Composition for depositing molybdenum-containing thin film, method for manufacturing molybdenum-containing thin film, and thin film

Abstract

Provided are a composition for depositing a molybdenum-containing thin film, a method for manufacturing a molybdenum-containing thin film, and a molybdenum-containing thin film manufactured using the method, the composition for depositing a molybdenum-containing thin film comprising: a precursor for thin film deposition, the precursor includes a monovalent molybdenum-based compound, a divalent molybdenum-based compound, a trivalent molybdenum-based compound, a tetravalent molybdenum-based compound, a pentavalent molybdenum-based compound, a hexavalent molybdenum-based compound, a zero-valent molybdenum-based compound bound to at least two organic ligands, or any combination thereof; and a reactant including a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof, in which a molar concentration of the reactant may be approximately 200 times or less of a molar concentration of the precursor for thin film deposition.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0173232 filed on December 4, 2023, and Korean Patent Application No. 10-2024-0129859 filed on September 25, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a composition for depositing a molybdenum-containing film, a method for making a molybdenum-containing film, and a molybdenum-containing film made therefrom. More specifically, the present disclosure relates to a method for making a molybdenum-containing film by reacting a molybdenum-based compound with a specific reactant as a precursor for thin film deposition, and a molybdenum-containing film made therefrom. Background Art

[0004] Molybdenum-containing thin films can be used in organic light-emitting diodes, liquid crystal displays, plasma display panels, field emission displays, thin-film solar cells, low-ohm resistors, and other electronic devices and semiconductor devices, and are mainly used as components of electronic parts such as barrier films.

[0005] Molybdenum, molybdenum oxide, and molybdenum nitride are widely used in various fields due to low resistance, large work function, and thermochemical stability. For example, metallic molybdenum has a low resistivity of less than or equal to about 15 μΩcm and can therefore be applied to wires of display devices. Molybdenum oxide MoO 2 Molybdenum trioxide (MoO) shows unusual metal-like conductivity and can therefore be applied in hydrocarbon oxidation catalysts, solid oxide fuel cell (SOFC) anodes, and high-capacity reversible lithium-ion battery (LIB) anodes. 3 ) show electrochromic and catalytic properties and can therefore be applied to solid-state lithium-ion batteries and gas sensors with nanostructures.

[0006] On the other hand, for thin film deposition in semiconductor devices, methods such as molecular beam epitaxy (MBE), chemical vapor deposition (CVD), physical vapor deposition (PVD), etc. are being studied. Recently, as the size of semiconductor devices has been reduced, as a thin film deposition method that satisfies low temperature processes, precise thickness control, and uniformity and coating properties of thin films, an atomic layer deposition (ALD) method based on a self-limiting surface reaction mechanism is being widely studied.

[0007] The raw materials for the chemical vapor growth method for producing a thin film including molybdenum oxide may include an organic molybdenum compound such as molybdenum carbonyl [Mo(CO) 6 ], molybdenum acetylacetonate, molybdenum chloride (MoCl 3 or MoCl5 ), molybdenum fluoride (MoF 6 )、MoO 2 (2,2,6,6-Tetramethylheptane-3,5-dione) 2 , biscyclopentadienyl molybdenum dihydride, bismethylcyclopentadienyl molybdenum dihydride, bisethylcyclopentadienyl molybdenum dihydride, bisisopropylcyclopentadienyl molybdenum dihydride, biscyclopentadienyl imide molybdenum, and molybdenum oxychloride (MoO 2 Cl 2 or MoOCl 4 ). Additionally, as a raw material for forming a thin film including molybdenum by ALD, an amideimide molybdenum compound has been reported.

[0008] However, a conventional molybdenum-containing thin film deposition process uses oxygen as a reaction gas, and thus has a problem of requiring a reduction process.

[0009] Therefore, there is a need for a method for manufacturing a high-purity molybdenum-containing thin film by reducing the content of impurities in the thin film through a simple process. Summary of the invention

[0010] One aspect of the present disclosure is to implement a composition for depositing a molybdenum-containing thin film that can form a high-purity molybdenum-containing thin film.

[0011] Another aspect of the present disclosure is to implement a method for manufacturing a molybdenum-containing thin film using a precursor and a specific reactant for depositing a molybdenum-containing thin film, and a molybdenum-containing thin film manufactured thereby.

[0012] A composition for depositing a molybdenum-containing thin film according to one aspect of the present disclosure comprises:

[0013] A precursor for thin film deposition, comprising a monovalent molybdenum-based compound, a divalent molybdenum-based compound, a trivalent molybdenum-based compound, a tetravalent molybdenum-based compound, a pentavalent molybdenum-based compound, a hexavalent molybdenum-based compound, a zero-valent molybdenum-based compound bonded to at least two organic ligands, or any combination thereof, and

[0014] a reactant comprising a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof,

[0015] Here, the molar concentration of the reactant may be about 200 times or less than the molar concentration of the precursor for thin film deposition.

[0016]

[0017] In Chemical Formula 1 and Chemical Formula 2,

[0018] A 1 To A 3 are each independently C, Si, Ge, Sn or Ti,

[0019] R 1 is hydrogen or a hydrocarbon group,

[0020] X 1 is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom,

[0021] n1 is an integer from 1 to 3, and

[0022] R 2 To R 5 are each independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom,

[0023] The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

[0024] A method for manufacturing a molybdenum-containing thin film according to another aspect of the present disclosure includes:

[0025] a) providing a substrate to a reaction chamber;

[0026] b) providing a delivery gas and a precursor for thin film deposition in a gas phase to a reaction chamber, wherein the precursor for thin film deposition comprises a monovalent platinum-based compound, a divalent platinum-based compound, a trivalent platinum-based compound, a tetravalent platinum-based compound, a pentavalent platinum-based compound, a hexavalent platinum-based compound, a zero-valent platinum-based compound bonded to at least two organic ligands, or any combination thereof; and

[0027] c) providing a reactant including a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof to a reaction chamber in a gas phase,

[0028] Therein, the reactant is supplied at a molar concentration of about 200 times or less (eg, 1 to 200 times) relative to a molar concentration of a precursor for thin film deposition supplied per second.

[0029]

[0030] In Chemical Formula 1 and Chemical Formula 2,

[0031] A 1 To A 3 are independently C, Si, Ge, Sn or Ti,

[0032] R 1 is hydrogen or a hydrocarbon group,

[0033] X 1 is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom,

[0034] n1 is an integer from 1 to 3, and

[0035] R 2 To R 5 are independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom,

[0036] The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

[0037] According to another aspect, a molybdenum-containing thin film manufactured using the aforementioned manufacturing method is provided.

[0038] A method for manufacturing a molybdenum-containing thin film according to an aspect of the present disclosure may provide a high-purity molybdenum-containing thin film by using a composition for depositing a molybdenum-containing thin film.

[0039] A method for manufacturing a molybdenum-containing thin film according to another aspect of the present disclosure may use various molybdenum-based compounds as precursors, and may minimize the content of impurities such as carbon by using a specific reactant other than oxygen. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Results of X-ray photoelectron spectroscopy (XPS) of an exemplary molybdenum-containing thin film according to Example 1 according to etching time are shown.

[0041] Figure 2 Results of X-ray photoelectron spectroscopy (XPS) of an exemplary molybdenum-containing thin film according to Example 2 according to etching time are shown.

[0042] Figure 3 Results of X-ray photoelectron spectroscopy (XPS) of an exemplary molybdenum-containing thin film according to Comparative Example 1 according to etching time are shown.

[0043] Figure 4 The resistivity results according to the silicon content are shown.

[0044] Figure 5 is a transmission electron microscope photograph of a substrate having a trench structure according to Example 1 on which an exemplary molybdenum-containing thin film is deposited.

[0045] Figure 6 Results of an energy dispersive X-ray spectroscopy (EDS) spectrum on a substrate of a trench structure having an exemplary molybdenum-containing thin film deposited thereon according to Example 1 are shown.

[0046] Figure 7 Results of EDS spectrum analysis of an exemplary trench structure according to Example 1 according to the positions of the top, middle, and bottom at high magnification are shown.

[0047] Figure 8 Results of EDS spectrum analysis of an exemplary trench structure according to Comparative Example 1 according to the positions of the top, middle, and bottom at high magnification are shown.

[0048] Fig. 9 An X-ray diffraction pattern of an exemplary molybdenum-containing thin film according to Example 1 is shown.

[0049] Fig.10 is a transmission electron microscope photograph of an exemplary molybdenum-containing thin film according to Example 1.

[0050] Fig.11 is a transmission electron microscope photograph showing the growth rate according to the amount of deposition of an exemplary molybdenum-containing thin film according to Example 9.

[0051] Fig.12 The correlation between the thickness and the resistivity according to the number of depositions of the exemplary molybdenum-containing thin film according to Example 9 is shown. DETAILED DESCRIPTION

[0052] The present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which example embodiments of the invention are shown. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

[0053] In order to clearly describe the present disclosure, throughout the specification, parts irrelevant to the description are omitted, and the same reference numerals denote the same or like components.

[0054] For better understanding and ease of description, the size and thickness of each constituent element as shown in the drawings are arbitrarily indicated, and the present disclosure is not necessarily limited to as shown. In the drawings, the thickness of layers, regions, etc. are exaggerated for clarity. In the drawings, the thickness of some layers and regions is exaggerated for ease of explanation.

[0055] In addition, it will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, the element can be directly on the other element, or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements. Furthermore, to be disposed "on" or "above" a reference portion means to be disposed above or below the reference portion, and does not necessarily mean "on" or "above" in the opposite direction of gravity.

[0056] In addition, unless explicitly described to the contrary, the word “comprise” and variations such as “comprising” or “including”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0057] As used herein, the term "about" when referring to a measurable value such as time, temperature, molar concentration, atomic percentage or other measurement, is meant to encompass variations of + / -10%, + / -5%, + / -1%, + / -0.5% or even + / -0.1% of the specified amount.

[0058] As used herein, "substituted" means that at least one hydrogen is replaced by a substituent selected from a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group or a combination thereof.

[0059] Additionally, throughout the specification, unless otherwise defined, "alkyl" can be a C1 to C10 alkyl. For example, it can be a C1 to C10 alkyl, a C2 to C10 alkenyl or a C2 to C10 alkynyl, and more specifically, a C1 to C10 alkyl or a C2 to C10 alkenyl. The C1 to C10 alkyl can be straight or branched, and can be chain or cyclic. In certain embodiments, it can be ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, etc. The C2 to C10 alkenyl can be straight or branched, and can be chain or cyclic. In certain embodiments, it can be vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc. All of the above alkenyls can have one or two double bonds.

[0060] Additionally, the "hydrocarbon group" of the present disclosure may or may not include a substituent, and when the "hydrocarbon group" is substituted, the substituent may be, for example, halogen, or C1 to C5 halogenated alkyl.

[0061] The present disclosure provides a composition for depositing a molybdenum-containing film, the composition for depositing a molybdenum-containing film comprising:

[0062] A precursor for thin film deposition, comprising a monovalent molybdenum-based compound, a divalent molybdenum-based compound, a trivalent molybdenum-based compound, a tetravalent molybdenum-based compound, a pentavalent molybdenum-based compound, a hexavalent molybdenum-based compound, a zero-valent molybdenum-based compound bonded to at least two organic ligands, or any combination thereof, and

[0063] a reactant comprising a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof,

[0064] Here, the molar concentration of the reactant supplied per second may be about 200 times or less than the molar concentration of the precursor for thin film deposition supplied per second.

[0065]

[0066] Wherein, in Chemical Formula 1 and Chemical Formula 2,

[0067] A 1 To A 3 are each independently C, Si, Ge, Sn or Ti,

[0068] R 1 is hydrogen or a hydrocarbon group,

[0069] X 1 is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom,

[0070] n1 is an integer from 1 to 3, and

[0071] R 2 To R 5 are each independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom,

[0072] The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

[0073] In some embodiments of Formula 1, when n1 is 2 or greater, each X 1 May be the same as or different from each other.

[0074] In some embodiments of Formula 1, when 4-n1 is 2 or greater, each R 1 May be the same as or different from each other.

[0075] Some halogen-containing molybdenum precursors that are in a solid state when depositing a thin film have limitations in terms of large-scale production, and some molybdenum precursors include organic ligands and are in a liquid state at room temperature. However, when these materials are used to deposit a thin film using an ALD method and a CVD method, carbon derived from the organic ligands remains in the thin film to form MoC x type film, thus causing resistance degradation problems. Because the Mo-C bond formation is much more thermodynamically stable than the Mo form, even when H 2 It may also be difficult to inhibit MoC when using (a reactive gas commonly used when depositing metal films) x formation, and it may be difficult to obtain a high-purity Mo film even using a post-treatment process under oxidizing conditions or reducing conditions.

[0076] In the present disclosure, a material having a specific structure containing halogen atoms is used as a reactant, and at the same time, specific process conditions can be applied to develop a composition and a film manufacturing method capable of forming a high-purity, low-resistance Mo film having a Mo content of 97 atomic percent (at%) or greater (the total amount of Mo and O when molybdenum oxide is included). In some embodiments, the method includes using a halogen-containing molybdenum precursor having a high melting point (over 100° C.) that does not contain an organic ligand. The method may also include using a molybdenum precursor that includes an organic ligand and exists as a liquid at room temperature.

[0077] For example, the molar concentration of the reactant supplied per second can be about 1 to about 200 times the molar concentration of the precursor supplied per second for thin film deposition, and can be adjusted within the above range 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), the molar concentration of the reactant supplied per second can be about 1 to about 100 times the molar concentration of the precursor supplied per second for thin film deposition, specifically, about 1 to about 50 times, and more specifically, 1 to 25 times.

[0078] For example, in some embodiments, a monovalent platinum-based compound, a divalent platinum-based compound, a trivalent platinum-based compound, a tetravalent platinum-based compound, and / or a pentavalent platinum-based compound may be combined with at least one organic ligand.

[0079] The zero-valent molybdenum-based compound may be combined with at least two organic ligands.

[0080] The organic ligand may be a substituted or unsubstituted C4 to C10 organic group including a carbonyl group or a conjugated structure (eg, a structure including alternating single bonds and double bonds).

[0081] As examples, in some embodiments, the organic ligand may be a carbonyl group, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted allyl group, or a substituted or unsubstituted benzene.

[0082] As specific examples, the organic ligand may be a carbonyl group, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted allyl group, a substituted or unsubstituted benzene, a substituted or unsubstituted xylene, a substituted or unsubstituted toluene, a substituted or unsubstituted aniline, a substituted or unsubstituted alkoxybenzene, or a substituted or unsubstituted alkyl benzoate.

[0083] In an embodiment of the present disclosure, the organic ligand may or may not include a substituent, and when the organic ligand is substituted, the substituent may be, for example, halogen, C1 to C10 aminoalkyl, C1 to C10 alkoxyalkyl, C1 to C10 alkylsilyl, C1 to C10 alkyl, C1 to C10 haloalkyl, or C1 to C10 alkoxy.

[0084] In some embodiments, the precursor for thin film deposition may be at least one selected from the following, or any combination thereof: molybdenum fluoride (MoF 6 ), (2-dimethylaminoethyl) cyclopentadienyl tricarbonyl molybdenum hydride, (2-methoxyethyl) cyclopentadienyl tricarbonyl molybdenum hydride, trimethylsilyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, isopropyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, molybdenum chloride (MoCl 3 or MoCl 5 ), molybdenum iodide (MoI 3 ), bis(η6-benzene) platinum), bis(η6-methylbenzene) platinum, bis(η6-ethylbenzene) platinum, bis(η6-1,2-o-xylene) platinum, bis(η6-tert-butylbenzene) platinum, bis(η6-fluorobenzene) platinum, bis(η6-trifluorotoluene) platinum, bis(η6-dimethylaniline) platinum, bis(η6-methoxybenzene) platinum, bis(η6-methylbenzoate) platinum, (η6-fluorobenzene)(η6-methylbenzene) platinum (η6-fluorobenzene)(η6-1,2-o-xylene) molybdenum, (η6-fluorobenzene)(η6-tert-butylbenzene) molybdenum, (η6-fluorobenzene)(η6-N,N-dimethylaniline) molybdenum, (η6-fluorobenzene)(η6-methoxybenzene) molybdenum, (η6-fluorobenzene)(η6-methylbenzoate) molybdenum, (η6-methylbenzoic acid)(η6-1,2-o-xylene) molybdenum, ((CH 3 ) 2 N(CH 2 ) 2 Cp)MoH(CO) 3 ,((CH 3 )O(CH 2 ) 2 Cp)MoH(CO) 3 , bis((2-dimethylaminoethyl)cyclopentadienyl)molybdenum dihydride (C 5 H 4 (CH 2 CH 2 N(CH 3 ) 2 )) 2 MoH 2 ), bis((2-methoxyethyl)cyclopentadienyl)molybdenum dihydride (C 5 H 4 (CH 2 CH 2 O(CH 3 ))) 2 MoH 2 ), bis(ethylcyclopentadienyl)molybdenum dihydride, and bis(isopropylcyclopentadienyl)molybdenum dihydride.

[0085] In an embodiment, the precursor for thin film deposition can be selected from (2-dimethylaminoethyl) cyclopentadienyl tricarbonyl molybdenum hydride, (2-methoxyethyl) cyclopentadienyl tricarbonyl molybdenum hydride, trimethylsilyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, isopropyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, bis(η6-phenyl) molybdenum, bis(η6-methylbenzene) molybdenum, bis(η6-ethylbenzene) molybdenum, bis((2-dimethylaminoethyl) cyclopentadienyl) dihydrogenated molybdenum (C 5 H 4 (CH 2 CH 2 N(CH 3 ) 2 )) 2 MoH 2 ), bis((2-methoxyethyl)cyclopentadienyl)molybdenum dihydride (C 5 H 4 (CH 2 CH 2 O(CH 3 ))) 2 MoH 2 ), at least one selected from bis(ethylcyclopentadienyl)molybdenum dihydride, and bis(isopropylcyclopentadienyl)molybdenum dihydride, or any combination thereof.

[0086] The reactants can be 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. (CH 3 ) 3 CI, CHBr 3 , CH 2 Br 2 , CH 3 CHBr 2 , CHCl 3 , CH 2 Cl 2 , (CH 3 ) 2 CHCl、SiHI3 、SiH 2 I 2 、SiH 3 I. SiHF 3 、SiH 2 F 2 、SiH 3 F. SiHCl 3 、SiH 2 Cl 2 、SiH 3 Cl、SiHBr 3 、SiH 3 Br, SnHI 3 SnH 2 I 2 SnH 3 I. SnHF 3 SnH 2 F 2 SnH 3 F. SnHCl 3 SnH 2 Cl 2 SnH 3 Cl, SnHBr 3 SnH 3 Br, SnH 2 Br 2 , CH 2 CHI, CH 2 C(I) 2 、ICHCHI、CH 2 CHCH 2 I. CH 2 CICH 3 and ICHCHCH 2 At least one selected from I, or any combination thereof.

[0087] In an embodiment, the reactant may be 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 CH2 I. (CH 3 ) 3 CI, SiHI 3 、SiH 2 I 2 , and SiH 3 At least one selected from I, or any combination thereof.

[0088] Hereinafter, a method for manufacturing a molybdenum-containing thin film using a composition for depositing a molybdenum-containing thin film, and a molybdenum-containing thin film using the method will be described.

[0089] In an embodiment of the present disclosure, a method for manufacturing a molybdenum-containing film includes:

[0090] a) providing a substrate to a reaction chamber;

[0091] b) providing a delivery gas and a precursor for thin film deposition in a gas phase to a reaction chamber, wherein the precursor for thin film deposition comprises a monovalent platinum-based compound, a divalent platinum-based compound, a trivalent platinum-based compound, a tetravalent platinum-based compound, a pentavalent platinum-based compound, a hexavalent platinum-based compound, a zero-valent platinum-based compound bonded to at least two organic ligands, or any combination thereof; and

[0092] c) providing a reactant including a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof to a reaction chamber in a gas phase,

[0093] Wherein the reactant is supplied at a molar concentration of about 200 times or less per second relative to the molar concentration of the precursor for thin film deposition supplied per second.

[0094]

[0095] Wherein, in Chemical Formula 1 and Chemical Formula 2,

[0096] A 1 To A 3 are each independently C, Si, Ge, Sn or Ti,

[0097] R 1 is hydrogen or a hydrocarbon group,

[0098] X 1 is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom,

[0099] n1 is an integer from 1 to 3, and

[0100] R 2 To R 5 are each independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom,

[0101] The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

[0102] In some embodiments, in Formula 1, when n1 is 2 or greater, each X 1 May be the same as or different from each other.

[0103] In some embodiments, in Formula 1, when 4-n1 is 2 or greater, each R 1 May be the same as or different from each other.

[0104] The method for manufacturing a molybdenum-containing thin film disclosed herein can provide a high-purity thin film having a controlled carbon content in the thin film by using a combination of a specific molybdenum precursor and a specific reactant for thin film deposition, and due to the high reactivity of the precursor and reactant for thin film deposition, not only carbon but also impurities other than carbon, such as halogens, silicon, etc., can be controlled. Specifically, in some embodiments, when the supply molar concentration ratio of the reactant per second is adjusted to 200 times or less relative to the precursor for thin film deposition, a high-purity Mo thin film with a total impurity of less than 3at% can be manufactured.

[0105] In an embodiment,

[0106] A in Chemical Formula 1 and Chemical Formula 2 1 To A 3 may each independently be C, Si, Sn or Ti, and

[0107] In Chemical Formula 1, R 1 may be each independently hydrogen or C1 to C5 alkyl, and X 1 It may be a halogen atom or a C1 to C5 halogenated alkyl group.

[0108] In addition, in the embodiment, R in Chemical Formula 2 2 To R 5 may be each independently hydrogen, a halogen atom, a C1 to C5 alkyl group, or a C1 to C5 halogenated alkyl group, and R 2 To R 5 At least one of them may be a halogen atom or a C1 to C5 haloalkyl group.

[0109] In a specific embodiment of the present disclosure,

[0110] A in Chemical Formula 1 and Chemical Formula 2 1 To A 3 may each independently be C, Si or Sn, and

[0111] In Chemical Formula 1, R 1may be hydrogen or a C1 to C5 alkyl group, and X 1 It may be Cl, Br, I, or a C1 to C5 alkyl group substituted with one or more of Cl, Br and I.

[0112] In addition, in the embodiment, R in Chemical Formula 2 2 To R 5 may be each independently: hydrogen; Cl; Br; I; C1 to C5 alkyl; or C1 to C5 alkyl substituted with one or more of Cl, Br and I, and R 2 To R 5 At least one of may be: Cl; Br; I; or a C1 to C5 alkyl group substituted with one or more of Cl, Br and I.

[0113] In the most specific embodiment of the present disclosure, X in Chemical Formula 1 1 It may be I, or a C1 to C5 alkyl group substituted with one or more I.

[0114] Alternatively, in the embodiment, R in Chemical Formula 2 2 To R 5 At least one of may be I; or a C1 to C5 alkyl group substituted with one or more I's.

[0115] In an embodiment, available substrates may include: a substrate including 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 display; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyether sulfone (PES) and polyester; a tungsten substrate, but is not limited thereto.

[0116] Any substrate according to the embodiment may be used as long as it is within a range recognized by those skilled in the art, and the temperature of the substrate is not limited, but may desirably be about 80° C. to about 600° C., specifically, about 100° C. to about 600° C., or about 200° C. to about 600° C. The temperature range may be due to the decomposition characteristics of the molybdenum-based precursor itself used as a precursor and the reaction characteristics with other substances (such as the reactant represented by Chemical Formula 1 or Chemical Formula 2).

[0117] In the method for manufacturing a molybdenum-containing thin film according to an embodiment, a molybdenum-based compound as a precursor for thin film deposition and a reactant represented by Chemical Formula 1 or Chemical Formula 2 may be supplied to a reaction chamber together or independently of each other. Additionally, the molybdenum-based compound and the reactant may each be supplied to the reaction chamber continuously or discontinuously, and the discontinuous supply may include a pulse form.

[0118] For example, the step of providing a precursor for thin film deposition in b) and the step of providing a reactant in c) may be continuously or discontinuously supplied to the reaction chamber, wherein step c) may be performed after step b), or step b) may be performed after step c).

[0119] In the method for manufacturing a molybdenum-containing thin film according to an embodiment, among the molybdenum-based compounds used as precursors for thin film deposition, in the case where they are liquid compounds at room temperature and room pressure, they can be converted into a gaseous state by heating or other methods, and then introduced into a reaction chamber for thin film deposition.

[0120] In the method for manufacturing a molybdenum-containing thin film according to an embodiment, the reactant represented by Chemical Formula 1 or Chemical Formula 2 is changed into a gas state by a method such as heating, and can be introduced into a reaction chamber where a substrate adsorbing a molybdenum-based compound as a precursor for thin film deposition exists.

[0121] According to an embodiment, a method for manufacturing a molybdenum-containing thin film may include atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), and in terms of having high purity and excellent physical properties, it can be performed by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0122] In the method for manufacturing a molybdenum-containing thin film according to an embodiment, the molybdenum-based compound may be supplied to the reaction chamber together with a delivery gas. Specifically, the delivery gas may be nitrogen (N 2 ), any one or two or more selected from hydrogen, argon and helium, and in the desired combination with the specific reactants of the present disclosure, the transport gas may be nitrogen (N 2 ), any one or two or more inert gases selected from argon and helium.

[0123] In the method for manufacturing a molybdenum-containing thin film according to an embodiment, post-treatment may be performed after step b) and / or step c).

[0124] In an embodiment, post-treatment is performed so that unreacted molybdenum compound gas, by-product gas, or unreacted reaction gas may be exhausted.

[0125] In another embodiment, post-processing may be performed to produce a molybdenum-containing film that additionally includes molybdenum oxide.

[0126] The post-treatment may include hydrogen treatment, heat treatment, ammonia treatment, oxygen treatment, ozone treatment, treatment using a reactant containing oxygen atoms, or a combination thereof.

[0127] Specifically, the heat treatment may be performed at about 200° C. to about 700° C. (desirably, at about 300° C. to about 600° C.).

[0128] In addition, the heat treatment may be performed for about 1 minute to about 4 hours, for example, about 5 minutes to about 1 hour.

[0129] Furthermore, heat treatment may be performed under a hydrogen atmosphere.

[0130] For example, the reactant containing an oxygen atom may be O 2 , O 3 , O 2 Plasma, H 2 O、NO 2 、NO、N 2 O (nitrous oxide), CO, CO 2 , H 2 O 2 , HCOOH, CH 3 COOH, (CH 3 CO) 2 O, alcohol, peroxide, at least one of sulfur oxide, or any combination thereof.

[0131] In addition, after step b) and / or step c), a purging step may be performed by supplying an inert gas in the reaction chamber to exhaust unreacted molybdenum-based compound gas, byproducts or unreacted reaction gas. The inert gas may be nitrogen (N 2 ), any one or two or more selected from argon and helium.

[0132] A method for manufacturing a molybdenum-containing thin film according to an embodiment of the present disclosure includes:

[0133] a) maintaining the temperature of the substrate mounted in the reaction chamber at about 80° C. to about 600° C.;

[0134] b) injecting a transport gas and a molybdenum-based compound; and

[0135] c) injecting a reactant to produce a molybdenum-containing thin film on a substrate, wherein the reactant is a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof.

[0136] In a method for manufacturing a molybdenum-containing thin film according to an embodiment, a molybdenum-based compound as a precursor for thin film deposition and a hydrocarbon compound containing at least one halogen atom as a reactant are used, and the reactants are supplied at a molar concentration of approximately 200 times or less per second relative to the molar concentration of the thin film deposition precursor supplied per second, and the corresponding thin film deposition conditions can be adjusted according to the desired structure or thermal properties of the thin film.

[0137] Deposition conditions according to an embodiment may include an input flow rate of a molybdenum-based compound of a precursor for thin film deposition, an input flow rate of a delivery gas, a pressure, a radio frequency (RF) power, a substrate temperature, etc., and non-limiting examples of these deposition conditions may include an input flow rate of about 1 cc / min to about 1000 cc / min or any range therein, a pressure of about 0.1 Torr to about 100 Torr or any range therein, an RF power of about 200 W to about 1000 W or any range therein, and a substrate temperature of about 80°C to about 600°C or any range therein (desirably, about 100°C to about 400°C), but are not limited thereto.

[0138] The reactant according to the embodiment can be supplied at a molar concentration of about 1 to about 200 times the molar concentration of the molybdenum-containing precursor per second, and the reactant according to the embodiment can be adjusted within the above range according to the thin film deposition conditions. For example, in the case of atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD), the reactant can be supplied at a molar concentration of about 10 to about 100 times (more desirably, about 1 to about 50 times, or most desirably, about 1 to about 25 times) of the molar concentration of the molybdenum-containing precursor per second.

[0139] The method for manufacturing a molybdenum-containing thin film according to an embodiment may include a process comprising step a), step b) and step c) which is considered to be 1 cycle, and the cycle may be repeated 20 or more cycles, 30 or more cycles, 40 or more cycles, 50 or more cycles, or 60 or more cycles, or more specifically, 100 or more cycles.

[0140] In some embodiments, the cycle may be repeated 50 to 800 times, more specifically 60 to 300 times.

[0141] For example, if a process including step a), step b) and step c) is repeated in two or more cycles, post-processing may be performed for each process cycle or after some cycles in the entire process cycle are repeated, or post-processing may be performed after some cycles in the entire process cycle are repeated and then further post-processing may be performed after completing the remaining cycles.

[0142] For example, in the case of repeating the process including steps a), b), and c) 800 times, post-processing may be performed after repeating 400 cycles as some of the total 800 cycles, and another post-processing may be performed after completing the remaining 400 cycles.

[0143] The molybdenum-containing film can be any film manufactured within the range identified by a person skilled in the art of manufacturing molybdenum-containing films by supplying a molybdenum precursor in the gas phase. As a specific and practical example, the molybdenum-containing film can be a generally conductive molybdenum single film, a molybdenum oxide film, a molybdenum nitride film, or a mixed film thereof. In addition, various high-quality films containing molybdenum can be manufactured within the range identified by a person skilled in the art.

[0144] In some embodiments, a molybdenum-containing thin film manufactured by the aforementioned method for manufacturing a molybdenum-containing thin film is provided, and the prepared molybdenum-containing thin film may have a resistivity less than or equal to about 200 μΩ·cm.

[0145] The molybdenum-containing thin film according to an embodiment may have a molybdenum content greater than or equal to about 97 at % (and specifically, greater than or equal to about 99 at %).

[0146] The molybdenum-containing thin film according to an embodiment may have a carbon content of less than about 1 at %.

[0147] In an embodiment of the present invention, the molybdenum-containing film may include molybdenum oxide, and the molybdenum oxide may be MoO 2 、MoO 3 or a combination thereof.

[0148] When the molybdenum-containing thin film includes molybdenum oxide, the molybdenum-containing thin film may have a total content of molybdenum (Mo) and oxygen (O) greater than or equal to about 97 at %.

[0149] The molybdenum-containing thin film according to an embodiment may have a silicon content less than or equal to about 3 at %.

[0150] The molybdenum-containing thin film according to an embodiment may have a content of other impurities such as halogens of less than about 1 at %.

[0151] By reacting a molybdenum-based compound with a halogen-containing hydrocarbon compound as a specific reactant, a molybdenum-containing thin film can be manufactured with high purity, high density, and high durability. In addition, in some embodiments, when manufacturing a molybdenum-containing thin film, the content of impurities can be minimized by using the aforementioned specific reactant instead of hydrogen, thereby preventing the contact resistance between the molybdenum-containing thin film and the underlying film from increasing due to oxides formed at the interface with the underlying film.

[0152] In addition, when manufacturing molybdenum-containing films, in some embodiments, by using molybdenum-based compounds and specific reactants to improve crystal quality, the resistivity of the film can be reduced to about 200 μΩ·cm or less (in some embodiments, desirably, about 100 μΩ·cm or less, and in some embodiments, more desirably, about 45 μΩ·cm or less), and the carbon content in the film can be reduced to less than about 1 at%.

[0153] Although the exemplary embodiments have been described above, the present disclosure is not limited to the foregoing exemplary embodiments, and various additions, omissions, substitutions, and changes may be made. Additionally, other embodiments may be provided by combining elements from different embodiments.

[0154] Hereinafter, the present disclosure will be explained in more detail through the following examples. The terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, and based on the principle that the inventor can appropriately define the concept of the term in order to explain his or her invention in the best way, it should be interpreted as the meaning and concept consistent with the technical idea of ​​the present disclosure.

[0155] Therefore, the construction shown in the embodiment described in this specification is only one of the most desirable embodiments of the present disclosure and does not represent the entire technical idea of ​​the present disclosure, so that it should be understood that there are various equivalents and modifications that can replace them when the present application is filed.

[0156] Furthermore, all of the following examples were performed using a 200 mm showerhead type ALD tool (CN1, Atomic Premium) in a single wafer format as a commercially proven device concept using known atomic layer deposition (ALD) methods.

[0157] The resistivity of the deposited Mo-containing films was measured using a sheet resistance meter (4-point probe, DASOLENG, ARMS-200C), and the resistivity of the deposited Mo-containing films was measured using a scanning electron microscope (Hitachi, S-4800) and a transmission electron microscope (FEI (Netherlands) Tecnai G 2F30S-Twin) was used to measure the thickness, and the properties of the formed thin films were analyzed by analyzing the components within the thin films using X-ray photoelectron spectroscopy (XPS) (ThermoFisherScientific, K-Alpha).

[0158] Fabrication of Molybdenum-containing Thin Films

[0159] Example 1, Example 2, and Comparative Example 1

[0160] By using bis(η6-ethylbenzene)molybdenum (Mo(EtBz)) as a molybdenum-containing precursor in an atomic layer deposition method 2 ) and diiodosilane (SiH 2 I 2 ) to form a molybdenum-containing film.

[0161] After placing the substrate on which titanium nitride was deposited on the silicon oxide layer in a vacuum holding chamber and then maintaining it at 375° C., bis(η6-ethylphenyl)molybdenum (Mo(EtBz)) as a molybdenum-containing precursor was added. 2 ) was filled in a stainless steel bubbler container and maintained at 98°C. The bis(η6-ethylbenzene)molybdenum (Mo(EtBz)) evaporated in the stainless steel bubbler container was 2 ) was delivered to the silicon oxide layer substrate at a supply molar concentration of 0.718 μmol / sec for 5 seconds to be absorbed therein by using argon gas (50 sccm) as a delivery gas. Subsequently, unreacted (unadsorbed) bis(η6-ethylphenyl)molybdenum (Mo(EtBz)) was removed by using argon gas (3000 sccm). 2 ) for 3 seconds. Then, SiH2O2 filled in a stainless steel bubbler container and evaporated at 13°C to 80°C was supplied. 2 I 2 The reactants were heated for 0.1 seconds to form a molybdenum-containing film. Finally, the reaction byproducts and residual reaction gas were removed therefrom by using argon gas (3000 sccm). Based on the molybdenum-containing precursor (bis(η6-ethylbenzene)molybdenum (Mo(EtBz) 2 )) at a molar concentration per second (0.718 μmol / sec), diiodosilane (SiH) as a reactant was supplied at a molar concentration of 25 times (18.0 μmol / sec, Example 1), 100 times (71.8 μmol / sec, Example 2), and 300 times (215 μmol / sec, Comparative Example 1), respectively. 2 I 2 The above process was repeated 800 times as one cycle to form a molybdenum-containing thin film. The detailed reaction conditions are shown in Table 1.

[0162] Table 1

[0163]

[0164] The sheet resistance of each of the formed thin films was measured by a four-point probe method and the thickness was measured by a scanning electron microscope (SEM), and the composition of each thin film was examined by X-ray photoelectron spectroscopy (XPS), wherein the sheet resistance and thickness measurement values ​​were substituted into Equation 1 to calculate the resistivity of each thin film.

[0165] [Equation 1]

[0166] Resistivity ρ[μΩcm] = film thickness × sheet resistance

[0167] Each of the molybdenum-containing films according to the number of moles per second of the reactants and the number of moles per second of the molybdenum-containing precursor used to deposit the film was analyzed by X-ray photoelectron spectroscopy (XPS) according to the etching time, and the results are shown in Figures 1 to 3 middle.

[0168] Figure 1 Results of X-ray photoelectron spectroscopy (XPS) of the molybdenum-containing thin film according to Example 1 according to etching time are shown.

[0169] Figure 2 Results of X-ray photoelectron spectroscopy (XPS) of the molybdenum-containing thin film according to Example 2 according to etching time are shown.

[0170] Figure 3 Results of X-ray photoelectron spectroscopy (XPS) of the molybdenum-containing thin film according to Comparative Example 1 according to etching time are shown.

[0171] Reference Figures 1 to 3 , Example 1 using a reactant at a concentration of 25 times a mole per second showed 99 at % or more Mo, compared to Comparative Example 1 using a reactant at a concentration of 300 times a mole per second showing less than 40 at % Mo, which confirmed that a high-purity molybdenum-containing thin film was obtained.

[0172] Specifically, Example 1 shows a Si content of almost 0 at % and Example 2 shows a Si content of about 3 at %, while Comparative Example 1 shows a Si content of 66 at %, wherein unfavorable resistivity results are expected.

[0173] In this regard, Figure 4 The resistivity results according to the silicon content are shown.

[0174] Reference Figure 4 ,like Figures 1 to 3 As expected in , the resistivity increases with increasing silicon content.

[0175] In other words, the molar number of reactants is adjusted to reduce the silicon content, thereby forming a high purity molybdenum-containing film with low resistivity.

[0176] at the same time, Figure 5 is a transmission electron microscope photograph of a substrate having a groove structure on which a molybdenum-containing thin film is deposited according to Example 1, and Figure 6 The result of an EDS (Energy Dispersive X-ray Spectroscopy) spectrum on the trench structure substrate on which the molybdenum-containing thin film was deposited according to Example 1 is shown.

[0177] Reference Figure 5 and Figure 6 , Mo is uniformly deposited inside the trench structure.

[0178] Figure 7 Results of EDS spectrum analysis of the trench structure according to Example 1 according to the positions of the top, middle, and bottom at high magnification are shown.

[0179] Figure 8 Results of EDS spectrum analysis of the trench structure according to Comparative Example 1 according to the positions of the top, middle, and bottom at high magnification are shown.

[0180] Reference Figure 7 , almost no silicon deposition, but reference Figure 8 , silicon and molybdenum are also deposited uniformly, wherein side effects (high resistivity) are to be expected depending on the silicon content.

[0181] Fig. 9 An X-ray diffraction pattern of the molybdenum-containing thin film according to Example 1 is shown.

[0182] Reference Fig. 9 , it was found that the peak corresponding to Mo has a high intensity.

[0183] Fig.10 is a transmission electron microscope photograph of the molybdenum-containing thin film according to Example 1.

[0184] Reference Fig.10 , to examine the crystal structure of Mo-containing films.

[0185] Comparative Example 2

[0186] Use of compound 1 as a molybdenum-containing precursor in an atomic layer deposition process and diiodomethane (CH 2 I 2 ) to form a molybdenum-containing film.

[0187] First, the silicon oxide layer substrate was kept at 250° C., and compound 1 was filled in a stainless steel bubbler container and kept at 70° C. Compound 1 evaporated in the stainless steel bubbler container was transferred to the silicon oxide layer substrate for 1 second (0.0003 g) by using argon (50 sccm) as a delivery gas to adsorb it in the silicon oxide layer substrate. Next, unreacted compound 1 was removed for 10 seconds by using argon (4000 sccm). Then, diiodomethane (CH 2 I 2 ) 0.5 seconds (0.00625g) to form a molybdenum-containing film. Finally, by using argon (4000sccm) for 30 seconds to remove reaction byproducts and residual reaction gas. The reactant (diiodomethane) is supplied at 22.2 times the molar concentration per second (based on the molar concentration per second of the molybdenum-containing precursor (compound 1)). This process is repeated as a cycle for 800 cycles to form a molybdenum-containing film. The detailed reaction conditions are shown in Table 2.

[0188] The formed molybdenum-containing thin film was heat-treated at 500° C. for 2 hours in a hydrogen atmosphere.

[0189] Table 2

[0190]

[0191]

[0192] Table 3 shows resistivity calculated by using the thickness and sheet resistance of the molybdenum-containing thin film of Comparative Example 2 and the composition thereof obtained by X-ray photoelectron spectroscopy.

[0193] Table 3

[0194]

[0195] Referring to Table 3, Comparative Example 2 differs from the present invention in that a zero-valent molybdenum-based compound combined with one organic ligand is used as a precursor for depositing a thin film, wherein Example 1, which uses a zero-valent molybdenum-based compound combined with at least two organic ligands as a precursor for depositing a thin film, has a higher Mo content but lower O and C contents than Comparative Example 2, and thus proves that a high-purity molybdenum-containing thin film is formed.

[0196] Example 3

[0197] In addition to changing the bis(η6-ethylbenzene) molybdenum (Mo(EtBz)) in Example 2 2 ) and diiodosilane (SiH 2 I 2 ) is implanted in the same manner as in Example 2.

[0198] The composition of the film was analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in Table 4.

[0199] Table 4

[0200]

[0201]

[0202] Referring to Table 4, even if the injection order is changed, a thin film having the same composition is obtained.

[0203] Example 4

[0204] After forming the molybdenum-containing thin film of Example 2, heat treatment was performed in a hydrogen atmosphere. The composition of the thin film was analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in Table 5.

[0205] Table 5

[0206]

[0207] Referring to Table 5, as a result of reducing the Si content by performing heat treatment as a post-treatment, the resistivity decreases.

[0208] Example 5

[0209] The molybdenum-containing film of Example 2 was formed, and after a predetermined amount of ammonia was injected therein, reaction byproducts and residual reaction gas were removed therefrom by using argon gas. The above series of processes were repeated for a predetermined cycle to form a molybdenum-containing film. The detailed conditions for manufacturing the film are shown in Table 6.

[0210] Table 6

[0211]

[0212]

[0213] The results of analyzing the composition of the thin film by X-ray photoelectron spectroscopy (XPS) are shown in Table 7.

[0214] Table 7

[0215]

[0216] Example 6

[0217] In addition to using monoiodosilane (SiH 3 I) A molybdenum-containing film was formed in the same manner as in Example 2 except that as a reactant.

[0218] The results of analyzing the composition of the thin film by X-ray photoelectron spectroscopy (XPS) are shown in Table 8.

[0219] Table 8

[0220]

[0221] Example 7

[0222] In addition to using monoiodosilane (SiH 3 I) A molybdenum-containing film was formed in the same manner as in Example 2 except that as a reactant.

[0223] The results of analyzing the composition of the thin film by X-ray photoelectron spectroscopy (XPS) are shown in Table 9.

[0224] Table 9

[0225]

[0226] Example 8

[0227] A molybdenum-containing thin film was formed in the same manner as in Example 2, except that molybdenum pentachloride was used as the molybdenum-containing precursor.

[0228] The results of analyzing the composition of the thin film by X-ray photoelectron spectroscopy (XPS) are shown in Table 10.

[0229] Table 10

[0230]

[0231] Example 9

[0232] In a conventional atomic layer deposition (thermal ALD) apparatus using a known atomic layer deposition (ALD) method, bis(η6-ethylbenzene)molybdenum (Mo(EtBz)) is deposited. 2 ) as a composition for depositing a molybdenum-containing film to form a molybdenum-containing metal layer, the film was evaluated based on process cycles (60 to 300 cycles). Here, diiodomethane (CH 2 I 2 ) and nitrogen as purge gas (N 2 ).

[0233] In the evaluation according to the process cycle, the silicon oxide layer substrate was set at a temperature of 400° C. The molybdenum precursor and diiodomethane were charged into a stainless steel bubbler container and maintained at 93° C. and 75° C., respectively.

[0234] First, by using 50sccm of nitrogen as a delivery gas, the molybdenum precursor evaporated in the stainless steel bubbler container is transferred to the silicon oxide layer substrate for 5 seconds (0.001g) so that it is adsorbed in the silicon oxide layer substrate. Secondly, the unadsorbed molybdenum precursor is removed by using 1,800sccm of nitrogen for about 10 seconds. Third, the diiodomethane evaporated in the stainless steel bubbler container is formed into a molybdenum-containing metal layer by flowing into 25sccm of nitrogen as a delivery gas for 0.5 seconds (0.009g), and finally, by using 1,800sccm of nitrogen for about 5 seconds, the reaction byproducts and residual reaction gas are removed therefrom. The reactant (diiodomethane) is supplied at a molar concentration of 10.3 times (7.40μmol / sec) per second (based on the molar concentration per second of the molybdenum precursor (0.718μmol / sec)). Repeat the process as a cycle for a predetermined number of cycles to form a molybdenum-containing metal film. The detailed conditions for forming the film are shown in Table 11.

[0235] Table 11

[0236]

[0237] Fig.11 and Fig.12 The growth rate of the molybdenum-containing metal layer according to the amount of deposition is shown. In addition, the thickness, growth rate and resistivity according to the amount of deposition are shown in Table 12.

[0238] Table 12

[0239]

[0240]

[0241] Fig.11 is a transmission electron microscope photograph showing the growth rate according to the amount of deposition of the molybdenum-containing thin film according to Example 9. Fig.12 The correlation between the thickness and the resistivity according to the amount of deposition of the molybdenum-containing thin film according to Example 9 is shown.

[0242] Refer to Table 12 and Fig.11 and Fig.12 , the thickness of the film according to the amount of deposition is proved to grow at a predetermined slope. In other words, the thickness and resistivity of the film can be controlled by adjusting the amount of deposition, which is expected to help achieve a molybdenum-containing film with low resistance by easily adjusting its thickness when necessary.

[0243] Therefore, a substrate temperature of 400° C., at which the thickness of a thin film can be easily controlled, may be very useful industrially.

[0244] Comparative Example 3

[0245] By using bis(η6-ethylbenzene)molybdenum (Mo(EtBz)) in a conventional atomic layer deposition (PEALD) apparatus using a known atomic layer deposition (ALD) method 2 ) as a composition for depositing a molybdenum-containing metal film, but using hydrogen (H 2 ) instead of diiodomethane (CH 2 I 2 ) as a reactant to form a molybdenum-containing metal film, and then the film is evaluated.

[0246] Use nitrogen (N 2 ) as purge gas.

[0247] In the evaluation according to temperature, the silicon substrate is set at a temperature of 400°C. The molybdenum precursor is filled in a stainless steel bubbler container and maintained at 93°C. First, the molybdenum precursor evaporated in the stainless steel bubbler container is transferred to the silicon oxide layer substrate for 2 seconds (0.0004g) by using 50sccm of nitrogen as a conveying gas to adsorb it in the silicon oxide layer substrate. Secondly, the unadsorbed molybdenum precursor is removed for about 10 seconds by using 1,800sccm of nitrogen. Third, 4000sccm of hydrogen as a reaction gas is flowed into it for 10 seconds to form a molybdenum-containing metal film, and finally, reaction byproducts and residual reaction gases are removed therefrom by using 1800sccm of nitrogen for about 5 seconds. This process, which is repeated as a cycle, is repeated for 300 cycles to form a molybdenum-containing metal layer. The detailed conditions for forming the film are shown in Table 13.

[0248] Table 13

[0249]

[0250]

[0251] The growth rate of the deposited amount of the molybdenum-containing metal layer according to Example 9 is shown in Fig.11 and Fig.12 For comparison, the thickness, growth rate, and resistivity of the deposited amount according to Comparative Example 3 are shown in Table 14.

[0252] Table 14

[0253]

[0254] Reference Fig.12 and Table 14 and Fig.11 and Fig.12 , the molybdenum-containing metal films deposited in Example 9 and Comparative Example 3 using diiodomethane and hydrogen as reactants showed a growth rate difference of about 2.5 times and a growth rate difference of about 25×10 8Referring to these results, the molybdenum precursor has very low reactivity with hydrogen but high reactivity with diiodomethane, thereby forming a film that is very favorable in terms of resistivity.

[0255] Example 10 and Example 11

[0256] After forming the molybdenum-containing thin films according to Examples 1 and 2, post-treatment with ozone was performed (process temperature: 300° C. or 350° C.; injection time: 600 sec; flow rate: 1000 sccm). The results of composition analysis using X-ray photoelectron spectroscopy (XPS) are shown in Table 15.

[0257] Table 15

[0258]

[0259] Referring to Table 15, as a result of performing the post-treatment with ozone, an oxidized molybdenum-containing film was formed, and the content of Mo included in the molybdenum oxide was high, and the contents of I and C were low, thereby forming a high-purity oxidized molybdenum-containing film.

[0260] Example 12 and Example 13

[0261] When forming the molybdenum-containing film according to Examples 1 and 2, after performing half (400 cycles) of the total process cycle (800 cycles), post-treatment with ozone (process temperature: 375°C; injection time: 300sec; flow rate: 1000sccm) was performed. After performing the remaining half (400 cycles) of the process cycle, post-treatment with ozone (process temperature: 375°C; injection time: 300sec; flow rate: 1000sccm) was performed to form the molybdenum-containing film. The results of the composition analysis using X-ray photoelectron spectroscopy (XPS) are shown in Table 16.

[0262] Table 16

[0263]

[0264] Referring to Table 16, as a result of performing the post-treatment with ozone, an oxidized molybdenum-containing film was formed, and the content of Mo included in the molybdenum oxide was high, and the contents of I and C were low, thereby forming a high-purity oxidized molybdenum-containing film.

[0265] While the disclosure has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but on the contrary is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A composition for depositing a molybdenum-containing film, comprising: A precursor for thin film deposition, comprising a monovalent molybdenum-based compound, a divalent molybdenum-based compound, a trivalent molybdenum-based compound, a tetravalent molybdenum-based compound, a pentavalent molybdenum-based compound, a hexavalent molybdenum-based compound, a zero-valent molybdenum-based compound bonded to at least two organic ligands, or any combination thereof, and a reactant comprising a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof, Wherein, the molar concentration of the reactant is 200 times or less than the molar concentration of the precursor for thin film deposition: Wherein, in Chemical Formula 1 and Chemical Formula 2, A 1 To A 3 are each independently C, Si, Ge, Sn or Ti, R 1 is hydrogen or a hydrocarbon group, X 1 is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom, n1 is an integer from 1 to 3, and R 2 To R 5 are each independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom, The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

2. The composition for depositing a molybdenum-containing film according to claim 1, wherein The molar concentration of the reactant is 1 to 50 times the molar concentration of the precursor used for thin film deposition.

3. The composition for depositing a molybdenum-containing film according to claim 1, wherein The molar concentration of the reactant is 1 to 25 times the molar concentration of the precursor used for thin film deposition.

4. The composition for depositing a molybdenum-containing film according to claim 1, wherein The organic ligand is a substituted or unsubstituted C4 to C10 organic group including a carbonyl group or a conjugated structure.

5. The composition for depositing a molybdenum-containing film according to claim 1, wherein The precursor for thin film deposition is at least one selected from the following: molybdenum fluoride (MoF6), (2-dimethylaminoethyl) cyclopentadienyl tricarbonyl molybdenum hydride, (2-methoxyethyl) cyclopentadienyl tricarbonyl molybdenum hydride, trimethylsilyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, isopropyl cyclopentadienyl dicarbonyl molybdenum 2-methylallyl, molybdenum chloride (MoCl3 or MoCl5), molybdenum iodide (MoI3), Bis(η6-benzene) molybdenum, bis(η6-methylbenzene) molybdenum, bis(η6-ethylbenzene) molybdenum, bis(η6-1,2-o-xylene) molybdenum, bis(η6-tert-butylbenzene) molybdenum, bis(η6-fluorobenzene) molybdenum, bis(η6-trifluorotoluene) molybdenum, bis(η6-dimethylaniline) molybdenum, bis(η6-methoxybenzene) molybdenum, bis(η6-methylbenzoate) molybdenum, (η6-fluorobenzene)(η6-methylbenzene) molybdenum, (η6-fluorobenzene)(η6-1 ,2-o-xylene) molybdenum, (η6-fluorobenzene)(6-tert-butylbenzene) molybdenum, (η6-fluorobenzene)(η6-N,N-dimethylaniline) molybdenum, (η6-fluorobenzene)(η6-methoxybenzene) molybdenum, (η6-fluorobenzene)(η6-methylbenzoate) molybdenum, (η6-methylbenzoate)(η6-1,2-o-xylene) molybdenum, ((CH3)2N(CH2)2Cp)MoH(CO)3, ((CH3)O( CH2)2Cp)MoH(CO)3, bis((2-dimethylaminoethyl)cyclopentadienyl)molybdenum dihydride (C5H4(CH2CH2N(CH3)2))2MoH2), bis((2-methoxyethyl)cyclopentadienyl)molybdenum dihydride (C5H4(CH2CH2O(CH3)))2MoH2), bis(ethylcyclopentadienyl)molybdenum dihydride, and bis(isopropylcyclopentadienyl)molybdenum dihydride.

6. The composition for depositing a molybdenum-containing film according to claim 1, wherein The reactants are selected from CH3I, CH2I2, CHI3, CH3CH2I, CH3CHI2, ICH2CH2I, CH3CH2CH2I, CH3CHICH3, ICH2CH2CH2I, (CH3)3CI, CHBr3, CH2Br2, CH3CHBr2, CHCl3, CH2Cl2, (CH3)2CHCl, SiHI3, SiH2I2, SiH3I, SiHF3, SiH2F2, SiH3F, SiH At least one selected from the group consisting of Cl3, SiH2Cl2, SiH3Cl, SiHBr3, SiH3Br, SnHI3, SnH2I2, SnH3I, SnHF3, SnH2F2, SnH3F, SnHCl3, SnH2Cl2, SnH3Cl, SnHBr3, SnH3Br, SnH2Br2, CH2CHI, CH2C(I)2, ICHCHI, CH2CHCH2I, CH2CICH3, and ICHCHCH2I.

7. A method for producing a molybdenum-containing film, comprising: a) providing a substrate to the reaction chamber; b) providing a delivery gas and a precursor for thin film deposition to the reaction chamber in a gas phase, wherein the precursor for thin film deposition comprises a monovalent molybdenum-based compound, a divalent molybdenum-based compound, a trivalent molybdenum-based compound, a tetravalent molybdenum-based compound, a pentavalent molybdenum-based compound, a hexavalent molybdenum-based compound, a zero-valent molybdenum-based compound bonded to at least two organic ligands, or any combination thereof; and c) providing a reactant including a compound represented by Chemical Formula 1, a compound represented by Chemical Formula 2, or a combination thereof to the reaction chamber in a gas phase, wherein the reactant is supplied at a molar concentration of 1 to 200 times the molar concentration of the precursor supplied per second for thin film deposition, Wherein, in Chemical Formula 1 and Chemical Formula 2, A 1 To A 3 are each independently C, Si, Ge, Sn or Ti, R 1 is hydrogen or a hydrocarbon group, X 1 is a halogen atom or a hydrocarbon group substituted with at least one halogen atom, n1 is an integer from 1 to 3, and R 2 To R 5 are each independently hydrogen, a halogen atom, a hydrocarbon group, or a hydrocarbon group substituted with at least one halogen atom, The prerequisite is R 2 To R 5 At least one of them is a halogen atom, or a hydrocarbon group substituted with at least one halogen atom.

8. The method for producing a molybdenum-containing thin film according to claim 7, wherein: The temperature of the substrate is maintained at 80° C. to 600° C. in a).

9. The method for producing a molybdenum-containing thin film according to claim 7, wherein: Perform c) after b).

10. The method for producing a molybdenum-containing thin film according to claim 7, wherein: Perform b) after c).

11. The method for producing a molybdenum-containing thin film according to claim 7, wherein: Post-processing is performed after b) and / or c).

12. The method for producing a molybdenum-containing thin film according to claim 11, wherein: The post-treatment includes hydrogen treatment, heat treatment, ammonia treatment, oxygen treatment, ozone treatment, treatment with a reactant containing oxygen atoms, or a combination thereof.

13. The method for producing a molybdenum-containing thin film according to claim 12, wherein: The heat treatment is performed at 200°C to 700°C.

14. The method for producing a molybdenum-containing film according to claim 12, wherein: The reactant containing the oxygen atoms is at least one of O2, O3, O2 plasma, H2O, NO2, NO, N2O, CO, CO2, H2O2, HCOOH, CH3COOH, (CH3CO)2O, alcohol, peroxide, sulfur oxide and combinations thereof.

15. A molybdenum-containing thin film, the molybdenum-containing thin film being manufactured according to the method of claim 7.

16. The molybdenum-containing film according to claim 15, wherein: The molybdenum-containing film has a molybdenum content greater than or equal to 97 atomic percent at %.

17. The molybdenum-containing film according to claim 15, wherein: The molybdenum-containing film has a carbon content of less than 1 at %.

18. The molybdenum-containing film according to claim 15, wherein: The molybdenum-containing film has a halogen content of less than 1 at %.

19. The molybdenum-containing film according to claim 15, wherein: The molybdenum-containing film includes molybdenum oxide, and The molybdenum oxide is MoO2, MoO3 or a combination thereof.

20. The molybdenum-containing film according to claim 19, wherein The molybdenum-containing thin film has a total content of molybdenum (Mo) and oxygen (O) greater than or equal to 97 at %.

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