium compound of Example 1.

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

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

[0055] Figure 6 is a drawing showing a ruthenium-containing thin film of Example 4 measured through a transmission electron microscope (TEM).

[0056] The method for manufacturing a ruthenium-containing thin film of the present invention, the composition for depositing a ruthenium-containing thin film, and the ruthenium-containing thin film manufactured using the same are described in detail below. However, unless otherwise defined, the technical and scientific terms used herein have meanings commonly understood by those of ordinary skill in the art to which this invention pertains, and in the following description, descriptions of known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0057] The substituents including “alkyl” and other “alkyl” moieties described herein include both straight-chain and branched forms and have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 3 carbon atoms.

[0058] In addition, the “alkene compound” described herein is an organic radical derived from a hydrocarbon containing one or more double bonds, which is an acyclic or cyclic hydrocarbon compound.

[0059] The present invention provides a method for producing a high-purity ruthenium-containing thin film by a simple process without requiring a separate reduction process by using a ruthenium compound as a precursor and a specific reaction gas such as iodine, (C1-C3) alkyl iodine, iodosilane or a mixture thereof, thereby enabling the production of a thin film with a uniform surface and high step coverage and void-free gap filling.

[0060] A ruthenium compound according to one embodiment of the present invention may be a ruthenium(0) compound in which a ruthenium atom has an oxidation state of +-0.

[0061] A method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention is as follows:

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

[0063] It may include a step of manufacturing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, 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 independently C1-C5 alkyl.)

[0068] The method for manufacturing a ruthenium-containing thin film of the present invention can manufacture a high-purity thin film without using oxygen, which is a conventionally used reaction gas, and can manufacture a ruthenium-containing thin film through a simple process without requiring a separate reduction process to remove oxygen contained in the thin film.

[0069] According to one embodiment of the present invention, R, R1 and R2 of the above chemical formula 1 may independently be C1-C3 alkyl.

[0070] According to one embodiment of the present invention, the ruthenium compound may be a compound represented by the following chemical formula 2.

[0071] [Chemical Formula 2]

[0072]

[0073] 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.

[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, monoC1-C3 alkylsilyl, diC1-C3 alkylsilyl or triC1-C3 alkylsilyl,

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

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

[0081] 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, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br 2, , CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0082] The method for manufacturing a ruthenium-containing thin film of the present invention is not limited to a method for manufacturing a ruthenium-containing thin film by reacting a ruthenium compound as a precursor with a reaction gas such as iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof. Preferably, the method for manufacturing a ruthenium-containing thin film according to an embodiment of the present invention is

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

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

[0085] C) A step of manufacturing a ruthenium-containing thin film on the substrate by injecting a reaction gas that is iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound or a mixture thereof; may be included.

[0086] A method for manufacturing a ruthenium-containing thin film according to another embodiment of the present invention is

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

[0088] b) a step of manufacturing a ruthenium-containing thin film on the substrate by injecting a reaction gas that is a ruthenium compound and iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof; may be included.

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

[0090] In a method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, the heat treatment may be performed under hydrogen gas.

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

[0092] In a method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, the reaction gas may be changed into a gaseous state by heating or the like and introduced into a process chamber where a substrate on which a ruthenium compound is adsorbed exists.

[0093] In a method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, the ruthenium compound and the reaction gas may be supplied to the chamber organically or independently of each other. In addition, the ruthenium compound and the reaction gas may be supplied to the chamber continuously or discontinuously, and the discontinuous supply may include a pulse form.

[0094] In the method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, it goes without saying that a purging step may be further performed by supplying an inert gas into the chamber to exhaust unreacted ruthenium compound gas, by-product gas, or unreacted reaction gas after step B) and / or step C. The inert gas may be one or more selected from nitrogen (N2), argon, and helium. The injection amount of the purge gas is not limited, but may be specifically provided in an injection amount in the range of 800 to 5,000 sccm, and more specifically, may be provided in an injection amount in the range of 1,000 to 3,000 sccm.

[0095] That is, a manufacturing method according to one embodiment of the present invention 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 transport gas and a ruthenium compound; D1) a purge step of purging the inside of the chamber using an inert gas; C) a step of injecting a reaction gas that is iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof to manufacture a ruthenium-containing thin film on the substrate; and D2) a purge step of purging the inside of the chamber using an inert gas.

[0096] In addition, in a manufacturing method according to another embodiment of the present invention, a purge step as described above may be further performed even after step b). Specifically, the method 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 that is a ruthenium compound and iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof to manufacture a ruthenium-containing thin film on the substrate; and D2) a purge step of purging the inside of the chamber using an inert gas.

[0097] According to one embodiment of the present invention, the substrate may be any usable material within the range recognized by those skilled in the art, and the temperature of the substrate is not limited, but may preferably be 200 to 400°C. The temperature range is a temperature range due to the decomposition characteristics of the ruthenium compound itself used as a precursor and the reaction characteristics with the reaction gas, which is iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound, or a mixture thereof used as a reaction gas.

[0098] In one embodiment of the present invention, usable substrates may include, but are not limited to, a substrate including one or more semiconductor materials selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon on insulator (SOI) 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), and polyester; and a tungsten substrate.

[0099] A method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention uses a ruthenium compound as a precursor and a reaction gas that is iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound or a mixture thereof, and the corresponding thin film deposition conditions can be adjusted according to the structure or thermal characteristics of the desired thin film.

[0100] Deposition conditions according to one embodiment of the present invention may include, but are not limited to, the input flow rate of a ruthenium compound as a precursor, the input flow rate of a transport gas, pressure, RF power, substrate temperature, etc., and non-limiting examples of such deposition conditions include, but are not limited to, the input flow rate of the ruthenium compound being 1 to 1000 cc / min, the input flow rate of the transport gas being 1 to 1000 cc / min, the flow rate of the reaction gas being 1 to 1000 cc / min, the pressure being 0.1 to 100 torr, the RF power being 200 to 1000 W, and the substrate temperature being 80 to 500°C, preferably 200 to 400°C.

[0101] 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 the ruthenium compound, but is not limited thereto, and can be adjusted depending on the thin film deposition conditions. For example, in the case of atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD), it can be used in an amount of 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.

[0102] A method for manufacturing 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 manufacturing 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 hour to 2 hours, and may be performed under a hydrogen atmosphere.

[0103] 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, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br 2, , CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0104] In a method for manufacturing a ruthenium-containing thin film according to one embodiment of the present invention, a ruthenium compound may be supplied to a chamber together with a transport gas. Specifically, the transport 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 in a preferred combination with a specific reaction gas of the present invention.

[0105] The ruthenium-containing thin film can be any thin film that can be manufactured within the scope recognizable by those skilled in the art in which a ruthenium precursor is supplied in the vapor phase to manufacture the ruthenium-containing thin film. As a specific and practical example, the ruthenium-containing thin film can be a conductive ruthenium film, a ruthenium oxide film, or a hybrid film thereof. In addition, various high-quality thin films containing ruthenium can be manufactured within the scope recognizable by those skilled in the art.

[0106] The present invention relates to a ruthenium compound represented by the following chemical formula 1; and

[0107] A composition for deposition of a ruthenium-containing thin film is provided, comprising iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas.

[0108] [Chemical Formula 1]

[0109]

[0110] (In the above chemical formula 1,

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

[0112] Preferably, the reaction gas according to one embodiment of the composition for ruthenium-containing thin film deposition of the present invention can 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 1 mole of the ruthenium compound represented by the chemical formula 1.

[0113] Preferably, the reaction gas according to one embodiment of the composition for ruthenium-containing thin film deposition 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, SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br 2, , CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, and more preferably CH2I2.

[0114] In addition, 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, and the manufactured ruthenium-containing thin film may have a resistivity of 130 μΩ·cm or less, preferably 100 μΩ·cm or less.

[0115] The ruthenium-containing thin film of the present invention can be manufactured by a simple process using a ruthenium compound represented by the above chemical formula 1 and a specific reaction gas such as iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound or a mixture thereof. In addition, when manufacturing the ruthenium-containing thin film, by using iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound or a mixture thereof instead of oxygen as a reaction gas, the lower film can be prevented from being oxidized during the deposition process, and the lower film of the ruthenium-containing thin film can be prevented from being oxidized even after being formed. As a result, an increase in contact resistance between the ruthenium-containing thin film and the lower film due to an oxide formed at the interface with the lower film can be prevented.

[0116] In addition, when manufacturing a ruthenium-containing thin film, by using a ruthenium compound and a specific reaction gas such as iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof, the crystal quality can be improved, thereby reducing the resistivity of the thin film to 130 μΩ·cm or less, preferably 100 μΩ·cm or less.

[0117] Hereinafter, the present invention will be described in more detail through the following examples. Prior to this, it should be noted that the terms and words used in this specification and claims should not be construed as limited to their conventional or dictionary meanings. Based on the principle that the inventor can appropriately define the concept of a term to best explain his or her invention, they should be construed as meanings and concepts consistent with the technical spirit of the present invention.

[0118] Therefore, the embodiments described in this specification and the configurations illustrated in the drawings are only the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention, so it should be understood that there are various equivalents and modified examples that can replace them at the time of filing this application.

[0119] In addition, all of the examples below were performed using a commercially available showerhead-type 200 mm single-wafer type ALD equipment (CN1, Atomic Premium) using a known atomic layer deposition (ALD) method. In addition, it is possible to perform the ALD using a commercially available showerhead-type 200 mm single-wafer type CVD (PECVD) equipment (CN1, Atomic Premium) using a known plasma-assisted vapor deposition (PAVD) method.

[0120] The resistivity of the deposited ruthenium-containing thin film was measured using a 4-point probe (DASOLENG, ARMS-200C) and the thickness was measured using a transmission electron microscope (FEI (Netherlands) Tecnai G²F30S-Twin). The composition of the thin film was analyzed using Time of Flight - Elastic Recoil Detection (TOF-ERD), NEC.

[0121]

[0122] [Example 1] Preparation of ruthenium compounds

[0123] Preparation of [(Ethylbenzene)RuCl2]2

[0124]

[0125] Ruthenium(III) chloride hydrate (RuCl 3·nH2O) (250.5 g, 1.01 mol) was added to ethanol solution (2003 ml, 32.94 mol), and then 1-ethyl-1,4-cyclohexadiene (389 ml, 3.03 mol) was added while maintaining the internal temperature at 66°C, and the mixture was stirred under reflux at 90°C for 5 hours. During this time, the internal temperature was maintained at 79°C. After completion of the reaction, the solid obtained by recrystallization was removed under reduced pressure to obtain 281.2 g of a brown solid compound. (Yield 100%)

[0126]

[0127] Preparation of (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene)

[0128]

[0129] Sodium carbonate (222.39 g, 2.10 mol) and 2-propanol solution (1912.4 ml, 24.98 mol) were added to the [(Ethylbenzene)RuCl2]2 (277.9 g, 0.5 mol) prepared above, and the turbid solution was stirred. 2,3-dimethyl-1,3-butadiene (226.0 ml, 2.00 mol) was added to the stirred turbid solution at room temperature, and the mixture was refluxed and stirred for 7 hours at 95°C. After the reaction was completed, the solution was filtered, and the solvent and volatile by-products were removed under reduced pressure, and then extracted using n-hexane. The n-hexane extract was filtered, and the filtrate obtained was distilled under reduced pressure to obtain 201.9 g of a yellow liquid compound. (Yield 69.8%) (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) obtained through the above process was defined as compound 1.

[0130] 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).

[0131]

[0132] In order to confirm the basic thermal properties of the ruthenium compound (compound 1) manufactured in Example 1 above, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were performed, and the results are shown in FIGS. 1 and 2.

[0133] Figure 1 shows the results of differential scanning calorimetry (DSC) analysis of compound 1, 3.7 mg, measured at a heating rate of 10°C up to 500°C in an argon atmosphere. No thermal decomposition peak was observed up to about 200°C, and thermal decomposition occurred at about 290°C.

[0134] Figure 2 shows the results of thermogravimetric analysis of compound 1 (29.5 mg) measured in an argon atmosphere at a heating rate of 10°C up to 500°C, with the vertical axis representing the percentage of weight loss with increasing temperature. It can be seen that compound 1 has a single evaporation step around 210°C and exhibits rapid vaporization characteristics with almost no residue mass at 300°C. The above results confirm that compound 1 has excellent thermal stability.

[0135] Additionally, the vapor pressure of compound 1 according to temperature change was measured and shown in Fig. 3. According to Fig. 3, a vapor pressure of approximately 1 Torr can be confirmed under 120°C conditions.

[0136]

[0137] [Example 2] Manufacturing of a ruthenium-containing thin film

[0138] A ruthenium-containing thin film was formed by atomic layer deposition using a Ru-containing precursor (Ethylbenzene)Ru(2,3-dimethyl-1,3-butadiene) and an iodine-containing precursor Diiodomethane(CH2I2) as a reaction gas.

[0139] The silicon oxide film substrate was maintained at 200-300℃, and compound 1 was filled into a stainless steel bubbler vessel and maintained at a constant temperature. The vaporized compound in the stainless steel bubbler vessel was supplied for 5 seconds (0.0084 g) using argon gas as a transport gas to be transferred to the silicon oxide film substrate and adsorbed onto the silicon oxide film substrate. Next, unreacted compounds were removed for 5 seconds using argon gas (2000 sccm). Thereafter, diiodomethane (CH2I2) heated to 90℃ 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 for 10 seconds using argon gas (2000 sccm). The reaction gas (diiodomethane) was used in an amount of 2.3 mol per 1 mol of compound 1. The above process was repeated 300 times, with one cycle being the process, to form a ruthenium-containing thin film. Detailed thin film manufacturing conditions are shown in Table 1 below.

[0140] Thin film manufacturing conditions Substrate temperature (℃) 220, 240, 260, 270, 280, 300Ru precursor Precursor injection time (sec) 5 Purge (Arcon) flow rate (sccm) 2000 Time (sec) 5 Diiodomethane (reaction gas) Reaction time Heating temperature (℃) 90 Precursor injection time (sec) 1.5 Purge (Arcon) flow rate (sccm) 2000 Time (sec) 10 Number of deposition cycles Cycles 300

[0141] The growth rate of the ruthenium-containing thin film manufactured through Example 2 according to the substrate temperature is shown in Fig. 4. According to Fig. 4, it can be seen that the deposition rate of the ruthenium-containing thin film of Example 1 has a constant saturation deposition rate in the range of 220 to 270°C. This shows that the ruthenium-containing thin film can have a safe deposition margin when mass-produced.

[0142] The thickness of the ruthenium-containing thin film formed depending on the temperature of the substrate was analyzed using a scanning electron microscope (SEM), and the results are shown in Fig. 5. This shows that a uniform surface thin film with a thickness of less than 2 nm can be produced in the ruthenium-containing thin film range of 220 to 270°C.

[0143]

[0144] [Example 3] Preparation of ruthenium-containing thin film

[0145] In Example 2, a ruthenium-containing thin film was heat-treated at 450°C for 30 minutes in a hydrogen atmosphere when the deposition temperature of the silicon oxide film substrate was 260°C.

[0146]

[0147] The resistivity values ​​of the ruthenium-containing thin film manufactured at deposition temperatures of 220°C, 250°C, 260°C, and 270°C in Example 2 and the ruthenium-containing thin film manufactured through Example 3 are shown in Table 2 below. According to Table 2, in the case of Example 2 without heat treatment, the resistivity value is about 100 μΩ·cm, and in the case of Example 3 after heat treatment, the resistivity is greatly improved to 25 μΩ·cm.

[0148] Conditional Deposition Temperature (℃) Heat Treatment Temperature (℃) Resistivity (μΩ*cm) Example 2 220-120 250-97 260-115 270-113 Example 3 260 450 25

[0149] In addition, the composition of the ruthenium-containing thin film of Example 2 when the deposition temperature was 260°C and the ruthenium-containing thin film of Example 3 were analyzed using a secondary ion mass spectrometer and are shown in Table 3 below.

[0150] It can be seen that the carbon (C), iodine (I), and hydrogen (H) elements were significantly reduced in Example 3 according to the heat treatment, and thus the resistivity was seen to have improved.

[0151] Condition Example 2 (deposition temperature 260℃) Example 3 Resistivity (uΩcm) 11525 Secondary ion mass analyzer Intensity (count / sec) Ru 2 4 3 4 13 2 8 0 5 O 5 6 15 4 C 6 6 2 6 10 7 I 7 14 6 9 H 19 9 6 0

[0152] [Example 4] Fabrication of ruthenium thin film

[0153] A ruthenium thin film was deposited under the conditions of Example 2 on a pattern with an aspect ratio of 27. The deposition pattern was measured using a transmission electron microscope (TEM) and is shown in Fig. 6. It was confirmed that the deposition aspect ratio (step coverage) of the ruthenium thin film was 100%.

[0154] Specifically, the appearance of the ruthenium-containing thin film in the trench structure manufactured in Example 2 (substrate temperature: 260°C) was measured using a transmission electron microscope (TEM) and is shown in Fig. 6. This shows that the ruthenium-containing thin film can be deposited uniformly and with excellent step coverage.

[0155]

[0156] As described above, the present invention has been described through specific matters and limited examples and comparative examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0157] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A ruthenium compound of the following chemical formula 1 is used as a precursor for thin film deposition, A method for producing a ruthenium-containing thin film, comprising: a step of producing a ruthenium-containing thin film using iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof as a reaction gas. [Chemical Formula 1] (In the above chemical formula 1, R, R1 and R2 are independently C1-C5 alkyl.) 2. In paragraph 1, A method for producing a ruthenium-containing thin film, wherein in the above chemical formula 1, R, R1 and R2 are independently C1-C3 alkyl.

3. In paragraph 1, A method for producing a ruthenium-containing thin film, wherein the above ruthenium compound is a compound represented by the following chemical formula 2. [Chemical Formula 2] 4. In paragraph 1, A method for producing a ruthenium-containing thin film, 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 above chemical formula 3 M is Sn or Si; R is hydrogen, C1-C3 alkyl, C2-C3 alkenyl, monoC1-C3 alkylsilyl, diC1-C3 alkylsilyl or triC1-C3 alkylsilyl, X is F, Cl, Br or I, n and m are integers from 0 to 3, and neither n nor m is 0 at the same time.) 5. In paragraph 1, The reaction 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, SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, SnH2Br 2, , CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3 or ICHCHCH2I, a method for producing a ruthenium-containing thin film.

6. In paragraph 1, The above manufacturing method 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 transport gas and a ruthenium compound; and C) A method for producing a ruthenium-containing thin film, comprising the step of producing a ruthenium-containing thin film by injecting a reaction gas that is iodine, (C1-C3) alkyl iodine, a halogen-containing silicon compound, a halogen-containing tin compound, or a mixture thereof.

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

8. In paragraph 6 or 7, A method for manufacturing a ruthenium-containing thin film, further comprising a heat treatment step after the step of manufacturing the ruthenium-containing thin film.

9. In paragraph 8, A method for manufacturing a ruthenium-containing thin film, wherein the above heat treatment is performed at 200 to 700°C.

10. In paragraph 8, A method for manufacturing a ruthenium-containing thin film, wherein the above heat treatment is performed under hydrogen gas.

11. A ruthenium compound represented by the following chemical formula 1; and A composition for deposition of a ruthenium-containing thin film, comprising iodine, (C1-C3) alkyl iodine, halogen-containing silicon compound, halogen-containing tin compound or a mixture thereof as a reaction gas. [Chemical Formula 1] (In the above chemical formula 1, R, R1 and R2 are independently C1-C5 alkyl.) 12. A ruthenium-containing thin film manufactured using the composition for thin film deposition of Article 11, and having a resistivity of 130 μΩ·cm or less.

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