Thin film forming material, thin film forming method, semiconductor substrate and semiconductor device manufactured thereby

Abstract

The present invention relates to a thin film-forming material, a thin film-forming method, and a semiconductor substrate and semiconductor device manufactured thereby. By using a predetermined substance capable of forming a metal thin film or a metal nitride thin film by a reduction or catalytic reaction as the thin film-forming material, it is possible to effectively manufacture a thin film having low resistance, reduce impurities in the thin film caused by ligands such as carbon, and improve the physical properties of the thin film such as resistivity and crystallinity. This has the effect of providing a thin film-forming material, a thin film-forming method, and a semiconductor substrate and semiconductor device manufactured thereby.

Description

[Technical Field]

[0001] The present invention relates to a thin film-forming material, a thin film-forming method, and a semiconductor substrate and semiconductor device manufactured thereby. More specifically, the present invention relates to a thin film-forming material, a thin film-forming method, and a semiconductor substrate and semiconductor device manufactured thereby, which use a predetermined substance capable of forming a metal thin film or a metal nitride thin film by a reduction or catalytic reaction as a thin film-forming material, thereby effectively manufacturing a thin film with low resistance, reducing impurities in the thin film caused by ligands such as carbon, and improving physical properties of the thin film such as roughness and crystallinity. [Background technology]

[0002] In recent years, with the demand for more advanced performance and higher integration of semiconductor elements, there has been an increasing need for electrode materials or diffusion prevention film materials with low resistivity.

[0003] These materials are available in the form of thin films formed using atomic layer deposition (ALD) processes, but the reduction processes used to form these thin films currently require the use of very strong reducing agents and high thermal energy.

[0004] However, highly reactive gases such as N2H4 hydrazine are difficult to handle due to their high toxicity and risk. Furthermore, the reduction to H2 requires high thermal energy, which can cause the precursor compound to thermally decompose, potentially resulting in poor step coverage, voids, or seams in highly integrated or complex substrates with high aspect ratios.

[0005] In addition, impurities (C, Cl) derived from the ligands of the precursor compounds were detected in the thin film. - , F -Not only will these substances (e.g., water) flow in and contaminate the thin film, but they will also disrupt the crystal arrangement and reduce the density of the thin film that is formed, which could lead to problems with electrical conductivity being hindered due to low density.

[0006] Therefore, there is currently a strong demand for the development of thin film forming materials that can provide thin films that are capable of forming uniform thin films with complex structures, that have excellent physical properties such as crystallinity, and that also have low resistance due to a low amount of residual thin film impurities caused by ligands such as carbon, as well as thin film forming methods and semiconductor substrates that use such materials.

[0007]

[0008] [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Republic of Korea Publication Patent No. 2000-0022014 Summary of the Invention [Problem to be solved by the invention]

[0010] In order to solve the above-mentioned problems of the prior art, the present invention aims to provide a thin film formation method and a semiconductor substrate manufactured thereby, which employ a novel material for forming a metal thin film or a metal nitride thin film by reduction or catalytic reaction, thereby effectively improving thin film and deposition characteristics such as reducing impurities and improving resistivity, thereby providing a thin film with excellent film thickness uniformity and low resistance even when formed on a substrate with a complex structure.

[0011] That is, the present invention aims to improve film quality such as electrical properties and film density by applying a novel material that forms a metal thin film or a metal nitride thin film by reduction or catalytic reaction as a thin film forming material.

[0012] Another object of the present invention is to provide a thin film with low resistance by using a novel material that forms a metal thin film or a metal nitride thin film by reduction or catalytic reaction as a thin film forming material.

[0013] The above and other objects of the present invention can all be achieved by the present invention described below. [Means for solving the problem]

[0014] To achieve the above object, the thin film-forming material according to the present invention may have a bond dissociation energy between iodine and hydrogen (H), carbon (C), or a halogen element (F, Cl, Br) of 242 kJ / mol or less, or 290 kJ / mol or more, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine, metal: LanL2DZ, other elements such as carbon and hydrogen: 6-31+G(dp))).

[0015] The thin film-forming material according to the present invention preferably has a bond dissociation energy between iodine and hydrogen (H), carbon (C), or a halogen element (F, Cl, Br) of 300 to 350 kJ / mol, or 150 to 242 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine, metals: LanL2DZ, other elements such as carbon and hydrogen: 6-31+G(dp))).

[0016] The thin film forming material is a material that forms a metal thin film or a metal nitride thin film using a reduction or catalytic reaction, and may include a compound in which iodine (I) is combined with hydrogen (H), carbon (C), or a halogen element (F, Cl, Br).

[0017] The thin film forming material may be one or more selected from the compounds represented by the following Chemical Formulas 1-1 to 1-11.

[0018] [Chemical formula 1-1~1-11]

[0019] [ka]

[0020] The thin film forming material is 3N to 15N hydrogen iodide alone, a gas mixture of 1 to 99% by weight of 3N to 15N hydrogen iodide and the balance of an inert gas to make the total 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 3N to 15N hydrogen iodide and the balance of water to make the total 100% by weight, where the inert gas can be nitrogen, helium, or argon with a purity of 4N to 9N. In this case, a reduction or catalytic reaction can be carried out to effectively form a low-resistance metal thin film or metal nitride thin film.

[0021]

[0022] The present invention can also provide a method for forming a thin film, which is characterized by using the thin film-forming material described above.

[0023] For example, the thin film formation method may include the steps of injecting a precursor compound into a chamber and adsorbing it on the surface of a substrate, and injecting the thin film forming material into the chamber and forming a metal thin film or a metal nitride thin film using a reduction reaction.

[0024] As another example, the thin film formation method may include the steps of injecting a precursor compound into a chamber to adsorb it on the surface of a substrate, injecting the thin film forming material into the chamber to reduce the activation energy of the reaction with a reactive gas, and supplying the reactive gas into the chamber to form a metal thin film or a metal nitride thin film using a reduction reaction.

[0025] Each of the steps may include purging the interior of the chamber with a purge gas.

[0026] The chamber can be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

[0027] The thin film may be a laminated film of one or more materials selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, and Ti.

[0028] The metal thin film or metal nitride thin film may be a thin film having a resistivity in the range of 5 μΩ·cm to 1000 μΩ·cm.

[0029] The thin film may be a wiring thin film or a diffusion barrier film.

[0030] The wiring thin film may be a metal thin film of Mo, W, Ru, Cu or Rh.

[0031] The diffusion barrier film may be a metal nitride thin film such as MoN, WN, TiN, or TaN.

[0032] The metal or metal nitride thin films can serve as precursor compounds for low resistivity thin films.

[0033] The precursor compound may be a molecule having a central metal atom (M) of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, or Ti and one or more ligands consisting of C, N, O, H, or X (halogen), and the bond dissociation energy between the central metal atom and the ligand calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(dp))) may be within 350 kJ / mol.

[0034] The precursor compound may be a molecule composed of one or more species selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, and Ti, and may be a compound having a vapor pressure at 25°C of more than 0.01 mTorr and not more than 100 Torr.

[0035] The substrate carried into the chamber may be heated to 100 to 800°C.

[0036] The reactive gas may be ammonia, hydrogen, or in the case of noble metals, oxygen.

[0037] The thin film may be an aluminum metal film, a copper metal film, a gold metal film, a molybdenum metal film, a silver metal film, a tungsten metal film, a platinum metal film, a tantalum metal film, a cobalt metal film, a ruthenium metal film, a rhodium metal film, a titanium metal film, an aluminum nitride film, a copper nitride film, a gold nitride film, a molybdenum nitride film, a silver nitride film, a tungsten nitride film, a platinum nitride film, a tantalum nitride film, a cobalt nitride film, a ruthenium nitride film, a rhodium nitride film, or a titanium nitride film.

[0038] The thin film is characterized by a low resistivity of 5 μΩ·cm to 1000 μΩ·cm.

[0039] The thin film is characterized in that the content of ligand-derived impurities, such as carbon, is 1% or less when measured by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS).

[0040] The films are characterized by improved impurity reduction within the films using stronger reduction of the crystalline silver metal precursor as measured by X-ray diffraction (XRD).

[0041] The present invention also provides a semiconductor substrate manufactured by the above-described thin film formation method.

[0042] The thin film may be a multi-layer structure of two or three layers.

[0043]

[0044] Furthermore, the present invention provides a semiconductor device comprising the semiconductor substrate described above. [Effects of the Invention]

[0045] According to the present invention, by applying a specific substance that can act as a catalyst or reducing agent as a thin film forming substance, it is possible to provide a reduction or catalytic reaction (reduction of the activation energy of the reaction with the reactant gas) at a process temperature at which the precursor is not thermally decomposed. This has the effect of forming a uniform thin film even when forming a thin film on a highly integrated substrate or a substrate having a complex structure, and improving impurities and film quality to provide a high-quality thin film forming method.

[0046] Furthermore, the present invention has the effect of more effectively reducing impurities and process by-products in the thin film caused by ligands such as carbon, which cause deterioration of film properties such as crystallinity and electrical properties during thin film formation, and improving the crystallinity and resistivity of the thin film by modifying the film quality, thereby improving the electrical properties of the thin film.Furthermore, the present invention has the effect of providing a thin film formation method using the same and a semiconductor substrate manufactured thereby. [Brief explanation of the drawings]

[0047] [Figure 1] 1 is a graph showing the results of analysis by Auger electron spectroscopy (AES) at different temperatures in Example 5 according to the present invention.

[0048] [Figure 2] 1 is a graph showing X-ray diffraction (XRD) analysis results for each process temperature in Example 5 according to the present invention and Comparative Example 3.

[0049] [Figure 3]1 is an XRD analysis graph of Example 6 according to the present invention and conventional Comparative Example 4.

[0050] [Figure 4] FIG. 10 shows the reaction activation energies required for the reduction of the CO and NO ligands of the Mo(CO) precursor and the (EtCp)Mo(CO)(NO) precursor, respectively, using H and HI in Example 8. [Figure 5] FIG. 10 shows the reaction activation energies required for reducing the CO and NO ligands of the Mo(CO) precursor and the (EtCp)Mo(CO)(NO) precursor, respectively, using H and HI in Comparative Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0051] The above-described thin film forming method and the semiconductor substrate produced thereby will be described in detail below.

[0052] The term "thin film forming material" in this description refers to novel materials that are capable of forming thin metal and metal nitride films through catalytic or reduction reactions.

[0053] In this description, the term "catalytic reaction", unless otherwise specified, refers to a reaction with a reactant gas that has the effect of reducing the activation energy of the reaction (a reaction that substitutes or partially reduces the ligands of a precursor compound), and may subsequently involve a reduction step using the reactant gas.

[0054] In this description, the term "reduction reaction" refers, unless otherwise specified, to a reaction that not only displaces the ligands of the precursor compound, but also reduces them to such an extent that reduction reactions provided using conventional reactant gases are omitted.

[0055] In this description, unless otherwise specified, the term "modification" means that a substance other than a precursor or reactant positively interacts with the reaction surface to improve film quality, such as reducing the resistivity of the deposited thin film, increasing density, or reducing impurities.

[0056] Unless otherwise indicated or mentioned in this description, % refers to % by weight.

[0057] The inventors have confirmed that by using a specific thin film forming material that can undergo a catalytic reaction or reduction reaction at a relatively low process temperature so that the precursor compound adsorbed on the surface of the substrate brought into the chamber is not thermally decomposed, the inflow of thin film impurities caused by ligands such as carbon can be prevented and film quality such as electrical properties and crystallinity can be improved, and after conducting research on this, the present invention has been completed.

[0058] The thin film can be provided as a precursor of one or more materials selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, and Ti, for example, and can provide a metal nitride thin film or a metal thin film. In this case, the effects to be achieved by the present invention can be sufficiently obtained.

[0059] Specific examples of the thin film include an aluminum metal film, a copper metal film, a gold metal film, a molybdenum metal film, a silver metal film, a tungsten metal film, a platinum metal film, a tantalum metal film, a cobalt metal film, a ruthenium metal film, a rhodium metal film, a titanium metal film, an aluminum nitride film, a copper nitride film, a gold nitride film, a molybdenum nitride film, a silver nitride film, a tungsten nitride film, a platinum nitride film, a tantalum nitride film, a cobalt nitride film, a ruthenium nitride film, a rhodium nitride film, and a titanium nitride film.

[0060] The thin film may include the aforementioned film compositions alone or in selective areas, but is not limited thereto, and may also include SiH, SiOH, and the like.

[0061] The thin film may be a laminated film of one or more materials selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, and Ti.

[0062] The thin film can be used in semiconductor devices as a low-resistance thin film, including commonly used wiring thin films or diffusion barrier films.

[0063] The thin film may have a resistivity in the range of 5 μΩ·cm to 1000 μΩ·cm.

[0064] The wiring thin film may be a metal thin film of Mo, W, Ru, Cu, or Rh.

[0065] The diffusion barrier film may be a metal nitride thin film such as MoN, WN, TiN, or TaN.

[0066] The metal or metal nitride thin films can serve as precursor compounds for low resistivity thin films.

[0067] The precursor compound may be, for example, a compound having a central metal atom (M) of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, or Ti as a ligand (L 1 , L 2 , L 3 , L 4 , L 5 and L 6 etc.) may have a structure bound thereto.

[0068] Specific examples of the precursor compound include a molecule having a central metal atom (M) of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, and Ti and one or more ligands consisting of C, N, O, H, and X (halogen), and the effect of using the thin film forming material can be maximized when the precursor has a vapor pressure of 0.01 mTorr to 100 Torr at 25°C.

[0069] As another specific example, the precursor compound may be a molecule having a central metal atom (M) of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh, or Ti and one or more ligands consisting of C, N, O, H, or X (halogen), wherein the bond dissociation energy between the central metal atom and the ligand calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(dp))) is 350 kJ / mol or less.

[0070] For example, when the central metal is divalent, L 1 and L 2 can attach to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can stick to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0071] As an example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are -H or -R, which may be the same or different, and -R is C1 to C 10 Alkyl, C1-C 10 Alkenes or C1-C 10 and wherein L is an alkane of the formula 1 , L 2 , L 3 and L 4 The n number of L can be 2 to 6 depending on the oxidation value of the central metal.

[0072] For example, when the central metal is divalent, L 1 and L 2can attach to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can stick to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0073] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are -H, -OR or -NR2, which may be the same or different, and where -R is H, C1 to C 10 Alkyl, C1-C 10 Alkenes, C1-C 10 The alkane may be iPr or TBu, which has a suitable degree of reaction energy to be replaced by the reaction gas described below.

[0074] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 is -H or -X, which may be the same or different, and in this case, -X may be F, Cl, Br, or I, and in this case, has a degree of reaction energy suitable for being replaced by the reaction gas described below.

[0075] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are -H or -R, which may be the same or different, and -R is C1 to C 10 Alkyl, C1-C 10 Alkenes or C1-C 10and may have a linear or cyclic structure, and in this case, have a degree of reaction energy suitable for being replaced by the reaction gas described below.

[0076] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are -H, -OR or -NR2, which may be the same or different, and where -R is H, C1 to C 10 Alkyl, C1-C 10 Alkenes, C1-C 10 The alkane may be iPr or tBu, which has a suitable degree of reaction energy to be replaced by the reaction gas described below.

[0077] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 is -H or -X, which may be the same or different, and in this case, -X may be F, Cl, Br, or I, and in this case, has a degree of reaction energy suitable for being replaced by the reaction gas described below.

[0078] Specifically, the precursor compound having molybdenum (Mo) as the central metal may be one or more compounds selected from compounds having structures represented by the following chemical formulas 2 and 3, and may contain a trimethylenemethane ligand and its derivatives, but the present invention is not limited thereto.

[0079] [Chemical formula 2]

[0080] [ka]

[0081] (In the above chemical formula 2, R1 to R5 are each independently selected from hydrogen, an amino group, a silyl group, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 8 carbon atoms, and does not include cases where R1 to R5 are simultaneously hydrogen.)

[0082] [Chemical formula 3]

[0083] [ka]

[0084] (In the above chemical formula 3, X is H; F; Cl; Br; I; NO; CN; amidinate; guanidinate; ethylenediamine; propylenediamine; -NR6R7; -OR8; R9Cp and linear and branched cyclic, saturated or unsaturated hydrocarbons substituted with one or more of carbon (C), nitrogen (N), oxygen (O), phosphorus (P), and sulfur (S), and R6, R7, R8, and R9 are each independently selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and n is an integer of 0 to 2.)

[0085] The derivative of the trimethylenemethane ligand may include, for example, a structure having a tribenzylidenemethane ligand, a dibenzylidenemethane ligand, or the like.

[0086] Examples of precursor compounds with molybdenum (Mo) as the central metal include hexacarbonylmolybdenum (Mo(CO)6), bis(ethylbenzene)molybdenum ((Ethylbenzene)2Mo), tricarbonyl(2,6-diisopropylaniline)molybdenum ((2,6-diisopropylaniline)Mo(CO)3), carbonyl(1,4-diisopropyl-1,4-diazabutadiene)molybdenum ((1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)), pentacarbonyl(dichloromethylphosphine)molybdenum (Mo(CO)5PCl2Me), and molybdenum acetate dimer. Dimer), bis(allyl)(ethylbenzene)molybdenum ((Ethylbenzene)Mo(allyl)2), dicarbonyl(allyl)(methylcyclopentadienyl)molybdenum (MeCpMo(CO)2(allyl)), dicarbonyl(allyl)(isopropylcyclopentadienyl)molybdenum (iprCpMo(CO)2(allyl)), tris(tetramethylheptanedionato)molybdenum (Mo(thd)3), tris(ethyl methacrylate)(methylcyclopentadienyl)molybdenum ((MeCp)Mo(EMA)3), bis(methylcyclopentadienyl)(tert-butylimido)molybdenum ((tert-butylimido)Mo(MeCp)2), tetrakis(dimethylamido)molybdenum Molybdenum (TDMAMo), dihydridobis(cyclopentadienyl)molybdenum (Cp2MoH2), tetrakis(dithiocarbamate)molybdenum (Mo(Dithiocarbamate)4), chlorobis(tert-butylimido)(aminothiolate)molybdenum ((tert-butylimido)2MoCl(aminothiolate)), (aminothiolate)bis(tert-butylimido)(tert-butylthiol)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), bis(aminothiolate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(aminothiolate)2),Bis(tert-butylthiol)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)2), bis(tert-butylamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylamine)2), (cyclopentadienylethyl methacrylate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(CpEMA)), dioxobis(isopropylamidinato)molybdenum ( MoO2(ipr-amidinate)2), bis(isopropylamidinato)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(ipr-amidinate)2), bis(tert-butoxy)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butoxy)2), (N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum triamine), chloro(hydrazido)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(hydrazido)Cl), dioxobis(dithiocarbamate)molybdenum (MoO2(Dithiocarbamate)2), bis(tert-butylimido)(1,4-di-tert-butyl-1,4-diazabutadiene)molybdenum ((1,4-ditert-butyl-1,4,diazabutadiene)Mo(tert-butylimido)2), dichlorodioxomolybdenum (MoO2Cl2), etc.

[0087] Here, the dichlorodioxomolybdenum (MoO2Cl2), bis(ethylbenzene)molybdenum ((Ethylbenzene)2Mo), tricarbonyl(2,6-diisopropylaniline)molybdenum ((2,6-diisopropylaniline)Mo(CO)3), tricarbonyl(benzene)molybdenum ((benzene)Mo(CO)3), and tricarbonyl(1,4-diisopropyl-1,4-diazabutadiene)molybdenum ((1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)3) may be compounds represented by the following chemical formulas 4-1 to 4-5, respectively.

[0088] [Chemical formula 4-1~4-5]

[0089] [ka]

[0090]

[0091] Here, the pentacarbonyl(dichloromethylphosphine)molybdenum (Mo(CO)5PCl2Me), molybdenum acetate dimer, bis(allyl)(ethylbenzene)molybdenum ((Ethylbenzene)Mo(allyl)2), dicarbonyl(allyl)(methylcyclopentadienyl)molybdenum (MeCpMo(CO)2(allyl)), and dicarbonyl(allyl)(isopropylcyclopentadienyl)molybdenum (iprCpMo(CO)2(allyl)) may be compounds represented by the following chemical formulas 4-6 to 4-10, respectively.

[0092] [Chemical formula 4-6~4-10]

[0093] [ka]

[0094] Here, the tris(tetramethylheptanedionato)molybdenum (Mo(thd)3), tris(ethyl methacrylate)(methylcyclopentadienyl)molybdenum ((MeCp)Mo(EMA)3), bis(methylcyclopentadienyl)(tert-butylimido)molybdenum ((tert-butylimido)Mo(MeCp)2), tetrakis(dimethylamido)molybdenum (TDMAMo), and dihydridobis(cyclopentadienyl)molybdenum (Cp2MoH2) may be compounds represented by the following chemical formulas 4-11 to 4-15, respectively.

[0095] [Chemical formula 4-11~4-15]

[0096] [ka]

[0097] Here, the tetrakis(dithiocarbamate)molybdenum (Mo(Dithiocarbamate)4), chlorobis(tert-butylimido)(aminothiolate)molybdenum ((tert-butylimido)2MoCl(aminothiolate)), (aminothiolate)bis(tert-butylimido)(tert-butylthiol)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), bis(aminothiolate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(aminothiolate)2), and bis(tert-butylthiol)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)2) may be compounds represented by the following chemical formulas 4-16 to 4-20, respectively.

[0098] [Chemical formula 4-16~4-20]

[0099] [ka]

[0100] Here, the bis(tert-butylamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylamine)2), (cyclopentadienylethyl methacrylate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(CpEMA)), dioxobis(isopropylamidinato)molybdenum (MoO2(ipr-amidinate)2), and bis(isopropylamidinato)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(ipr-amidinate)2) may be compounds represented by the following chemical formulas 4-20 to 4-24, respectively.

[0101] [Chemical formula 4-20~4-24]

[0102] [ka]

[0103] Here, the bis(tert-butoxy)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butoxy)2) and (N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum triamine), chloro(hydrazido)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(hydrazido)Cl), dioxobis(dithiocarbamate)molybdenum (MoO2(Dithiocarbamate)2), bis(tert-butylimido)(1,4-di-tert-butyl-1,4,diazabutadiene)molybdenum ((1,4-ditert-butyl-1,4,diazabutadiene)Mo(tert-butylimido)2), dichlorodioxomolybdenum (MoO2Cl2), bis(dimethylamido)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(dimethylamide)2), and bis(methylbenzene)molybdenum ((Methylbenzene)2Mo) can be compounds represented by the following chemical formulas 4-25 to 4-31, respectively.

[0104] [Chemical formula 4-25~4-31]

[0105] [ka]

[0106] For example, the precursor compound can be used by mixing with a non-polar solvent, which has the advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0107]

[0108] The thin film-forming material of the present invention can lower the activation energy of a precursor compound adsorbed on a substrate and carry out a catalytic reaction that effectively replaces ligands. Depending on the structure, the material may even have reducing power to carry out a reduction reaction, thereby eliminating the reduction step using a reaction gas that is required after the catalytic reaction.

[0109] The ligand may be substituted, for example, on the entire substrate or a portion of the substrate on which the thin film is formed using the thin film forming material and, if necessary, a reaction gas described below.

[0110] The thin film forming material may be a material that forms a metal thin film or a metal nitride thin film, and an example thereof includes a compound in which iodine (I) is combined with hydrogen (H), carbon (C), or a halogen element (F, Cl, Br).

[0111] The reaction material may undergo a reduction or catalytic reaction to form a metal thin film or a metal nitride thin film.

[0112] The thin film forming material may have an overall bond dissociation energy calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, other elements such as carbon and hydrogen: 6-31+G(dp)) of, for example, 242 kJ / mol or less or 290 kJ / mol or more. In this case, the content of thin film impurities caused by ligands such as carbon can be reduced, effectively providing a thin film with low resistance.

[0113] Among the thin film forming materials, iodine compounds bonded with carbon or halogen elements (F, Cl, Br) exhibit a reducing effect and the appropriate carbon-iodine bond dissociation energy to prevent carbon impurities from remaining may be 242 kJ / mol or less.

[0114] Hydrogen-bonded iodine compounds effective in the present invention may have bond dissociation energies of 290 kJ / mol or greater.

[0115] The thin film forming material may be one or more selected from the compounds represented by the following Chemical Formulas 1-1 to 1-11.

[0116] [Chemical formula 1-1~1-11]

[0117] [ka]

[0118] The thin film forming material may be, for example, 3N to 15N hydrogen iodide alone, a gas mixture of 1 to 99% by weight of 3N to 15N hydrogen iodide and the balance of an inert gas to make the total 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 3N to 15N hydrogen iodide and the balance of water to make the total 100% by weight. Here, the inert gas may be nitrogen, helium, or argon having a purity of 4N to 9N. In this case, a reduction or catalytic reaction is carried out to reduce impurities, thereby effectively forming a low-resistance metal thin film or metal nitride thin film.

[0119] The thin film-forming material is preferably 5N to 6N hydrogen iodide alone, a gas mixture of 1 to 99% by weight of 5N to 6N hydrogen iodide and the balance of an inert gas to bring the total to 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 5N to 6N hydrogen iodide and the balance of water to bring the total to 100% by weight, where the inert gas can be nitrogen, helium, or argon with a purity of 4N to 9N. In this case, not only can side reactions be suppressed during thin film formation, the growth rate of the thin film be adjusted, process by-products in the thin film are reduced, corrosion and deterioration are reduced, and the crystallinity of the thin film is improved, thereby improving film quality. Furthermore, the uniformity of the thin film thickness can be significantly improved, even when the thin film is formed on a highly integrated substrate or a substrate with a complex structure.

[0120] In this case, by providing sufficient catalytic or reduction effects to the precursor compound adsorbed on the substrate at a relatively low process temperature where the precursor is not thermally decomposed, the uniformity of the film thickness can be significantly improved even when forming a thin film on a highly integrated substrate or a substrate having a complex structure. This has the advantages of effectively protecting the substrate surface by preventing the adsorption of not only the thin film precursor but also the process by-products, reducing the reaction rate, and effectively removing the process by-products.

[0121] The thin film-forming material may preferably be a compound with a purity of 99.9% or more, a compound with a purity of 99.95% or more, or a compound with a purity of 99.99% or more. For reference, if a compound with a purity of less than 99% is used, impurities may remain in the thin film or may cause side reactions with the precursor or reactant, so it is preferable to use a material with a purity of 99% or more whenever possible.

[0122]

[0123] The thin film may contain, for example, 100 ppm or less of halogen compounds. For reference, if an excessive amount of halogen remains, for example, when a nitriding agent described later is used under a temperature condition of 200 to 300°C, chlorides such as NH4Cl are generated and remain in the thin film, which is undesirable.

[0124] The thin film can be used as a diffusion barrier film or a wiring thin film, but the present invention is not limited to these.

[0125] In particular, a relatively rough thin film is formed, and the growth rate of the formed thin film is significantly reduced, ensuring the uniformity of the thin film even when applied to a substrate with a complex structure. In particular, it is possible to deposit a thin thin film, and it is possible to provide the effect of improving the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was previously difficult to reduce.

[0126]

[0127] A thin film formation method according to one aspect of the present invention includes the steps of injecting a precursor compound into a chamber and adsorbing it on the surface of a substrate, and injecting the thin film-forming material into the chamber and forming a metal thin film or a metal nitride thin film using a reduction reaction. In this case, the reduction of the precursor adsorbed on the substrate can be effectively carried out at a relatively low process temperature at which the precursor is not thermally decomposed, and the growth rate of the thin film can be appropriately reduced, thereby significantly improving the thickness uniformity of the thin film and providing a thin film with low resistance, even when the thin film is formed on a highly integrated substrate or a substrate having a complex structure.

[0128] The thin film forming material and precursor compound can be delivered into the chamber by the VFC method, DLI method, or LDS method.

[0129] The ratio (mg / cycle) of the precursor compound to the thin film forming material input into the chamber may be 1:1 to 1:20.

[0130] In the step of injecting the thin film forming material onto the surface of the substrate, the feeding time (seconds) of the thin film forming material onto the surface of the substrate is preferably 0.01 to 10 seconds per cycle, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 4 seconds. Within this range, there are advantages such as a low thin film growth rate, excellent step coverage, and cost-effectiveness.

[0131] In this description, the feeding time of the thin film forming material is based on a flow rate of 0.1 to 8,000 mg / cycle with a chamber volume of approximately 15 to 20 L, and more specifically, a flow rate of 10 to 5,000 mg / cycle with a chamber volume of approximately 18 L.

[0132]

[0133] As a specific example, the thin film formation method may include the steps of injecting a precursor compound into a chamber and adsorbing it onto the surface of a substrate, first purging the interior of the chamber with a purge gas, injecting the thin film forming material into the chamber and injecting the adsorbed precursor compound, and forming a metal thin film or a metal nitride thin film using a reduction reaction, and second purging the interior of the chamber with a purge gas.

[0134] The entire process described above can be considered as a unit cycle, and the cycle can be repeated until a thin film having a desired thickness is obtained. When the thin film-forming material is added sequentially after the precursor compound in one cycle to improve film quality, the process by-products produced are effectively removed, the resistivity of the thin film is reduced, and step coverage is significantly improved. In addition, the thickness uniformity of the thin film is improved, and film qualities such as electrical properties, dielectric properties, and thin film density are improved, resulting in the provision of a thin film with low resistance.

[0135] The chamber can be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0136] The substrate carried into the chamber may be heated to 100 to 800°C.

[0137] The thin film forming material or precursor compound may be subjected to a plasma post-treatment step after being vaporized and injected, which can improve the thin film growth rate while reducing process by-products.

[0138]

[0139] Another aspect of the present invention provides a method for forming a thin film, which includes the steps of injecting a precursor compound into a chamber and adsorbing it on the surface of a substrate, injecting a thin film-forming material into the chamber and forming a deposited film using a catalytic reaction, and injecting a reactive gas into the chamber to form a nitride film. In this case, the precursor adsorbed on the substrate is effectively reduced to appropriately reduce the growth rate of the thin film, thereby significantly improving film quality such as electrical properties and thin film density, even when a thin film is formed on a highly integrated substrate or a substrate having a complex structure.

[0140]

[0141] As a specific example, the thin film formation method may include the steps of injecting a precursor compound into a chamber and allowing it to adsorb onto the surface of a substrate, a first step of purging the interior of the chamber with a purge gas, a step of injecting the thin film forming material into the chamber and forming a vapor deposition film using a catalytic reaction, a second step of purging the interior of the chamber with a purge gas, a step of injecting a reaction gas into the chamber to form a thin film, and a third step of purging the interior of the chamber with a purge gas.

[0142] The entire process described above can be considered as a unit cycle, and can be repeated until a thin film of a desired thickness is obtained. When the thin film-forming material is sequentially added after the precursor compound within one cycle to improve film quality, process by-products can be significantly reduced, step coverage can be significantly improved, and the crystallinity of the thin film can be increased, thereby reducing the resistivity of the thin film. Even when applied to semiconductor devices with a large aspect ratio, the uniformity of the thin film thickness can be significantly improved, ensuring the reliability of the semiconductor device. In addition, the process can provide a thin film with low resistance while improving film quality such as electrical properties and thin film density.

[0143] The chamber can be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0144] The substrate carried into the chamber may be heated to 100 to 800°C.

[0145] The reaction gas is not particularly limited as long as it is a gas used to manufacture a metal thin film or a metal nitride thin film, and examples thereof include nitrogen, ammonia, and hydrogen.

[0146] In this description, the reaction gas feeding time is based on a flow rate of 0.1 to 8,000 mg / cycle for a chamber volume of 15 to 20 L, and more specifically, a flow rate of 10 to 5,000 mg / cycle for a chamber volume of 18 L.

[0147]

[0148] In the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the ALD chamber is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor compound, but for example, it may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the precursor compound introduced into the ALD chamber. Within this range, the unadsorbed precursor compound can be sufficiently removed, resulting in the formation of a uniform thin film and preventing deterioration of film quality. Here, the amounts of the purge gas and precursor compound introduced are each based on one cycle, and the volume of the precursor compound refers to the volume of vaporized precursor compound vapor.

[0149]

[0150] Furthermore, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the ALD chamber may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times the volume of the reaction gas introduced into the ALD chamber, and the desired effects can be sufficiently obtained within these ranges. Here, the amounts of the purge gas and reaction gas introduced are each based on one cycle.

[0151]

[0152] The thin film-forming materials, precursor compounds, and reactant gases can be preferably delivered into the ALD chamber by a vapor flow control (VFC) method, a direct liquid injection (DLI) method, or a liquid delivery system (LDS) method, and more preferably delivered into the chamber by a VFC method.

[0153] The substrate loaded into the chamber may be heated to, for example, 100 to 800°C, specifically, 300 to 600°C, and the thin film-forming material or precursor compound may be injected onto the substrate either unheated or heated. Depending on the deposition efficiency, the thin film-forming material or precursor compound may be injected unheated and then the heating conditions may be adjusted during the deposition process. For example, the thin film-forming material or precursor compound may be injected onto the substrate at a temperature of 50 to 400°C for 1 to 20 seconds.

[0154]

[0155] The ratio (mg / cycle) of the precursor compound to the thin film-forming material introduced into the chamber may preferably be 1:1 to 1:400, more preferably 1:2 to 1:350, even more preferably 1:2 to 1:300, and even more preferably 1:2.5 to 1:200. Within this range, the effect of improving step coverage and the effect of reducing process by-products are significant.

[0156]

[0157] The thin film formation method may be carried out at a deposition temperature in the range of, for example, 100 to 800°C, preferably 300 to 600°C, more preferably 300 to 500°C, and even more preferably 300 to 400°C. Within this range, ALD process characteristics are provided and a thin film with excellent film quality is grown.

[0158] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, a thin film with a uniform thickness can be obtained.

[0159] In this description, the deposition temperature and deposition pressure may be measured as the temperature and pressure formed in the deposition chamber, or may be measured as the temperature and pressure applied to the substrate in the deposition chamber.

[0160] The thin film formation method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the precursor compound into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the precursor compound into the chamber.

[0161]

[0162] In the thin film formation method, the strength (c / s) of residual impurities (carbon or halogen elements) in the thin film, measured by SIMS, with a film thickness of 100 Å as a guideline, is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred embodiment, it is 5,000 or less, more preferably 10 to 4,000, and even more preferably 10 to 3,000. Within such ranges, there is an outstanding effect of preventing deterioration of crystallinity and electrical properties.

[0163] In this description, the purge flow rate is preferably 1,000 to 50,000 sccm (standard cubic centimeters per minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition is performed as or close to an atomic monolayer, which is advantageous in terms of film quality.

[0164]

[0165] Furthermore, the present invention may provide a thin-film production apparatus capable of providing the thin-film production method, the thin-film production apparatus including an ALD chamber, a first vaporizer that vaporizes a precursor compound, a first transport means that transports the vaporized precursor compound into the ALD chamber, a second vaporizer that vaporizes a thin-film-forming material, a second transport means that transports the vaporized thin-film-forming material into the ALD chamber, and a third transport means that transports a reactant gas into the ALD chamber. Here, the vaporizer and transport means are not particularly limited as long as they are vaporizers and transport means that are commonly used in the technical field to which the present invention pertains.

[0166] To explain the thin film formation method in detail, first, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of depositing atomic layers.

[0167] The substrate may encompass semiconductor substrates such as silicon substrates, silicon oxide, and the like.

[0168] The substrate may further have a conductive or insulating layer formed thereon.

[0169] To deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned thin film forming material, precursor compound, or a mixture of the precursor compound and a non-polar solvent is prepared.

[0170] Then, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (hereinafter referred to as the "thin film forming composition") is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto a substrate, and the unadsorbed precursor compound or the mixture of the precursor compound and a non-polar solvent is purged.

[0171] The non-polar solvent may preferably be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, the non-polar solvent has the advantage of containing an organic solvent with very low reactivity and solubility, making it easy to control moisture, while improving step coverage even when the deposition temperature is increased during thin film formation.

[0172] In a more preferred example, the non-polar solvent is a C1 to C 10 Alkanes of C3 to C 10 The cycloalkanes may include cycloalkanes of the formula C3 to C6. 10 In this case, the reactivity and solubility are very low, and it is advantageous to be able to easily control the amount of water.

[0173] In this description, C1, C3, etc. refer to the number of carbon atoms.

[0174] The cycloalkane is preferably a C3 to C 10Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, so it is suitable for the vapor deposition process, but is not limited thereto.

[0175] The non-polar solvent has, for example, a solubility in water (25°C) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantage of low reactivity with the precursor compound and easy water management.

[0176] In this description, the solubility is not particularly limited to the measurement methods and standards commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by high performance liquid chromatography (HPLC).

[0177] The non-polar solvent preferably comprises 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0178] If the content of the non-polar solvent exceeds the upper limit, impurities are generated, increasing the resistance and the number of impurities in the thin film. If the content of the organic solvent is below the lower limit, the effect of improving step coverage and reducing impurities such as chlorine (Cl) ions by adding the solvent is not very effective.

[0179]

[0180] Then, the prepared thin film forming material is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber for adsorption, and the unadsorbed thin film forming material is purged.

[0181] In this description, the method for delivering the thin film forming material and precursor compounds to the deposition chamber may be, for example, a method for delivering a vaporized gas using a mass flow controller (MFC) (Vapor Flow Control; VFC) or a method for delivering a liquid using a liquid mass flow controller (LMFC) (Liquid Delivery System; LDS), and preferably, a VFC method is used.

[0182] In this case, the carrier gas or dilution gas for transporting the thin film forming material and precursor compound onto the substrate may be one or a mixture of two or more gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He), but is not limited thereto.

[0183] In this description, the purge gas may be, for example, an inert gas, and preferably, the carrier gas or dilution gas.

[0184]

[0185] Next, a reaction gas is supplied as needed. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and preferably includes a nitriding gas such as nitrogen gas (N), hydrazine gas (NH) or a mixture of nitrogen gas and hydrogen gas, and a reducing gas such as hydrogen gas (H).

[0186] The nitriding gas reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0187] The reducing gas reacts with the precursor compound adsorbed on the substrate to form a metal film.

[0188] The remaining unreacted reactant gas is then purged with an inert gas, which removes not only the excess reactant gas but also any by-products that are produced.

[0189]

[0190] As described above, the thin film formation method, for example, has a unit cycle consisting of a step of adsorbing a precursor compound onto a substrate, a step of purging the unadsorbed precursor compound, a step of adsorbing a thin film forming substance onto a substrate, a step of purging the unadsorbed thin film forming substance, a step of supplying a reactive gas as needed, and a step of purging the remaining reactive gas as needed, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0191] The unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film properties are effectively exhibited.

[0192]

[0193] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described above. In such a case, the thin film has significantly superior uniformity in film thickness, and has excellent density and electrical properties.

[0194]

[0195] The thin film thus produced preferably has a thickness of 30 nm or less, a resistivity of 5 to 2,000 μΩ·cm when the thin film is 10 nm thick, an impurity content of 10,000 ppm or less, and a step coverage of 90% or more. Within these ranges, the thin film exhibits excellent performance as a diffusion barrier film and excellent effectiveness as a metal wiring material, but is not limited thereto.

[0196] The thin film may have a thickness of, for example, 0.1 to 30 nm, preferably 1 to 20 nm, and more preferably 2 to 10 nm, and within this range, the thin film has excellent thin film properties.

[0197] For example, the thin film may have a resistivity of 0.1 to 400 μΩ·cm, preferably 0.1 to 200 μΩ·cm, and more preferably 0.1 to 20 μΩ·cm, based on a film thickness of 10 nm. Within this range, the thin film has the effect of exhibiting excellent thin film properties.

[0198] The thin film preferably has an impurity content of 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 1 to 8,500 ppm, and even more preferably 1 to 1,000 ppm. Within this range, the thin film has excellent crystallinity and improved resistivity. Here, the impurities remaining in the thin film are impurities that remain in the thin film due to insufficient reduction of the metal precursor ligand, and may be, for example, carbon, nitrogen, oxygen, or halogen elements. The lower the amount of impurities remaining in the thin film, the better the film quality, and therefore the more preferable it is.

[0199] The thin film is characterized in that the content of impurities such as carbon derived from the ligand is reduced to 1% or less when measured by XPS.

[0200] The thin film has, for example, a step coverage of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even thin films with complex structures can be easily deposited on substrates, and have the advantage of being applicable to next-generation semiconductor devices.

[0201] The thin film thus produced preferably has a thickness of 20 nm or less, a content of impurities such as carbon, nitrogen, oxygen, and halogen of 10,000 ppm or less based on a thickness of 10 nm, and a step coverage of 90% or more. Within these ranges, the thin film has the effect of exhibiting excellent performance as a dielectric film or a blocking film, but is not limited thereto.

[0202] The thin films are characterized by improved crystallinity as measured by XRD.

[0203] The thin film is characterized by an improved resistivity.

[0204]

[0205] Below, preferred examples and drawings are presented to help understand the present invention better. However, the following examples and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the technical idea thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0206]

[0207] [Example]

[0208] Example 1

[0209] The ALD process was carried out using 5N HI as the thin film forming material and a BTBMMo precursor of the following chemical formula as the precursor compound.

[0210] [ka]

[0211] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBMMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0212] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0213] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0214]

[0215] Example 2

[0216] The ALD process was carried out using 5N HI as the thin film forming material, NH3 as the reactive gas, and the BTBMMo precursor of the following chemical formula as the precursor compound.

[0217] [ka]

[0218]

[0219] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBMMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0220] Next, the prepared HI thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a catalytic reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. NH3 reaction gas was then supplied into the chamber at a flow rate of 1000 sccm, followed by argon gas at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0221] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0222]

[0223] Example 3

[0224] The ALD process was carried out using 5N HI as the thin film forming material and BTBTBMo precursor of the following chemical formula as the precursor compound.

[0225] [ka]

[0226] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBTBMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0227] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0228] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0229]

[0230] Example 4

[0231] The ALD process was carried out using 5N HI as the thin film forming material, NH3 as the reactive gas, and BTBTBMo precursor of the following chemical formula as the precursor compound.

[0232] [ka]

[0233] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBTBMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0234] Next, the prepared HI thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a catalytic reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. NH3 reaction gas was then supplied into the chamber at a flow rate of 1000 sccm, followed by argon gas at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0235] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0236]

[0237] Example 5

[0238] The ALD process was carried out using 5N HI as the thin film forming material and Mo(CO)6 precursor of the following chemical formula as the precursor compound.

[0239] [ka]

[0240] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While Ar gas was flowing at 50 sccm as a carrier gas, the Mo(CO) precursor was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0241] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 375°C, and this process was repeated 50 to 200 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0242] The fabricated thin film (Mo metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as film thickness and refractive index. The film thickness was measured by dividing the measured film thickness by the number of cycles to calculate the film thickness deposited per cycle, which was 10 nm. The sheet resistance was measured using a four-probe measurement method, and the specific resistance was calculated using the measured film thickness. The crystallinity of the Mo thin film was confirmed using XRD analysis.

[0243]

[0244] Example 6

[0245] The ALD process was carried out using 5N HI as the thin film forming material and Mo(tol)2 precursor of the following chemical formula as the precursor compound.

[0246] [ka]

[0247] First, the prepared precursor compound was placed in a separate canister and heated to 130°C. While Ar gas was flowing as a carrier gas at 50 sccm, the Mo(tol) precursor was introduced into the deposition chamber for 10 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0248] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 250°C, and this process was repeated 30 to 300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0249] The film thickness of the fabricated thin film (Mo metal film) was measured using an ellipsometer, a device that can measure optical properties such as the film thickness and refractive index of thin films using the polarization characteristics of light, and the film thickness deposited per cycle was calculated by dividing the measured film thickness by the number of cycles, resulting in a value of 10 nm.The sheet resistance was measured using the four-probe measurement method, and the specific resistance value was calculated using the measured film thickness.

[0250]

[0251] Example 7

[0252] The ALD process was carried out using 5N HI and 99% I-7 as thin film forming materials and MoCl5 precursor of the following chemical formula as a precursor compound.

[0253] [ka]

[0254] First, the prepared precursor compound was placed in a separate canister and heated to 140°C. While Ar gas as a carrier gas was flowing at 100 sccm, the MoCl precursor was introduced into the deposition chamber for 5 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 5.0 Torr.

[0255] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 5.0 Torr. The deposition temperature was maintained at 400-600°C, and this process was repeated 30-300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0256]

[0257] Example 8

[0258] The bond dissociation energies of the thin film-forming materials and metal precursors of the present invention are important factors for reducing the precursors at low temperatures. The computer simulation program used to calculate the bond dissociation energies was Gaussian 16, with the computer simulation method DFT-D3 / B3LYP, and the basis set for iodine and the central metal (e.g., Mo) being LanL2DZ, and the other elements being 6-31+G(d,p).

[0259] The activation energies of the reactions between the Mo(CO)6 and (EtCp)Mo(CO)2(NO) precursors and the thin film-forming materials were also calculated in the same manner as above. The DFT / TS-Berny method was used to search for the transition state, and the intrinsic reaction coordinate (IRC) was 40 pts.

[0260]

[0261] Example 9

[0262] 5N HI was used as the thin film forming substance, and the precursor compounds were MoO2Cl2, MoCl5, BTBMMo, Mo(CO)6, Mo(Tol)2, (CP)Mo(NO)(CO)2, and (cycloheptatriene)Mo(CO)3 precursors with the following chemical formulas. In order to compare the effect of the low-temperature reduction process depending on the bond dissociation energy of the ligand, the ALD process was carried out at temperatures of 250 to 400°C.

[0263] First, the prepared precursor compounds were placed in separate canisters and introduced into the deposition chamber under a vapor pressure of 0.1 to 1 torr, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging, while the pressure inside the reaction chamber was controlled at 5.0 Torr.

[0264] Next, the prepared thin-film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin-film forming material, vaporized in the vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 3 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 5.0 Torr. This process was repeated 30 to 300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0265]

[0266] Example 10

[0267] The thin film forming materials were I-1, I-3, I-5, I-7, I-8, I-10, and I-12, which had a purity of 99% or more and were selected from the materials in Table 5 for which the bond dissociation energies were calculated. The ALD process was performed using NH3 as a reactant for the nitridation process and TiCl4 precursor as a precursor compound.

[0268] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While Ar gas was flowing at 100 sccm as a carrier gas, the TiCl precursor was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 3000 sccm for 5 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.0 Torr.

[0269] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 10 sccm. The thin film forming material vaporized in the vaporizer was then introduced into the deposition chamber containing the substrate for 3 seconds to carry out a reduction reaction. Argon gas was then supplied at 3000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.0 Torr.

[0270] Next, NH3 was supplied to the chamber at 1000 sccm to inject the reaction gas. The deposition temperature was maintained at 550°C, and this process was repeated 50 to 150 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0271]

[0272] Comparative Example

[0273] Comparative Example 1

[0274] The ALD process was carried out using NH3 as the thin film forming material and a BTBMMo precursor having the following chemical formula as the precursor compound.

[0275] [ka]

[0276] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBMMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0277] Next, NH3, the prepared thin film forming material, was supplied to the chamber at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0278] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0279]

[0280] Comparative Example 2

[0281] The ALD process was carried out using NH3 as the reactive gas and BTBTBMo precursor of the following chemical formula as the precursor compound.

[0282] [ka]

[0283] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBTBMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. The pressure inside the reaction chamber was controlled at 2.5 Torr.

[0284] Next, the prepared reaction gas NH3 was supplied to the chamber at a flow rate of 1000 sccm. The reaction gas, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a 10 nm thick self-limiting atomic layer thin film.

[0285] The fabricated thin film (MoN metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as the thickness and refractive index of thin films. The film thickness was measured by dividing the measured thickness by the number of cycles, and the calculated thickness was 10 nm. The thin film's components were analyzed using AES and SIMS. The sheet resistance was then measured using the four-probe measurement method, and the specific resistance was calculated using the measured film thickness.

[0286]

[0287] Comparative Example 3

[0288] The ALD process was carried out using NH3 as the reactive gas and Mo(CO)6 precursor with the following chemical formula as the precursor compound.

[0289] [ka]

[0290] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While Ar gas was flowing at 50 sccm as a carrier gas, the Mo(CO) precursor was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0291] Next, the prepared reaction gas, NH3, was supplied to the chamber at a flow rate of 1000 sccm. The reaction gas, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 375°C, and this process was repeated 50 to 200 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0292] The fabricated thin film (Mo metal film) was measured using an ellipsometer, a device that uses the polarization characteristics of light to measure optical properties such as film thickness and refractive index. The film thickness was measured by dividing the measured film thickness by the number of cycles to calculate the film thickness deposited per cycle, which was 10 nm. The sheet resistance was measured using a four-probe measurement method, and the measured film thickness was used to calculate the resistivity. The crystallinity of the Mo thin film was confirmed by XRD analysis.

[0293]

[0294] Comparative Example 4

[0295] The ALD process was carried out using NH3 as the reactive gas and Mo(tol)2 precursor of the following chemical formula as the precursor compound.

[0296] [ka]

[0297] First, the prepared precursor compound was placed in a separate canister and heated to 130°C. While Ar gas was flowing as a carrier gas at 50 sccm, the Mo(tol) precursor was introduced into the deposition chamber for 10 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0298] Next, the prepared reaction gas, NH3, was supplied to the chamber at a flow rate of 1000 sccm. The reaction gas, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 250 and 300°C, respectively, and this process was repeated 30 to 300 times to form a 10 nm thick self-limiting atomic layer thin film.

[0299] The film thickness of the fabricated thin film (Mo metal film) was measured using an ellipsometer, a device that can measure optical properties such as the film thickness and refractive index of thin films using the polarization characteristics of light, and the film thickness deposited per cycle was calculated by dividing the measured film thickness by the number of cycles, resulting in a value of 10 nm.The sheet resistance was measured using the four-probe measurement method, and the specific resistance value was calculated using the measured film thickness.

[0300]

[0301] Comparative Example 5

[0302] The bond dissociation energies of the thin film-forming materials and metal precursors of the present invention are important factors for reducing the precursors at low temperatures. The computer simulation program used to calculate the bond dissociation energies was Gaussian 16, with the computer simulation method DFT-D3 / B3LYP, and the basis set for iodine and the central metal (e.g., Mo) being LanL2DZ, and the other elements being 6-31+G(d,p).

[0303] The activation energies of the reactions of Mo(CO)6 and (EtCp)Mo(CO)2(NO) precursors with H2 were also calculated in the same manner as above. The transition state was searched for using the DFT / TS-Berny method, and the intrinsic reaction coordinate (IRC) was 40 pts.

[0304]

[0305] Comparative Example 6

[0306] The ALD process was carried out using 99% I-1 as the thin film forming material and MoCl5 precursor of the following chemical formula as the precursor compound.

[0307] [ka]

[0308] First, the prepared precursor compound was placed in a separate canister and heated to 140°C. While Ar gas as a carrier gas was flowing at 100 sccm, the MoCl precursor was introduced into the deposition chamber for 5 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 5.0 Torr.

[0309] Next, the prepared thin film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin film forming material, vaporized in the vaporizer, was then introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Argon gas was then supplied at 5000 sccm for 10 seconds to perform an argon purge. The pressure inside the reaction chamber was controlled at 5.0 Torr. The deposition temperature was maintained at 400-600°C, and this process was repeated 30-300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0310]

[0311] Comparative Example 7

[0312] The ALD process was carried out using NH3 as the reactant for the nitridation process and TiCl4 precursor as the precursor compound.

[0313] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While Ar gas was flowing at 100 sccm as a carrier gas, the TiCl precursor was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 3000 sccm for 5 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.0 Torr.

[0314] Next, NH3 was supplied to the chamber at 1000 sccm to inject the reaction gas. The deposition temperature was maintained at 550°C, and this process was repeated 50 to 150 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0315]

[0316] [Test example]

[0317] For each of the obtained thin films of Examples 1 to 10 and Comparative Examples 1 to 7, the impurity content, the type and content of elements constituting the surface of the material, the deposition rate, the crystal structure, the orientation, etc. were confirmed by the following methods.

[0318] *Analysis of C impurities using secondary ion mass spectrometry (SIMS): The ion sputter was driven into the thin film in the axial direction, and when the sputtering process time reached 50 seconds, which is when it is thought that there is little contamination on the surface layer of the substrate, the C impurity counts were taken into account and the C impurity value was confirmed from the SIMS graph.

[0319] *Auger electron spectroscopy (AES): A focused electron beam is irradiated onto the surface of a material, and the energy of the emitted Auger electrons is measured to analyze the type and content of elements that make up the surface of the material.

[0320] *Measurement of deposition rate (GPC: Growth Per Cycle, growth amount per cycle): The deposition rate (GPC) was measured for each of the obtained thin films in Examples 1 to 6 and Comparative Examples 1 to 4 by the following method. Specifically, the deposition rate of a thin film having a thickness of 3 to 30 nm was measured using an ellipsometer, and the unit was Å / cycle.

[0321] * Grazing incidence X-ray diffraction method (incident angle (θ) = 3°): In order to confirm information such as the crystal structure and orientation, a diffraction analysis of the surface was performed using Cu-Kα X-rays.

[0322] [Table 1]

[0323] As shown in Table 1 above, by utilizing the process of using the HI thin film forming material alone or the process of using the HI thin film forming material and NH3 reactive gas in combination according to the present invention, it was confirmed that the amount of C impurity generated when NH3 reactive gas is used alone is rapidly reduced. Furthermore, as is clear from Examples 1 and 2, the AES analysis results confirmed that the C impurity was reduced to 0% during thin film formation, and the SIMS analysis results confirmed that the number of detected C ions was reduced by more than 91%.

[0324] Furthermore, the film density increased from 6.0 to 6.8, indicating that a MoN film of extremely high quality was formed.

[0325] [Table 2]

[0326] As shown in Table 2 above, when the HI thin film forming material according to the present invention is used alone or in combination with NH3 reactive gas, the resistivity of the formed thin film is rapidly reduced compared to when NH3 reactive gas is used alone. The order of C impurities is Comparative Example 2 > Example 4 > Example 3, suggesting that the HI thin film forming material alone is also the most effective in reducing the resistivity of the formed thin film.

[0327] [Table 3]

[0328] As shown in Table 3 above, when the HI thin film forming material according to the present invention was used, the resistivity of the formed thin film was rapidly reduced and the deposition rate was increased by more than three times compared to when NH3 reactant gas was used alone. In particular, XRD analysis was performed for each process temperature, and the results are shown in Figure 2 below. Figure 2 is a graph of XRD analysis for each process temperature for Example 5 of the present invention and Comparative Example 3.

[0329] As is clear from FIG. 2 below, in Example 5, a pure Mo metal thin film was formed.

[0330] Furthermore, the AES analysis results for each temperature in Example 5 are shown in FIG. 1 below.

[0331] 1 is a graph showing the results of AES analysis at different temperatures in Example 5 of the present invention. As is clear from FIG. 1 below, the changes in the types and contents of constituent elements at different process temperatures were confirmed.

[0332] [Table 4]

[0333] As shown in Table 4 above, when the HI thin film forming material according to the present invention was used, the resistivity of the formed thin film was significantly reduced and the deposition rate was more than doubled compared to when only NH3 reactive gas was used. In particular, XRD analysis was performed, and the results are shown in Figure 3 below. Figure 3 is an XRD analysis graph of Example 6 of the present invention and Comparative Example 4.

[0334] As is clear from FIG. 3 below, in Example 6, a partially pure Mo metal thin film was formed.

[0335] [Table 5]

[0336] As shown in Table 5, when the HI thin film forming material according to the present invention was used, a Mo metal thin film with low resistivity was formed at a low temperature of 400°C. Furthermore, when iodine bonded to carbon was used, a Mo thin film was formed without carbon impurities when I-7, which has a low bond dissociation energy, was used. However, when I-1, which has a strong carbon-iodine bond of 250 kJ / mol, not only did the resistivity increase by more than 10 times, but carbon impurities were also present in the thin film. This is because carbon is a factor in increasing the resistivity, acting as an impurity inside the thin film. The mechanism by which thin film impurities remain is that when the bond dissociation energy between carbon and iodine is high, the iodine bond does not dissociate, or the dissociated carbon molecules bind strongly to the surface of the substrate and do not detach.

[0337] In Example 8, the bond dissociation energies of carbon or hydrogen compounds bonded to iodine were calculated, and the results are shown in Table 6 below.

[0338] [Table 6]

[0339] Meanwhile, in Example 8 and Comparative Example 5, the reaction activation energies required to reduce the CO and NO ligands of the Mo(CO) precursor and the (EtCp)Mo(CO)(NO) precursor, respectively, are compared between H and HI and are shown in Figures 4 and 5 below.

[0340] As can be seen from Figures 4 and 5 below, the energy required to reduce the CO ligand in the Mo(CO) precursor using H2 is 341.67 KJ / mol, but when HI is used, the activation energy is extremely low at 157.12 KJ / mol. This result suggests that reduction is possible at a lower process temperature without C and O impurities.

[0341] The energy required to reduce the NO ligand in the (EtCp)Mo(CO)2(NO) precursor using H2 is 323.77 KJ / mol, while the activation energy when using HI is an extremely low 82.91 KJ / mol. This result suggests that reduction can be achieved without N and O impurities and at lower process temperatures.

[0342] The bond dissociation energies of Mo precursors applicable to low-temperature processes are shown in Table 7 below.

[0343] [Table 7]

[0344] As is clear from Table 7 above, it can be confirmed that reduction occurs at temperatures of 400°C or less when the bond dissociation energy between Mo and the ligand bound thereto is 350 KJ / mol or less.

[0345]

[0346] Table 8 below shows the resistivity results according to the bond dissociation energy of the inventive substances used to reduce the reaction activation energy between TiCl4 and NH3 reactive gases when forming a TiN thin film.

[0347] [Table 8]

[0348] As is clear from Table 8, except for I-12 which does not have a bond between carbon and iodine, in the case of iodine bonded to carbon, it was confirmed that not only the deposition rate but also the resistivity were improved only for materials of 242 kJ / mol or less.

[0349] In particular, it was confirmed that the greater the bond dissociation energy between carbon and iodine, the greater the deterioration in resistivity.

[0350]

[0351] As a result, it was confirmed that by using a specific thin film forming material that can undergo a catalytic reaction or reduction reaction at a relatively low process temperature so that the precursor compound adsorbed on the surface of the substrate brought into the chamber is not thermally decomposed, it is possible to prevent the inflow of thin film impurities caused by ligands such as carbon while improving film quality such as electrical properties and crystallinity.

Claims

1. A thin film-forming material characterized in that the bond dissociation energy between iodine and hydrogen (H), carbon (C), or halogen elements (F, Cl, Br) bonded thereto, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen elements: 6-31+G(d.p)), is 242 kJ / mol or less, or 290 kJ / mol or more.

2. 2. The thin film forming material according to claim 1, wherein the thin film forming material is a material that forms a metal thin film or a metal nitride thin film using a reduction or catalytic reaction, and includes a compound in which iodine (I) is combined with hydrogen (H), carbon (C), or a halogen element (F, Cl, Br).

3. 2. The thin film forming material according to claim 1, wherein the thin film forming material is at least one selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-11. [Chemical formulas 1-1 to 1-11] 【Chemistry 1】

4. 2. The thin film-forming material according to claim 1, wherein the thin film-forming material is 3N to 15N hydrogen iodide alone, a gas mixture of 1 to 99% by weight of 3N to 15N hydrogen iodide and the balance of an inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 3N to 15N hydrogen iodide and the balance of water to make the total amount 100% by weight, wherein the inert gas is nitrogen, helium, or argon having a purity of 4N to 9N.

5. A method for forming a thin film, comprising using the thin film forming substance according to any one of claims 1 to 4.

6. 6. The method for forming a thin film according to claim 5, comprising the steps of injecting a precursor compound into a chamber and adsorbing it on the surface of a substrate, and injecting the thin film-forming material into the chamber and forming a metal thin film or a metal nitride thin film using a reduction reaction.

7. 6. The thin film formation method according to claim 5, characterized in that it comprises the steps of injecting a precursor compound into a chamber and adsorbing it on the surface of the substrate, injecting the thin film forming substance into the chamber to reduce the activation energy of the reaction with a reactive gas, and supplying a reactive gas into the chamber to form a metal thin film or a metal nitride thin film using a reduction reaction.

8. 8. The thin film forming method according to claim 6, wherein each of said steps includes a step of purging the inside of a chamber with a purge gas.

9. 8. The method of claim 6 or 7, wherein the chamber is an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

10. 6. The thin film forming method according to claim 5, wherein the thin film is a laminated film of one or more elements selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, and Ti.

11. 6. The thin film forming method according to claim 5, wherein the thin film is a metal thin film having a resistivity in the range of 5 μΩ·cm to 1000 μΩ·cm, or a metal nitride thin film.

12. 2. The method of claim 1, wherein the precursor compound is a molecule having Mo as a central metal atom (M) and one or more ligands consisting of C, N, O, H, and X (halogens), and the bond dissociation energy between the central metal atom and the ligand is 350 kJ / mol or less, as calculated using a Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(d.p)) in order to reduce Mo metal even at a low process temperature of 400°C or less.

13. 8. The thin film forming method according to claim 6, wherein the substrate carried into the chamber is heated to 100 to 800°C.

14. 6. The thin film forming method according to claim 5, wherein the thin film is an aluminum metal film, a copper metal film, a gold metal film, a molybdenum metal film, a silver metal film, a tungsten metal film, a platinum metal film, a tantalum metal film, a cobalt metal film, a ruthenium metal film, a rhodium metal film, a titanium metal film, an aluminum nitride film, a copper nitride film, a gold nitride film, a molybdenum nitride film, a silver nitride film, a tungsten nitride film, a platinum nitride film, a tantalum nitride film, a cobalt nitride film, a ruthenium nitride film, a rhodium nitride film, or a titanium nitride film.

15. A semiconductor substrate comprising a thin film produced by the thin film formation method according to claim 6 or 7.

16. A semiconductor device comprising the semiconductor substrate of claim 15.

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