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WO2019088722A1 - Procédé de production d'un film mince contenant du ruthénium, et film mince contenant du ruthénium produit par celui-ci - Google Patents

Procédé de production d'un film mince contenant du ruthénium, et film mince contenant du ruthénium produit par celui-ci Download PDF

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Publication number
WO2019088722A1
WO2019088722A1 PCT/KR2018/013160 KR2018013160W WO2019088722A1 WO 2019088722 A1 WO2019088722 A1 WO 2019088722A1 KR 2018013160 W KR2018013160 W KR 2018013160W WO 2019088722 A1 WO2019088722 A1 WO 2019088722A1
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Prior art keywords
ruthenium
thin film
containing thin
compound
alkyl
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English (en)
Korean (ko)
Inventor
김명운
이상익
조성우
한미정
임행돈
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DNF Co Ltd
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DNF Co Ltd
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Priority claimed from KR1020180131423A external-priority patent/KR102374140B1/ko
Application filed by DNF Co Ltd filed Critical DNF Co Ltd
Priority to US16/760,417 priority Critical patent/US11827650B2/en
Priority to JP2020543444A priority patent/JP7355746B2/ja
Priority to CN201880072781.1A priority patent/CN111357080B/zh
Publication of WO2019088722A1 publication Critical patent/WO2019088722A1/fr
Anticipated expiration legal-status Critical
Priority to JP2023109937A priority patent/JP7751610B2/ja
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • H10P14/42—
    • H10P95/00—
    • H10P95/90—

Definitions

  • the present invention relates to a process for producing a ruthenium-containing thin film and a ruthenium-containing thin film prepared therefrom, and more particularly, to a process for producing a ruthenium-containing thin film using iodine, alkyl iodide, Silyl iodide or a mixture thereof to produce a ruthenium-containing thin film, and a ruthenium-containing thin film prepared therefrom.
  • Bimetallic ruthenium or ruthenium oxide is widely used in semiconductor devices due to its low resistance, large work function and thermal and chemical stability.
  • metal ruthenium is superior in electric characteristics to ruthenium oxide and is preferable as a thin film electrode material for a semiconductor device.
  • the ruthenium (Ru) thin film is used as a seed layer in a wiring structure of a semiconductor device, or as an electrode of a gate or a capacitor of a transistor. Due to the high integration and miniaturization of semiconductor devices, Thin films also require improved uniformity and coating properties.
  • MBE molecular beam epitaxy
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • ALD atomic layer deposition
  • Ru (OD) 3 tris ( 2,4-octanedionato) Ruthenium (III)]
  • Ru (EtCP) 2 bis (ethylcyclopentadienyl ) Ruthenium (II)]
  • Ru (OD) 3 contains oxygen, which makes it difficult to deposit pure ruthenium on the reaction substrate, and further RuO x is formed on a part of the substrate.
  • Ru (EtCP) 2 is because cyclopentadiene (Cyclopentadiene) not breaking the nature of the ruthenium atom is chemically bonded in the series to be easily decomposed remains the problem has not only a lot of impurities to be difficult ruthenium thin film to exist independently O 2 Since the RuO 2 film is formed by vapor deposition using a plasma, there is a problem that a process of reducing H 2 again is required in order to obtain a Ru film. In the case of the Ru (0) compound, although the formation of the RuO x thin film was reduced by controlling the amount of the reactive gas O 2, the problem still remains.
  • the present invention provides a method for producing a ruthenium-containing thin film using a ruthenium (0) -based hydrocarbon compound as a ruthenium-containing thin film deposition precursor and a specific reaction gas and a ruthenium- do.
  • the present invention also provides a ruthenium-containing thin film deposition composition comprising a ruthenium (0) based hydrocarbon compound and a specific reaction gas.
  • the present invention provides a method for producing a high-purity ruthenium-containing thin film by a simple process using a ruthenium (0) based hydrocarbon compound as a precursor and a specific reaction gas.
  • the method for producing a ruthenium-containing thin film of the present invention comprises:
  • the method for preparing a ruthenium-containing thin film according to an exemplary embodiment of the present invention may be applied to various thin film deposition methods such as atomic layer deposition (ALD), vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition , (PECVD) or plasma enhanced atomic layer deposition (PEALD).
  • ALD atomic layer deposition
  • CVD vapor deposition
  • MOCVD metalorganic chemical vapor deposition
  • LPCVD low pressure vapor deposition
  • PECVD plasma enhanced vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • the method for producing a ruthenium-containing thin film according to an embodiment of the present invention comprises
  • a reactive gas which is iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof to prepare a ruthenium-containing thin film on the substrate.
  • the reaction gas according to an embodiment of the present invention may be used in an amount of 0.1 to 200 moles per mole of the ruthenium (0) based hydrocarbon compound.
  • the method for producing a ruthenium-containing thin film according to an embodiment of the present invention may further include a step of performing heat treatment after step c), and the heat treatment may be performed at 200 to 700 ° C.
  • the ruthenium (0) based hydrocarbon compound according to one embodiment of the present invention may be represented by the following formula (1).
  • L is a non-cyclic alkene compound having 2 to 10 carbon atoms, a cyclic alkene compound having 3 to 10 carbon atoms, an alkenyl compound having 2 to 10 carbon atoms and 1 to 4 hetero atoms selected from nitrogen or oxygen, 8 is a neutral ligand which is a compound selected from the group consisting of acyclic or cyclic heteroalkene-like structural compounds or carbonyl group-containing compounds;
  • R 1 to R 6 are independently of each other hydrogen or (C 1 -C 7 ) alkyl.
  • the ruthenium (0) based hydrocarbon compound of Formula 1 may be represented by Formula 1-1 or 1-2 below.
  • R 1 to R 10 independently from each other are hydrogen or (C 1 -C 7) alkyl
  • a 1 is a single bond or - (CR 11 R 12 ) m -, R 11 and R 12 are each independently hydrogen or (C 1 -C 7) alkyl, m is an integer of 1 to 3,
  • a 2 is - (CR 11 R 12 ) n -, R 11 and R 12 are each independently hydrogen or (C 1 -C 7) alkyl, and n is an integer of 1 to 3.
  • the ruthenium (0) based hydrocarbon compound according to one embodiment of the present invention may be represented by the following general formula (2) or (3).
  • R 1 to R 6 independently of one another are hydrogen or (C 1 -C 7 ) alkyl
  • R 7 to R 10 independently from each other are hydrogen or (C 1 -C 7 ) alkyl
  • a 1 is a single bond or - (CR 11 R 12 ) m -, R 11 and R 12 are independently of each other hydrogen or (C 1 -C 7) alkyl, and m is an integer of 1 to 3.
  • the reaction gas according to an exemplary embodiment of the present invention includes at least one of I 2 , CH 3 I, CH 2 I 2 , CHI 3 , CH 3 CH 2 I, CH 3 CHI 2 , ICH 2 CH 2 I, CH 3 CH 2 CH 2 I, CH 3 CHICH 3 , ICH 2 CH 2 CH 2, or SiH 2 I 2
  • the transport gas may be any one or two or more selected from nitrogen (N 2 ), hydrogen, argon and helium.
  • the present invention also provides a ruthenium-containing thin film deposition composition
  • a ruthenium-containing thin film deposition composition comprising a ruthenium (0) based hydrocarbon precursor compound and a reaction gas which is iodine, (C1-C3) alkyl iodide, iodide silane or a mixture thereof.
  • 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 per mole of the ruthenium (0) based hydrocarbon compound, and the ruthenium (0) , Ruthenium (0) -based hydrocarbon compounds represented by the general formulas (2) and (3), or a combination thereof.
  • the reaction gas according to one embodiment of the ruthenium-containing thin film deposition composition of the present invention is at least one selected from the group consisting of I 2 , CH 3 I, CH 2 I 2 , CHI 3 , CH 3 CH 2 I, CH 3 CHI 2 , ICH 2 CH 2 I, may be CH 3 CH 2 CH 2 I, CH 3 CHICH 3, ICH 2 CH 2 CH 2 , or SiH 2 I 2.
  • the present invention also provides a ruthenium-containing thin film prepared using the ruthenium-containing thin film deposition composition according to an embodiment of the present invention, wherein the ruthenium-containing thin film has a specific resistance of 100 ⁇ ? ⁇ Cm or less, Can be less than 3 at%.
  • the ruthenium-containing thin film of the present invention may have a carbon content of 3 at% or less.
  • the method for producing a ruthenium-containing thin film of the present invention uses a ruthenium (0) -based hydrocarbon compound as a precursor for thin film deposition, but uses a reactive gas such as iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof as a specific reaction gas And thus a ruthenium-containing thin film can be produced by a simple process since no oxygen is contained and no separate reduction process is required.
  • the method for producing a ruthenium-containing thin film of the present invention can produce a thin film having a uniform surface at a thickness of 2 nm or less and enables gap fill without high step coverage and voids .
  • the method for producing a ruthenium-containing thin film of the present invention minimizes the content of impurities such as carbon, oxygen and hydrogen by using iodine, (C1-C3) alkyl iodide, iodide silane or a mixture thereof without using oxygen as a reaction gas
  • impurities such as carbon, oxygen and hydrogen
  • the ruthenium-containing thin film of the present invention can be produced by using various ruthenium (0) -based hydrocarbon compounds as precursors.
  • the ruthenium-containing thin film deposition composition of the present invention can be produced by using iodine, (C1-C3) alkyl iodide, iodide silane, or a mixture thereof as a reaction gas, thereby providing excellent step coverage and gap fill And a high-purity thin film having high density can be easily obtained.
  • the ruthenium-containing thin film produced by the method of the present invention can be deposited uniformly and with excellent step coverage for a trench, contact or via pattern having a high aspect ratio due to miniaturization of the semiconductor device.
  • FIG. 1 is a graph showing the results of a Gap fill by TEM analysis after the ruthenium thin film of Example 1 was heat-treated in a hydrogen atmosphere
  • Fig. 2 is a diagram showing a result (a) and a step coverage (b) of a Gap fill through TEM analysis of the ruthenium thin film of Example 2.
  • Fig. 3 is a graph showing a result (a) and a step coverage result (b) of a Gap fill through TEM analysis of the ruthenium thin film of Example 2
  • Example 5 shows the growth rate of the ruthenium thin film according to the injection time of the ruthenium precursor in Example 7
  • FIG. 6 - Figs. 8 to 10 show the growth rates of ruthenium thin films with time of ruthenium precursor injection
  • Alkyl " and other " alkyl " moieties as used herein includes both straight-chain or branched forms and includes 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 3 Carbon atoms.
  • alkene compound described in the present specification is an organic radical derived from a hydrocarbon containing at least one double bond as a non-cyclic or cyclic hydrocarbon compound,
  • heteroalkene-like compound is an alkene compound containing at least one heteroatom in the alkene compound, and may be a noncyclic or cyclic type, and the heteroatom may be selected from nitrogen, oxygen, sulfur, phosphorus and the like, And may contain one or more of oxygen or nitrogen.
  • the carbonyl-containing compound described in this specification can be used as a ligand of a ruthenium (0) -based hydrocarbon compound, and any compound having a carbonyl group can be used, but a preferable example thereof is CO or acetylacetonate, but is not limited thereto.
  • the present invention uses a ruthenium (0) based hydrocarbon compound as a precursor and uses a specific reaction gas such as iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof,
  • a specific reaction gas such as iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof.
  • the present invention provides a method for producing a ruthenium-containing thin film having a thickness of 2 nm or less, and can produce a thin film having a uniform surface with a thickness of 2 nm or less and enables a gap fill without a high step coverage and a void.
  • the method for producing a ruthenium-containing thin film of the present invention comprises:
  • the method for producing a ruthenium-containing thin film of the present invention can produce a thin film of high purity without using oxygen, which is a reaction gas used in the prior art. Since a separate reduction process for removing oxygen contained in the thin film is not necessary, A ruthenium-containing thin film can be produced.
  • the method for preparing a ruthenium-containing thin film according to an exemplary embodiment of the present invention may be applied to various thin film deposition methods such as atomic layer deposition (ALD), vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), and may be an atomic layer deposition (ALD) method or a vapor deposition (CVD) method in view of high purity and excellent physical properties.
  • ALD atomic layer deposition
  • CVD vapor deposition
  • MOCVD metalorganic chemical vapor deposition
  • LPCVD low pressure vapor deposition
  • PECVD plasma enhanced vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • PEALD plasma enhanced atomic layer deposition
  • the method for producing a ruthenium-containing thin film of the present invention is a method for producing a ruthenium-containing thin film by reacting a precursor ruthenium (0) based hydrocarbon compound with a reaction gas of iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof
  • the method for producing a ruthenium-containing thin film according to an embodiment of the present invention preferably includes
  • a reactive gas which is iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof to prepare a ruthenium-containing thin film on the substrate.
  • the ruthenium (0) -based hydrocarbon compound used as the precursor may be changed into a gaseous state by heating or the like to be deposited in the process chamber have.
  • the reaction gas is changed to a gaseous state by heating or the like, and then the reaction gas is introduced into a process chamber where a substrate on which a ruthenium (0) .
  • the ruthenium (0) -based hydrocarbon compound and the reaction gas may be supplied to the chamber either organically or independently of each other. Further, the ruthenium (0) based hydrocarbon compound and the reaction gas may be continuously or discontinuously supplied to the chamber, respectively, and the discontinuous supply may include a pulse form.
  • unreacted ruthenium (0) hydrocarbon compound gas, by-produced gas, or unreacted reaction gas after b) and / It is of course possible to carry out a step of purging by supplying an inert gas in the chamber.
  • the inert gas may be any one or two or more selected from nitrogen (N2), argon and helium.
  • the amount of the purge gas to be injected is not limited. Specifically, the purge gas may be supplied in an amount ranging from 800 to 5,000 sccm, and more specifically, in an amount ranging from 1,000 to 3,000 sccm.
  • a manufacturing method includes the steps of: a) maintaining a temperature of a substrate mounted in a chamber at 80 to 500 ⁇ ; b) injecting a transfer gas and a ruthenium (0) based hydrocarbon compound; d1) purging the interior of the chamber using an inert gas; c) injecting a reactive gas that is iodine, (C1-C3) alkyl iodide, iodide silane, or a mixture thereof to produce a ruthenium-containing thin film on the substrate; And d2) purging the interior of the chamber using an inert gas.
  • the substrate according to an exemplary embodiment of the present invention may be any substrate that can be used within a range recognized by a person skilled in the art.
  • the temperature of the substrate is not particularly limited, but may be preferably 200 to 400 ° C. (C1-C3) alkyl iodide, iodinated silane, or a mixture thereof, which is used as the reaction gas, and the decomposition characteristics of the ruthenium (0) based hydrocarbon compound itself and the reaction gas.
  • a substrate usable in one embodiment of the present invention includes a substrate comprising at least one semiconductor material selected from the group consisting of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP; An SOI (Silicon On Insulator) substrate; Quartz substrate; Or glass substrate for display; Polyimide, polyethylene terephthalate, polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyether sulfone (PES), and polyester (Polyester); Tungsten substrate, but is not limited thereto.
  • the method for producing a ruthenium-containing thin film according to an embodiment of the present invention includes using a ruthenium (0) -based hydrocarbon compound as a precursor and a reaction gas of iodine, (C1-C3) alkyl iodide, silane iodide or a mixture thereof
  • a reaction gas of iodine, (C1-C3) alkyl iodide, silane iodide or a mixture thereof The thin film deposition conditions other than the above can be controlled according to the structure or thermal property of the desired thin film.
  • Examples of the deposition conditions according to an embodiment of the present invention include a flow rate of a ruthenium (0) based hydrocarbon compound as a precursor, a feed flow rate of a transfer gas, a pressure, an RF power and a substrate temperature.
  • the flow rate of the ruthenium (0) based hydrocarbon compound is 1 to 1000 cc / min
  • the feed gas is 1 to 1000 cc / min
  • the flow rate of the reaction gas is 1 to 1000 cc / torr
  • RF power of 200 to 1000 W and substrate temperature of 80 to 500 ° C, preferably 200 to 400 ° C, but is not limited thereto.
  • the reaction gas according to an embodiment of the present invention may be used in an amount of 0.1 to 200 moles per mole of the ruthenium (0) based hydrocarbon compound, but is not limited thereto and may be controlled according to the thin film deposition conditions.
  • ALD atomic layer deposition
  • PEALD plasma enhanced atomic layer deposition
  • CVD vapor deposition
  • 1 to 100 moles more preferably 1 to 100 moles per 1 mole of ruthenium (0) To 50 moles, and more preferably from 2 to 30 moles.
  • the method for producing a ruthenium-containing thin film according to an embodiment of the present invention may further include a step of performing heat treatment after step c), and the heat treatment is performed at a temperature of 200 to 700 ° C for 30 minutes to 4 hours, , For 1 hour to 2 hours, and can be carried out under a hydrogen atmosphere.
  • the ruthenium (0) -based hydrocarbon compound according to an embodiment of the present invention can be any ruthenium (0) -based hydrocarbon compound usable as a ruthenium-containing thin film deposition precursor, but the reaction gas iodine, (C1- Iodide silane, or a mixture thereof, the ruthenium (0) based hydrocarbon compound may be represented by the following general formula (1).
  • L is a non-cyclic alkene compound having 2 to 10 carbon atoms, a cyclic alkene compound having 3 to 10 carbon atoms, an alkenyl compound having 2 to 10 carbon atoms and 1 to 4 hetero atoms selected from nitrogen or oxygen, 8 is a neutral ligand which is a compound selected from the group consisting of acyclic or cyclic heteroalkene-like structural compounds or carbonyl group-containing compounds;
  • R 1 to R 6 are independently of each other hydrogen or (C 1 -C 7 ) alkyl.
  • L in formula (1) is a monocyclic alkene compound having 2 to 10 carbon atoms, a cyclic alkene compound having 3 to 10 carbon atoms, And may be one kind of neutral ligand compound selected from the group consisting of acyclic or cyclic heteroalkene-like structural compounds having 2 to 8 carbon atoms and CO and / or acetylacetonate, more preferably L is a linear or branched, , A cyclic alkene compound having 3 to 10 carbon atoms or CO present in the presence of 1 to 4 double bonds.
  • the ruthenium (0) based hydrocarbon compound of Formula 1 may be represented by Formula 1-1 or Formula 1-2.
  • R 1 to R 10 independently from each other are hydrogen or (C 1 -C 7) alkyl
  • a 1 is a single bond or - (CR 11 R 12 ) m -, R 11 and R 12 are each independently hydrogen or (C 1 -C 7) alkyl, m is an integer of 1 to 3,
  • a 2 is - (CR 11 R 12 ) n -, R 11 and R 12 are each independently hydrogen or (C 1 -C 7) alkyl, and n is an integer of 1 to 3.
  • R 1 to R 10 independently represent hydrogen or (C 1 -C 5) alkyl
  • a 1 represents a single bond or - (CR 11 R 12) m - and, a 2 is - (CR 11 R 12) n -
  • R 11 and R 12 are independently hydrogen or (C1-C5) alkyl each other
  • m is an integer from 1 to 2
  • n is And may be an integer of 1 to 2.
  • the ruthenium (0) -based hydrocarbon compound according to a preferable combination of iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof as a reaction gas is represented by the following formula .
  • R 1 to R 6 independently of one another are hydrogen or (C 1 -C 7 ) alkyl
  • R 7 to R 10 independently from each other are hydrogen or (C 1 -C 7 ) alkyl
  • a 1 is a single bond or - (CR 11 R 12 ) m -, R 11 and R 12 are independently of each other hydrogen or (C 1 -C 7) alkyl, and m is an integer of 1 to 3.
  • R 1 to R 6 in the formula (2) or (3) according to an embodiment of the present invention are independently of each other hydrogen or (C 1 -C 5) alkyl and R 7 to R 10 independently of one another are hydrogen or A 1 is a single bond or - (CR 11 R 12 ) m -, R 11 and R 12 are independently of each other hydrogen or (C 1 -C 5) alkyl, and m is an integer of 1 to 2.
  • the ruthenium (0) based hydrocarbon compound according to an embodiment of the present invention may be a compound selected from the following structures, but is not limited thereto.
  • R 1 to R 10 are independently of each other hydrogen or (C 1 -C 7) alkyl
  • the reaction gas according to an exemplary embodiment of the present invention includes at least one of I 2 , CH 3 I, CH 2 I 2 , CHI 3 , CH 3 CH 2 I, CH 3 CHI 2 , ICH 2 CH 2 I, CH 3 CH 2 CH 2 I, CH 3 CHICH 3 ICH 2 CH 2 CH 2 I or SiH 2 I 2 , more preferably CH 3 CH 2 I, CH 2 I 2 , ICH 2 CH 2 CH 2 I or SiH 2 I 2 Lt; / RTI >
  • a ruthenium (0) based hydrocarbon compound may be supplied to the chamber together with the transfer gas.
  • the transfer gas may be any one or two or more selected from nitrogen (N 2 ), hydrogen, argon and helium, and may be selected from nitrogen (N 2 ), argon and helium in a preferred combination with the particular reaction gas of the present invention And may be any one or two or more inert gases.
  • the ruthenium-containing thin film may be any thin film that can be manufactured within a range that can be recognized by those skilled in the art to produce a ruthenium-containing thin film by vapor-phase supplying a ruthenium precursor.
  • the ruthenium-containing thin film may be ruthenium, ruthenium oxide, or a mixed film of ruthenium and ruthenium, which usually have conductivity.
  • various high-quality thin films containing ruthenium can be produced within a range that can be recognized by those skilled in the art.
  • the present invention also provides a ruthenium-containing thin film deposition composition
  • a ruthenium-containing thin film deposition composition comprising a ruthenium (0) based hydrocarbon precursor compound and a reaction gas which is iodine, (C1-C3) alkyl iodide, iodide silane or a mixture thereof.
  • the reaction gas according to one embodiment of the ruthenium-containing thin film deposition composition of the present invention is used in an amount of 0.1 to 200 moles, preferably 1 to 100 moles, more preferably 1 to 100 moles per 1 mole of the ruthenium (0)
  • the ruthenium (0) -based hydrocarbon compound may be used in an amount of 1 to 50 mol, and more preferably 2 to 30 mol, in the ruthenium (0) -based hydrocarbon compound represented by the above formulas Or more.
  • the reaction gas according to one embodiment of the ruthenium-containing thin film deposition composition of the present invention is at least one selected from the group consisting of I 2 , CH 3 I, CH 2 I 2 , CHI 3 , CH 3 CH 2 I, CH 3 CHI 2 , ICH 2 CH 2 I, may be CH 3 CH 2 CH 2 I, CH 3 CHICH 3, ICH 2 CH 2 CH 2 I , or SiH 2 I 2.
  • the present invention also provides a ruthenium-containing thin film prepared using the ruthenium-containing thin film deposition composition according to an embodiment of the present invention, wherein the ruthenium-containing thin film has a specific resistance of 100 ⁇ ? ⁇ Cm or less, preferably 50 ⁇ ⁇ cm or less, more preferably 30 ⁇ ⁇ cm or less, and the oxygen content may be 3 at% or less, preferably 1 at% or less.
  • the ruthenium-containing thin film according to an embodiment of the present invention may have a carbon content of 3 at% or less, preferably 1 at% or less.
  • the ruthenium-containing thin film of the present invention can be obtained by using a ruthenium-containing thin film having high purity, high density and high durability by using a ruthenium (0) -based hydrocarbon compound and a specific reaction gas iodine, (C1- C3) alkyl iodide, It can be manufactured by a simple process. Further, by using iodine, (C1-C3) alkyl iodide, silane iodide, or a mixture thereof instead of oxygen as a reaction gas in the production of the ruthenium-containing thin film, the lower film may not be oxidized during the deposition process, The film may not be oxidized. Thus, it is possible to prevent an increase in the contact resistance between the ruthenium-containing thin film and the lower film due to the oxide formed at the interface with the lower film.
  • the crystal quality is improved by using a ruthenium (0) based hydrocarbon compound and a specific reactive gas such as iodine, (C1-C3) alkyl iodide, silane iodide or a mixture thereof.
  • a specific reactive gas such as iodine, (C1-C3) alkyl iodide, silane iodide or a mixture thereof.
  • cm or less preferably 50 ⁇ ⁇ cm m or less, more preferably 30 ⁇ ⁇ cm m or less
  • the content of oxygen in the thin film can be reduced to 3 at% or less, preferably 1% or less .
  • the resistivity of the deposited ruthenium-containing thin film was measured using a sheet resistance meter (4pointprobe, DASOLENG, ARMS-200C) and the thickness was measured through a transmission electron microscope (FEI (Netherlands) Tecnai G2F30S-Twin)
  • FEI Transmission electron microscope
  • the composition of thin films was analyzed by time-of-flight (Elastic Recoil Detection (TOF-ERD), NEC).
  • Ru-containing precursor compound (Compound 1) was used as a reaction gas, and a ruthenium-containing thin film was formed by atomic layer deposition using iodine ethane (CH 3 CH 2 I) as a reaction gas.
  • the silicon oxide film substrate was maintained at 250 DEG C, and compound 1 was filled in a stainless steel bubbler container and maintained at 110 DEG C.
  • the vaporized compound 1 was supplied to the silicon oxide film substrate for 3 seconds (0.0015 g) using argon gas (50 sccm) as a transfer gas to be adsorbed on the silicon oxide film substrate.
  • argon gas 50 sccm
  • unreacted Compound 1 was removed for 1 second by using argon gas (3000 sccm).
  • iodoethane (CH 3 CH 2 I) heated to 30 ° C was supplied for 0.1 second (0.002 g) to form a ruthenium-containing thin film.
  • reaction by-products and the residual reaction gas were removed using argon gas (3000 sccm) for 1 second.
  • the reaction gas (iodine ethane) was used at 2.7 mol based on 1 mol of the ruthenium (0) type hydrocarbon compound (Compound 1).
  • the ruthenium-containing thin film was formed by repeating 1500 cycles with one cycle as described above.
  • the formed ruthenium thin film was annealed at 450 ° C. for 2 hours in a hydrogen atmosphere in a furnace, and the result of the Gap fill through TEM analysis is shown in FIG.
  • Example 1 Substrate temperature ( ⁇ ) 250 Ru precursor Precursor heating temperature ( ⁇ ) 110 Precursor injection time (sec) 3 Purge (argon) Flow rate (sccm) 3000 Time (seconds) One Iodine ethane (reaction gas) Reaction gas heating temperature ( ⁇ ) 30 Reaction gas injection time (sec) 0.1 Purge (argon) Flow rate (sccm) 3000 Time (seconds) One Number of deposits cycle 1500
  • the ruthenium-containing thin film deposited in Example 1 easily formed a gap fill after heat treatment in a hydrogen atmosphere.
  • Ru-containing precursor compound (Compound 1) was used as a starting material and ruthenium-containing thin film was formed by atomic layer deposition using diiodo methane (CH 2 I 2 ) as a reaction gas.
  • the silicon oxide film substrate was kept at 280 DEG C, and compound 1 was filled in a stainless steel bubbler container and maintained at 110 DEG C.
  • the vaporized compound 1 was supplied to the silicon oxide film substrate for 2 seconds (0.001 g) using argon gas (50 sccm) as a transfer gas to be adsorbed on the silicon oxide film substrate.
  • argon gas 50 sccm
  • unreacted Compound 1 was removed for 0.5 second by using argon gas (3000 seem).
  • diantiomethane (CH 2 I 2 ) heated to 90 ° C was supplied for 0.4 second (0.005 g) to form a ruthenium-containing thin film.
  • reaction by-products and the residual reaction gas were removed using argon gas (3000 sccm) for 0.1 second.
  • the reaction gas (diiodo-methane) was used in an amount of 5.9 mol based on 1 mol of the ruthenium (0) type hydrocarbon compound (Compound 1).
  • the ruthenium-containing thin film was formed by repeating the above 800 cycles by one cycle. Gap fill results and step coverage results through TEM analysis of the formed ruthenium thin films are shown in FIG.
  • the ruthenium-containing thin film prepared in Example 2 shows easy Gap fill formation (FIG. 2 (a)) and excellent step coverage (FIG. 2 (b)).
  • Ru-containing precursor compound (Compound 1) was used as a reaction gas, and diethoxymethane (CH 2 I 2 ) was used as a reaction gas to form a ruthenium-containing thin film by a vapor deposition (CVD) method.
  • CVD vapor deposition
  • the silicon oxide film substrate was kept at 280 DEG C, and compound 1 was filled in a stainless steel bubbler container and maintained at 110 DEG C.
  • vaporized compound 1 was introduced into the reaction chamber for 70 minutes (2.1 g) using argon gas (50 sccm) as a transfer gas, and at the same time, diiodo methane (CH 2 I 2 )
  • the ruthenium-containing thin film was formed by injecting argon gas (25 sccm) as a transfer gas into the reaction chamber for 70 minutes (52.5 g).
  • argon gas (5000 sccm) was injected and the process was performed for 70 minutes to form a ruthenium-containing thin film.
  • the reaction gas (diiodomethane) was used in an amount of 25.0 mol based on 1 mol of the ruthenium (0) type hydrocarbon compound (compound 1).
  • the detailed reaction conditions are shown in Table 3 below.
  • the ruthenium-containing thin film was prepared in the same manner as in Example 1 except that oxygen instead of iodine ethane was used as the reaction gas in Example 1.
  • the ruthenium-containing thin film deposition conditions are shown in Table 4 below.
  • the ruthenium-containing thin film was prepared in the same manner as in Example 1, except that hydrogen was used instead of iodine ethane as the reaction gas in Example 1.
  • the ruthenium-containing thin film deposition conditions are shown in Table 5.
  • FIG. 4 The results of TEM analysis of the ruthenium-containing thin films deposited in Comparative Example 1 and Comparative Example 2 are shown in FIG. As shown in FIG. 4, the ruthenium-containing thin film was formed in Comparative Example 1 using oxygen as the reaction gas, but the ruthenium-containing thin film was not formed in Comparative Example 2 where hydrogen was used as the reaction gas.
  • Ru-containing precursor compound Compound 1
  • a ruthenium-containing thin film was formed by atomic layer deposition using diiodosilane (SiH 2 I 2 ) as a reaction gas.
  • the silicon oxide film substrate was kept at 280 DEG C, and compound 1 was filled in a stainless steel bubbler container and maintained at 110 DEG C.
  • the vaporized compound 1 was supplied to the silicon oxide film substrate for 2 seconds (0.001 g) using argon gas (50 sccm) as a transfer gas to be adsorbed on the silicon oxide film substrate.
  • argon gas 50 sccm
  • unreacted Compound 1 was removed for 0.5 second by using argon gas (3000 seem).
  • diazodosilane (SiH 2 I 2 ) heated to 34 ° C was supplied for 1 second (0.003 g) to form a ruthenium-containing thin film.
  • reaction by-products and the residual reaction gas were removed using argon gas (3000 sccm) for about 0.1 second.
  • the reaction gas (diiodosilane) was used in an amount of 3.4 mol based on 1 mol of the ruthenium (0) type hydrocarbon compound (Compound 1).
  • the ruthenium-containing thin film was formed by repeating the above 800 cycles by one cycle. The detailed reaction conditions are shown in Table 6 below.
  • Ru-containing precursor compound (Compound 2) was used as a reaction gas, and a ruthenium-containing thin film was formed by atomic layer deposition using diiodo methane (CH 2 I 2 ) as a reaction gas.
  • the silicon oxide film substrate was maintained at 300 ⁇ , and Compound 2 was filled in a stainless steel bubbler container and maintained at 36 ⁇ .
  • the vaporized compound 2 was fed to the silicon oxide film substrate for 2 seconds (0.002 g) using argon gas (10 sccm) as a transfer gas, and adsorbed on the silicon oxide film substrate.
  • argon gas 10 sccm
  • unreacted compound 2 was removed for 5 seconds using argon gas (3000 sccm).
  • diantiomethane (CH 2 I 2 ) heated to 90 ° C was supplied for 0.4 second (0.005 g) to form a ruthenium-containing thin film.
  • reaction by-products and the residual reaction gas were removed using argon gas (3000 sccm) for 5 seconds.
  • the reaction gas (diiodo methane) was used in an amount of 2.5 mol based on 1 mol of the ruthenium (0) type hydrocarbon compound (compound 2).
  • the ruthenium-containing thin film was formed by repeating the above 800 cycles by one cycle.
  • Ru-containing precursor compound containing thin film was formed by atomic layer deposition using (isoprene) Ru (CO) 3 , compound 3, and diiodo methane (CH 2 I 2 ) as a reaction gas.
  • the silicon oxide film substrate was maintained at 250 ⁇ , and Compound 3 was filled in a stainless steel bubbler container and maintained at 24 ⁇ .
  • the vaporized compound 3 was supplied to the silicon oxide film substrate for 2 seconds (0.0016 g) using argon gas (50 sccm) as a transfer gas to be adsorbed on the silicon oxide film substrate.
  • argon gas 50 sccm
  • unreacted compound 3 was removed for 5 seconds using argon gas (3000 seem).
  • diantiomethane (CH 2 I 2 ) heated to 90 ° C was supplied for 0.4 second (0.005 g) to form a ruthenium-containing thin film.
  • reaction by-products and the residual reaction gas were removed using argon gas (3000 sccm) for 5 seconds.
  • the reaction gas (diiodo methane) was used in an amount of 3.0 moles per mole of the ruthenium (0) type hydrocarbon compound (compound 3).
  • the ruthenium-containing thin film was formed by repeating the above 400 cycles with one cycle. The detailed reaction conditions are shown in Table 8 below.
  • the resistivity of the ruthenium-containing thin film prepared in Examples 1 to 6 and Comparative Examples 1 to 2 and the composition of the prepared ruthenium-containing thin film were analyzed by TOF-ERD (Time of Flight-Elastic Recoil Detection) Are shown in Table 9 below.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 1 except that the injection time of the compound 1 in Example 1 was changed from 0.5 second to 5 seconds.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 2, except that the injection time of compound 1 in Example 2 was changed from 0.5 second to 5 seconds.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 5 except that the injection time of the compound 2 in Example 5 was changed from 0.5 second to 5 seconds.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 6, except that the injection time of the compound 3 in Example 6 was changed from 0.5 second to 5 seconds.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 1, except that the injection time of iodine ethane was changed from 0.1 second to 5 seconds in Example 1.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 2, except that the injection time of diiodo methane in Example 2 was changed from 0.1 second to 5 seconds.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 4, except that the injection time of the diiodosilane was changed from 0.1 second to 5 seconds in Example 4.
  • a ruthenium-containing thin film was prepared in the same manner as in Comparative Example 1, except that the oxygen gas injection time was changed from 0.1 second to 5 seconds in Comparative Example 1.
  • the growth rate of the ruthenium-containing thin film becomes constant as compared with the case of using oxygen.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 1, except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ .
  • a ruthenium-containing thin film was prepared in the same manner as in Example 2 except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ in Example 2.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 4 except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ in Example 4.
  • the ruthenium-containing thin film was produced in the same manner as in Comparative Example 1, except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ in Comparative Example 1.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 5 except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ in Example 5.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 6 except that the substrate temperature was changed from 200 ⁇ to 360 ⁇ in Example 6.
  • FIG. 8 and 9 show the growth rate saturation results of the ruthenium-containing thin films prepared in Examples 14 to 18 and Comparative Example 4 analyzed by transmission electron microscope according to the substrate temperature.
  • the growth rate of the ruthenium-containing thin film at a wide range of substrate temperatures is constant Respectively.
  • a ruthenium-containing thin film was prepared in the same manner as in Example 2, except that the number of deposition cycles was varied from 10 cycles to 300 cycles.
  • FIG. 10 shows the results of thin film growth for the number of times of deposition of the ruthenium-containing thin film prepared in Example 19.
  • FIG. 10 it was confirmed that ruthenium nuclei were generated at a deposition frequency of 20 cycles or less, and the ruthenium thin film was grown from 20 cycles or more. Also, it was confirmed that the growth of the ruthenium thin film has a constant slope as the number of deposition increases.
  • the method for producing a ruthenium-containing thin film of the present invention uses a ruthenium (0) -based hydrocarbon compound as a precursor for thin film deposition, but uses a reactive gas such as iodine, (C1-C3) alkyl iodide, iodine silane or a mixture thereof as a specific reaction gas And thus a ruthenium-containing thin film can be produced by a simple process since no oxygen is contained and no separate reduction process is required.
  • the method for producing a ruthenium-containing thin film of the present invention can produce a thin film having a uniform surface at a thickness of 2 nm or less and enables gap fill without high step coverage and voids .
  • the method for producing a ruthenium-containing thin film of the present invention minimizes the content of impurities such as carbon, oxygen and hydrogen by using iodine, (C1-C3) alkyl iodide, iodide silane or a mixture thereof without using oxygen as a reaction gas
  • impurities such as carbon, oxygen and hydrogen
  • the ruthenium-containing thin film of the present invention can be produced by using various ruthenium (0) -based hydrocarbon compounds as precursors.
  • the ruthenium-containing thin film deposition composition of the present invention can be produced by using iodine, (C1-C3) alkyl iodide, iodide silane, or a mixture thereof as a reaction gas, thereby providing excellent step coverage and gap fill And a high-purity thin film having high density can be easily obtained.
  • the ruthenium-containing thin film produced by the method of the present invention can be deposited uniformly and with excellent step coverage for a trench, contact or via pattern having a high aspect ratio due to miniaturization of the semiconductor device.

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Abstract

La présente invention concerne un procédé de production d'un film mince contenant du ruthénium et un film mince contenant du ruthénium produit par celui-ci. Le procédé de production d'un film mince contenant du ruthénium selon la présente invention utilise un composé hydrocarboné à base de ruthénium (0) et un gaz de réaction spécifique, et est ainsi capable de produire facilement un film mince de haute pureté au moyen d'un procédé simple.
PCT/KR2018/013160 2017-11-01 2018-11-01 Procédé de production d'un film mince contenant du ruthénium, et film mince contenant du ruthénium produit par celui-ci Ceased WO2019088722A1 (fr)

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US16/760,417 US11827650B2 (en) 2017-11-01 2018-11-01 Method of manufacturing ruthenium-containing thin film and ruthenium-containing thin film manufactured therefrom
JP2020543444A JP7355746B2 (ja) 2017-11-01 2018-11-01 ルテニウム含有薄膜の製造方法およびこれにより製造されたルテニウム含有薄膜
CN201880072781.1A CN111357080B (zh) 2017-11-01 2018-11-01 含钌薄膜的制造方法及由该制造方法制造的含钌薄膜
JP2023109937A JP7751610B2 (ja) 2017-11-01 2023-07-04 ルテニウム含有薄膜の製造方法およびこれにより製造されたルテニウム含有薄膜

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KR10-2017-0144420 2017-11-01
KR1020180131423A KR102374140B1 (ko) 2017-11-01 2018-10-31 루테늄함유 박막의 제조방법 및 이로부터 제조된 루테늄함유 박막
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JPWO2021153640A1 (fr) * 2020-01-31 2021-08-05
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KR20230038543A (ko) * 2020-08-04 2023-03-20 영남대학교 산학협력단 루테늄 박막의 형성 방법

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CN112779520A (zh) * 2019-11-05 2021-05-11 有进科技材料股份有限公司 利用表面保护物质的薄膜形成方法
JP2023509959A (ja) * 2020-01-10 2023-03-10 アプライド マテリアルズ インコーポレイテッド 触媒増強された継ぎ目なしのルテニウム間隙充填
JP7699264B2 (ja) 2020-01-10 2025-06-26 アプライド マテリアルズ インコーポレイテッド 触媒増強された継ぎ目なしのルテニウム間隙充填
JP2024105324A (ja) * 2020-01-10 2024-08-06 アプライド マテリアルズ インコーポレイテッド 触媒増強された継ぎ目なしのルテニウム間隙充填
JP7479479B2 (ja) 2020-01-10 2024-05-08 アプライド マテリアルズ インコーポレイテッド 触媒増強された継ぎ目なしのルテニウム間隙充填
WO2021153639A1 (fr) * 2020-01-31 2021-08-05 田中貴金属工業株式会社 Matiere premiere de compose organique de ruthenium pour depot chimique en phase vapeur et procede de depot chimique en phase vapeur mettant en oeuvre cette matiere premiere pour depot chimique en phase vapeur
CN115038810A (zh) * 2020-01-31 2022-09-09 田中贵金属工业株式会社 由有机钌化合物构成的化学蒸镀用原料及使用该化学蒸镀用原料的化学蒸镀法
TWI762168B (zh) * 2020-01-31 2022-04-21 日商田中貴金屬工業股份有限公司 包含有機釕化合物之化學蒸鍍用原料及使用該化學蒸鍍用原料之化學蒸鍍法
JP7372352B2 (ja) 2020-01-31 2023-10-31 田中貴金属工業株式会社 有機ルテニウム化合物からなる化学蒸着用原料及び該化学蒸着用原料を用いた化学蒸着法
JP7372353B2 (ja) 2020-01-31 2023-10-31 田中貴金属工業株式会社 有機ルテニウム化合物からなる化学蒸着用原料及び該化学蒸着用原料を用いた化学蒸着法
US11913110B2 (en) 2020-01-31 2024-02-27 Tanaka Kikinzoku Kogyo K.K. Raw material for chemical deposition containing organoruthenium compound, and chemical deposition method using the raw material for chemical deposition
JPWO2021153639A1 (fr) * 2020-01-31 2021-08-05
CN115038810B (zh) * 2020-01-31 2024-07-19 田中贵金属工业株式会社 由有机钌化合物构成的化学蒸镀用原料及使用该化学蒸镀用原料的化学蒸镀法
WO2021153640A1 (fr) * 2020-01-31 2021-08-05 田中貴金属工業株式会社 Matiere premiere de compose organique de ruthenium pour depot chimique en phase vapeur et procede de depot chimique en phase vapeur mettant en oeuvre cette matiere premiere pour depot chimique en phase vapeur
JPWO2021153640A1 (fr) * 2020-01-31 2021-08-05
KR20230038543A (ko) * 2020-08-04 2023-03-20 영남대학교 산학협력단 루테늄 박막의 형성 방법
KR102800710B1 (ko) 2020-08-04 2025-04-29 영남대학교 산학협력단 루테늄 박막의 형성 방법

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