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

Abstract

The present invention relates to a thin film forming substance, a thin film forming method, and a semiconductor substrate and a semiconductor device manufactured by the method, and has the following effects: a predetermined substance capable of forming a metal thin film or a metal nitride film through a reduction or catalytic reaction is used as the thin film forming substance; the present invention relates to a thin film forming material, a thin film forming method, and a semiconductor substrate and a semiconductor device manufactured by the method, whereby not only a low-resistance thin film can be effectively manufactured, but also impurities in the thin film caused by a ligand such as carbon can be reduced, and thin film physical properties such as resistivity and crystallinity can be improved.

Description

Technical Field

[0001] The present invention relates to a thin film forming material, a thin film forming method, a semiconductor substrate and a semiconductor device manufactured by the method. More specifically, the present invention relates to a thin film forming method, a semiconductor substrate and a semiconductor device manufactured by the method. By adopting a prescribed substance that can form a metal thin film or a metal nitride film through a reduction or catalytic reaction as the thin film forming material, it can not only effectively manufacture a low-resistance thin film, but also reduce impurities in the thin film caused by ligands such as carbon, thereby improving the thin film properties such as roughness and crystallinity. Background Art

[0002] With the demand for higher performance and higher integration of semiconductor devices, electrode materials or diffusion barrier materials with lower resistivity are needed.

[0003] This material is provided in the form of a thin film through an atomic layer deposition (ALD) process, and the reduction process used to form this film requires the use of extremely strong reducing agents or high heat energy.

[0004] However, highly reactive gases such as hydrazine (N2H4) are highly toxic and dangerous, and therefore need to be handled with care. In addition, high thermal energy is required for H2 reduction. If high thermal energy is applied, the precursor compound will undergo thermal decomposition, which may cause a decrease in step coverage or the appearance of voids or seams on highly integrated or complex substrates with high aspect ratios.

[0005] In addition, impurities (C, Cl - 、F - etc.) to cause contamination and also destroy the crystal arrangement, thereby reducing the density of the formed film, so the conductivity suppression problem caused by low density may occur.

[0006] Therefore, it is necessary to develop a thin film forming material that can form a uniform thin film with a complex structure, excellent thin film properties such as crystallinity, and low residual amount of thin film impurities caused by ligands such as carbon, so as to provide a low-resistance thin film, a thin film forming method using the same, a semiconductor substrate, etc.

[0007] Prior art literature

[0008] Patent document: Korean Patent Publication No. 2000-0022014 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] In order to solve the problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a thin film forming method and a semiconductor substrate manufactured using the method, which adopts a new substance that forms a metal thin film or metal nitride film through reduction or catalytic reaction as a thin film forming material, effectively improving the thin film and deposition characteristics such as reducing impurities and improving resistivity, so that even when a thin film is formed on a substrate with a complex structure, a thin film with uniform thickness and low resistance can be provided.

[0011] That is, the object of the present invention is to improve film quality such as electrical characteristics and film density by using a novel substance that forms a metal thin film or a metal nitride film by a reduction or catalytic reaction as a thin film forming substance.

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

[0013] The above-mentioned and other objects of the present invention can be achieved by the present invention described below.

[0014] Means used to solve problems

[0015] To achieve the above-mentioned purpose, the bond dissociation energy of iodine with hydrogen (H), carbon (C) or halogen elements (F, Cl, Br) calculated by the Gaussian16 software program according to the thin film-forming material of the present invention can be less than 242 kJ / mol or greater than 290 kJ / mol, wherein the Gaussian16 software program adopts DFT-D3 / B3LYP, and for iodine and metals, the basis set (basisset) is LanL2DZ, and for other elements such as carbon and hydrogen, the basis set is 6-31+G(d,p).

[0016] According to the thin film forming material of the present invention, the bond dissociation energy between iodine and hydrogen (H), carbon (C) or halogen elements (F, Cl, Br) calculated using the Gaussian 16 software program can be in the range of 300 to 350 kJ / mol or 150 to 242 kJ / mol, wherein the Gaussian 16 software program adopts DFT-D3 / B3LYP, and for iodine and metals, the basis set is LanL2DZ, and for other elements such as carbon and hydrogen, the basis set is 6-31+G(d,p).

[0017] The thin film forming substance is a substance that forms a metal thin film or a metal nitride film through reduction or catalytic reaction, and may include a compound of iodine (I) combined with hydrogen (H), carbon (C) or halogen elements (F, Cl, Br).

[0018] The thin film forming substance may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-11.

[0019] [Chemical Formula 1-1] to [Chemical Formula 1-11]

[0020]

[0021] The thin film forming substance is pure 3N to 15N hydrogen iodide, or a gas mixture of 1 weight percent to 99 weight percent of 3N to 15N hydrogen iodide and an inert gas as a remainder to make the total amount reach 100 weight percent, or an aqueous solution mixture of 0.5 weight percent to 70 weight percent of 3N to 15N hydrogen iodide and water as a remainder to make the total amount reach 100 weight percent, wherein 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 metal film or metal nitride film with low resistance.

[0022] Furthermore, the present invention can provide a thin film forming method characterized by using the above-mentioned thin film forming substance.

[0023] As an example, the thin film forming method may include: a step of injecting a precursor compound into a chamber so that it is adsorbed on the surface of a substrate; and a step of injecting the above-mentioned thin film forming substance into the chamber and forming a metal thin film or a metal nitride film through a reduction reaction.

[0024] As another example, the thin film forming method may include: a step of injecting a precursor compound into a chamber so that it is adsorbed on the surface of a substrate; a step of injecting the above-mentioned thin film forming substance into the chamber to reduce the activation energy of the reaction with the reaction gas; and a step of supplying the reaction gas into the chamber and forming a metal thin film or a metal nitride film through a reduction reaction.

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

[0026] The chamber may 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 stacked film of one or more 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 film may be a thin film having a resistivity in a range of 5 μΩ·cm to 1000 μΩ·cm.

[0029] The film may be a wiring film or an anti-diffusion film.

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

[0031] The anti-diffusion film may be a metal nitride film of MoN, WN, TiN or TaN.

[0032] The metal thin film or metal nitride film can be provided by a thin film precursor compound having low resistance.

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

[0034] The precursor compound may be a molecule composed of one or more selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, and Ti, and may have a vapor pressure of more than 0.01 mTorr and less than 100 Torr at 25° C.

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

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

[0037] The thin film can 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, etc.

[0038] The thin film is characterized in that it has a low resistivity of 5 μΩ·cm to 1000 μΩ·cm.

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

[0040] The thin film is characterized in that the stronger reduction effect of the metal precursor has the effect of reducing impurities inside the thin film, thereby improving the crystallinity measured by X-ray diffraction (XRD).

[0041] Furthermore, the present invention provides a semiconductor substrate characterized by being manufactured using the above-mentioned thin film forming method.

[0042] The film may be a multilayer structure of two or three layers.

[0043] Furthermore, the present invention provides a semiconductor device, characterized by including the aforementioned semiconductor substrate.

[0044] Effects of the Invention

[0045] According to the present invention, by adopting a specified substance that can act as a catalyst or a reducing agent as a thin film forming substance, it is possible to provide a reduction or catalytic reaction (reducing the reaction activation energy with the reaction gas) at a process temperature at which the precursor does not undergo thermal decomposition. Therefore, even when a thin film is formed on a highly integrated substrate or a substrate with a complex structure, a uniform thin film can be formed, and impurities and film quality can be improved, thereby having the effect of providing a high-quality thin film formation method.

[0046] Furthermore, the present invention can more effectively reduce impurities and process byproducts within the thin film caused by ligands such as carbon, which can degrade film properties (crystallinity, electrical properties, etc.) during thin film formation, and improve film quality to improve film crystallinity and resistivity, thereby improving the electrical properties of the thin film. Furthermore, the present invention can provide a thin film formation method using the present invention and a semiconductor substrate manufactured using the method. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0048] Figure 2 1 and 2 are X-ray diffraction (XRD) analysis diagrams of Example 5 according to the present invention and Comparative Example 3 according to the prior art at different process temperatures.

[0049] Figure 31 is an X-ray diffraction (XRD) analysis chart between Example 6 according to the present invention and Comparative Example 4 according to the prior art.

[0050] Figure 4 and Figure 5 Graph showing the activation energy required for the reduction of the CO ligand and NO ligand of the Mo(CO)6 precursor and the (EtCp)Mo(CO)2(NO) precursor, respectively, in Example 8 and Comparative Example 5, compared with H2 and HI. DETAILED DESCRIPTION

[0051] Hereinafter, the thin film forming method of this specification and the semiconductor substrate manufactured by the method will be described in detail.

[0052] In this specification, the term "thin film forming substance" refers to a novel substance that can form a metal thin film and a metal nitride film through a catalytic reaction or a reduction reaction.

[0053] In this specification, unless otherwise specifically defined, the term "catalytic reaction" refers to a reaction (reaction of substituting or partially reducing a ligand of a precursor compound) accompanied by a reduction effect of the reaction activation energy with a reaction gas, which can then be accompanied by a reduction process using a reaction gas.

[0054] In this specification, unless otherwise specifically defined, the term "reduction reaction" refers to a reaction that not only replaces a ligand of a precursor compound but also reduces the precursor compound to such an extent that a reduction reaction provided by using a reaction gas in the prior art can be omitted.

[0055] In this specification, unless otherwise specifically defined, the term "modification" means that substances other than precursors and reactive substances actively interact on the reaction surface to improve film quality, such as reducing the resistivity of the deposited film, increasing density, reducing impurities, etc.

[0056] In this specification, unless otherwise specifically defined, % means % by weight.

[0057] The inventors have confirmed that the precursor compounds adsorbed on the surface of the substrate loaded inside the chamber use specified thin film forming substances that can undergo catalytic reactions or reduction reactions at lower process temperatures (temperatures at which the precursor does not undergo thermal decomposition), thereby preventing and preventing the influx of impurities into the thin film caused by ligands such as carbon, while improving the film quality such as electrical properties and crystallinity, and have devoted themselves to related research to ultimately complete the present invention.

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

[0059] As a specific example, the thin film may 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 or a titanium nitride film, etc.

[0060] The thin film may include the aforementioned film components alone or in a selective area, but is not limited thereto and may also include SiH, SiOH, etc.

[0061] The thin film may be a stacked film of one or more 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 as a thin film having low resistance including a generally used wiring film or a diffusion prevention film in a semiconductor device.

[0063] The resistivity of the thin film may be 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 anti-diffusion film may be a metal nitride film of MoN, WN, TiN or TaN.

[0066] The metal thin film or metal nitride film can be provided by a low-resistance thin film precursor compound.

[0067] As an example, the precursor compound may have a structure having Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh and Ti as the central metal atom (M) and combined with a ligand (L1, L2, L3, L4, L5, L6, etc.).

[0068] As a specific example, the precursor compound can be a molecule with Al, Cu, Au, Mo, Ag, W, Pt, Ta, Co, Ru, Rh and Ti as the central metal atom (M) and one or more ligands composed of C, N, O, H, X (halogen), and when the precursor has a vapor pressure of 0.01mTorr to 100Torr at 25°C, the use effect of the thin film forming substance can be maximized.

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

[0070] As an example, when the central metal is divalent, L1 and L2 can be bound to the central metal as ligands, and when the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 can be bound to the central metal. The ligands corresponding to L1 to L6 can be the same as or different from each other.

[0071] As an example, L1, L2, L3, L4, L5 and L6 are -H or -R, which can be the same as or different from each other, wherein -R can be a C1-C10 alkyl group, a C1-C10 alkene or a C1-C10 alkane, and can be linear or cyclic, and the number n of L in L1, L2, L3 and L4 can be formed to be 2 to 6 according to the oxidation valence of the central metal.

[0072] As an example, when the central metal is divalent, L1 and L2 can be bound to the central metal as ligands, and when the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 can be bound to the central metal. The ligands corresponding to L1 to L6 can be the same as or different from each other.

[0073] As a specific example, L1, L2, L3, L4, L5 and L6 are -H, -OR or -NR2, which can be the same as or different from each other, wherein -R can be H, C1-C10 alkyl, C1-C10 olefin, C1-C10 alkane, iPr or TBu, and in this case, has reaction energy suitable for being replaced by the reaction gas described later.

[0074] As a specific example, L1, L2, L3, L4, L5 and L6 are -H or -X, which can be the same as or different from each other, wherein -X can be F, Cl, Br or I, and in this case, has reaction energy suitable for being replaced by the reaction gas described later.

[0075] As a specific example, L1, L2, L3, L4, L5 and L6 are -H or -R, which can be the same as or different from each other, wherein -R can be a C1-C10 alkyl, a C1-C10 olefin or a C1-C10 alkane, and can have a linear or cyclic structure. In this case, it has reaction energy suitable for being replaced by the reaction gas described later.

[0076] As a specific example, L1, L2, L3, L4, L5 and L6 are -H, -OR or -NR2, which can be the same as or different from each other, wherein -R can be H, C1-C10 alkyl, C1-C10 olefin, C1-C10 alkane, iPr or tBu, and in this case, has reaction energy suitable for being replaced by the reaction gas described later.

[0077] As a specific example, L1, L2, L3, L4, L5 and L6 are -H or -X, which can be the same as or different from each other, wherein -X can be F, Cl, Br or I, and in this case, has reaction energy suitable for being replaced by the reaction gas described later.

[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 to 3, and may also include trimethylenemethane ligands and derivatives thereof, but is not limited thereto.

[0079] [Chemical Formula 2]

[0080]

[0081] (In the chemical formula 2, R1 to R5 are independently selected from hydrogen, amino, silyl, alkyl with 1 to 8 carbon atoms, and aryl with 6 to 8 carbon atoms, excluding the case where R1 to R5 are all hydrogen.)

[0082] [Chemical Formula 3]

[0083]

[0084] (In Chemical Formula 3, X is H; F; Cl; Br; I; NO; CN; amidino; guanidino; ethylenediamine; propylenediamine; -NR6R7; -OR8; R9Cp, and a linear, branched, or cyclic saturated or unsaturated hydrocarbon substituted with one or more carbon (C), nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); 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 from 0 to 2.)

[0085] As an example, the derivative of the trimethylenemethane ligand may include a structure having a tribenzylmethylenemethane ligand, a dibenzylmethylenemethane ligand, and the like.

[0086] As an example, the precursor compound with molybdenum (Mo) as the central metal may be molybdenum hexacarbonyl (Mo(CO)6), bis(ethylbenzene) molybdenum ((Ethylbenzene)2Mo), 2,6-diisopropylaniline tricarbonyl molybdenum ((2,6-diisopropylaniline)Mo(CO)3), (1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)((1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)), Mo(CO)5PCl2Me, Molybdenum Acetate Dimer, (Ethylbenzene)Mo(allyl)2, MeCpMo(CO)2(allyl), iprCpMo(CO)2(allyl), Mo(thd)3, (MeCp)Mo(EMA)3, (tert-butylimido)Mo(MeCp)2, TDMAMo, Dimethoxysilane Molybdenum dihydrogenate (Cp2MoH2), Molybdenum dithiocabate (Mo(Dithiocabate)4), (tert-butylimido)2MoCl(aminothiolate)), (tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), (tert-butylimido)2Mo(tert-butylthiol)(aminothiolate) ((tertbutylimido)2Mo(aminothiolate)2), (tert-butylimide)2Mo(tert-butylthiol)2((tert-butylimido)2Mo(tert-butylthiol)2), (tert-butylimido)2Mo(tert-butylthiol)2) (tert-butylimido)2Mo(tert-butylamine)2), (tert-butylimido)2Mo(CpEMA)((tert-butylimido)2Mo(CpEMA) )、MoO2(ipr-amidinate)2)、((tert-butylimido)2Mo(ipr-amidinate)2)、(tert-butylimido)2Mo(tert-butylimido)2Mo(tert-butoxy)2)、(tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)((tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine)), (tert-butylimide) 2Mo(hydrazido)Cl((tert-butylimido) 2Mo(hydrazido)Cl), MoO2(Dithiocarbamate)2), (1,4-ditert-butyl-1,4-diazabutadiene) Mo(tert-butylimido)2), molybdenum dioxide dichloride (MoO2Cl2), etc.

[0087] Among them, the molybdenum dioxide dichloride (MoO2Cl2), bis(ethylbenzene) molybdenum ((Ethylbenzene)2Mo), 2,6-diisopropylaniline tricarbonyl molybdenum ((2,6-diisopropylaniline)Mo(CO)3), (benzene)Mo(CO)3((benzene)Mo(CO)3, (1,4-diisopropyl-1,4-diazabutaiene)Mo(CO)3) can be compounds represented by the following chemical formulas 4-1 to 4-5, respectively.

[0088] [Chemical Formula 4-1] to [Chemical Formula 4-5]

[0089]

[0090] Among them, the (Mo(CO)5PCl2Me), molybdenum acetate (II) dimer (Molybdenum Acetate Dimer), (Ethylbenzene)Mo(allyl)2 ((Ethylbenzene)Mo(allyl)2), MeCpMo(CO)2(allyl)), i prCpMo(CO)2(allyl)( i prCpMo(CO)2(allyl)) may be compounds represented by the following Chemical Formulas 4-6 to 4-10, respectively.

[0091] [Chemical Formula 4-6] to [Chemical Formula 4-10]

[0092]

[0093] Among them, the Mo(thd)3, (MeCp)Mo(EMA)3, (tert-butylimido)Mo(MeCp)2((tert-butylimido)Mo(MeCp)2), TDMAMo, and dihydrogenated molybdenumocene (Cp2MoH2) can be compounds represented by the following chemical formulas 4-11 to 4-15, respectively.

[0094] [Chemical Formula 4-11] to [Chemical Formula 4-15]

[0095]

[0096] Among them, the molybdenum dithiocarbamate (Mo(Dithiocabate)4, (tert-butylimido)2MoCl(aminothiolate)), (tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), (tert-butylimido)2Mo(aminothiolate)2((tert-butylimido)2Mo(aminothiolate)2), (tert-butylimido)2Mo(tert-butylthiol)2) can be compounds represented by the following chemical formulas 4-16 to 4-20, respectively.

[0097] [Chemical Formula 4-16] to [Chemical Formula 4-20]

[0098]

[0099] Among them, the (tert-butylimide)2Mo(tert-butylamine)2((tert-butylimido)2Mo(tert-butylamine)2), (tert-butylimide)2Mo(CpEMA)((tert-butylimido)2Mo(CpEMA)), MoO2(ipr-amidinate)2(MoO2(ipr-amidinate)2), and (tert-butylimide)2Mo(ipr-amidinate)2((tert-butylimido)2Mo(ipr-amidinate)2) can be compounds represented by the following chemical formulas 4-20 to 4-24, respectively.

[0100] [Chemical Formula 4-20] to [Chemical Formula 4-24]

[0101]

[0102] Among them, the (tert-butylimido)2Mo(tert-butoxy)2, (tert-butylimido)2Mo(N,N-dimethyldiethylenetriamine) triamine)), (tert-butylimide)2Mo(hydrazido)Cl((tert-butylimido)2Mo(hydrazido)Cl), MoO2(dithiocarbamate)2(MoO2(Dithiocarbamate)2), 1,4-ditert-butyl-1,4-diazabutadiene)Mo(tert-butylimide)2(1,4-ditert-butyl-1,4-diazabutadiene)Mo(tert-butylimido)2), dichloromolybdenum dioxide (MoO2Cl2), (tert-butylimide)2Mo(dimethylamide)2((tert-butylimido)2Mo(dimethylamide)2), and (toluene)2Mo((Methylbenzene)2Mo) can be compounds represented by the following chemical formulas 4-25 to 4-31, respectively.

[0103] [Chemical Formula 4-25] to [Chemical Formula 4-31]

[0104]

[0105] As an example, the precursor compound may be mixed with a non-polar solvent for use. In this case, there is an advantage that the viscosity or vapor pressure of the precursor compound can be easily adjusted.

[0106] The thin film forming material of the present invention can carry out a catalytic reaction of effectively replacing the ligand by reducing the activation energy of the precursor compound adsorbed on the substrate, and according to the structure, it also has the corresponding reducing ability to carry out a reduction reaction, thereby eliminating the reduction process using a reaction gas, wherein the reaction gas is required in the process after the catalytic reaction.

[0107] As an example, the ligand substitution may be performed on the entire substrate or a portion of the substrate on which the thin film is to be formed using the thin film-forming substance (using a reaction gas described later as necessary).

[0108] The thin film forming substance is characterized in that a substance for forming a metal thin film or a metal nitride film can be used, and as an example, it is a compound including iodine (I) combined with hydrogen (H), carbon (C) or a halogen element (F, Cl, Br).

[0109] The reaction-forming substance may form a metal thin film or a metal nitride film by undergoing a reduction or catalytic reaction.

[0110] As an example, the thin film-forming substance can be a substance having a total bond dissociation energy calculated using the Gaussian 16 software program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, other elements such as carbon, hydrogen: 6-31+G(d, p)) of 242 kJ / mol or less or 290 kJ / mol or more. In this case, the content of impurities (carbon, etc.) in the thin film caused by the ligand can be reduced, and a low-resistance thin film can be effectively provided.

[0111] In the case of iodine compounds bonded to carbon or halogen elements (F, Cl, Br) among the thin film forming substances, a reducing effect is exhibited, and in order to prevent carbon impurities from remaining, the appropriate bond dissociation energy of the carbon-iodine bond can be 242 KJ / mol or less.

[0112] In the case of the iodine compound bonded to hydrogen that exhibits the effect of the present invention, the bond dissociation energy thereof may be 290 kJ / mol or more.

[0113] The thin film forming substance may be one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-11.

[0114] [Chemical Formula 1-1] to [Chemical Formula 1-11]

[0115]

[0116] As an example, the thin film forming substance is pure 3N to 15N hydrogen iodide, or a gas mixture of 1 weight percent to 99 weight percent of 3N to 15N hydrogen iodide and an inert gas as a balance to make the total amount 100 weight percent, or an aqueous solution mixture of 0.5 weight percent to 70 weight percent of 3N to 15N hydrogen iodide and water as a balance to make the total amount 100 weight percent, wherein the inert gas can be nitrogen, helium or argon with a purity of 4N to 9N. In this case, impurities can be reduced by performing a reduction or catalytic reaction, and a metal thin film or metal nitride film with low resistance can be effectively formed.

[0117] Preferably, the thin film forming substance may be pure 5N to 6N hydrogen iodide, or a gas mixture of 1 wt% to 99 wt% 5N to 6N hydrogen iodide and an inert gas with the remainder making up 100 wt% of the total, or an aqueous solution mixture of 0.5 wt% to 70 wt% 5N to 6N hydrogen iodide and water with the remainder making up 100 wt% of the total, wherein the inert gas may be nitrogen, helium or argon with a purity of 4N to 9N. In this case, side reactions occurring during thin film formation are suppressed, the film growth rate is adjusted, and corrosion or degradation is reduced due to the reduction of process byproducts in the thin film. In addition, not only is film quality improved, such as improved film crystallinity, but also the thickness uniformity of the thin film can be greatly improved when the thin film is formed on a highly integrated substrate or a substrate having a complex structure.

[0118] In this case, at a relatively low process temperature where the precursor does not thermally decompose, the precursor compound adsorbed on the substrate is fully provided with the effect of a catalytic reaction or a reduction reaction, thereby having the advantage of significantly improving the thickness uniformity of the thin film when forming a thin film on a highly integrated substrate or a substrate having a complex structure, effectively protecting the surface of the substrate by preventing adsorption not only through the thin film precursor but also through the process by-products, reducing the reaction rate, and effectively removing the process by-products.

[0119] Preferably, the film-forming substance may be a compound having a purity of 99.9% or more, a compound having a purity of 99.95% or more, or a compound having a purity of 99.99% or more. For reference, when a compound having a purity of less than 99% is used, impurities may remain in the film or may cause side reactions with precursors or reactants, so substances having a purity of 99% or more are used whenever possible.

[0120] As an example, the film may include 100 ppm or less of halogen compounds. For reference, if the residual halogen content is too high, for example, when using a nitriding agent described later at a temperature of 200°C to 300°C, chlorides such as NH4Cl will be generated, and these chlorides will remain in the film, which is not preferred.

[0121] The film may be used as a diffusion prevention film, a wiring film, or the like, but is not limited thereto.

[0122] In particular, while forming a relatively sparse film, the growth rate of the formed film is significantly reduced. Therefore, even when applied to substrates with complex structures, the uniformity of the film can be ensured. In particular, deposition with a thin thickness can be achieved, and it can provide an effect that not only improves the residual amount of O, Si, metal, and metal oxides that remain as process by-products, but also improves the residual carbon amount that has been difficult to reduce in the past.

[0123] According to an example of the present invention, a thin film forming method is provided, which is characterized by comprising: a step of injecting a precursor compound into a chamber so that it is adsorbed on the surface of a substrate; and a step of injecting the above-mentioned thin film forming substance into the chamber and forming a metal thin film or a metal nitride film through 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 to ensure that the precursor does not undergo thermal decomposition, and the film growth rate can be appropriately reduced, thereby having the effect of greatly improving the uniformity of the film and providing a low-resistance film even when forming a thin film on a highly integrated substrate or a substrate having a complex structure.

[0124] The film forming materials and precursor compounds may be delivered into the chamber via variable flow control (VFC), direct liquid injection (DLI), or liquid delivery system (LDS).

[0125] The ratio of the precursor compound to the film forming material input into the chamber (mg / cycle) may be 1:1 to 1:20.

[0126] In the step of injecting the thin film forming substance into the substrate surface, the time for supplying the thin film forming substance to the substrate surface (Feeding Time, seconds (sec)) 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 further preferably 0.05 to 4 seconds. Within this range, the film has the advantages of low growth rate, excellent step coverage and economy.

[0127] In this specification, the feeding time of the film-forming material is based on a flow rate of 0.1 mg / cycle to 8000 mg / cycle when the volume of the chamber is 15L to 20L. More specifically, in a chamber volume of 18L, the flow rate is based on a flow rate of 10 mg / cycle to 5000 mg / cycle.

[0128] As a specific example, the thin film forming method may include: a step of injecting a precursor compound into the chamber so that it is adsorbed on the surface of the substrate; a step of performing a first purge on the interior of the chamber using a purge gas; a step of injecting the above-mentioned thin film forming substance into the chamber and forming a metal thin film or a metal nitride film through a reduction reaction with the adsorbed precursor compound; and a step of performing a second purge on the interior of the chamber using a purge gas.

[0129] All the above steps can be taken as a unit cycle and the cycle can be repeated until a film of desired thickness is obtained. When the film-forming material is added sequentially after the precursor compound in one cycle in this way to improve the film quality, the following advantages can be achieved: the generated process by-products can be effectively removed to reduce the resistivity of the film, and the step coverage can be greatly improved. While improving the uniformity of the film, the film quality such as electrical properties, dielectric properties, and film density can be improved, thereby providing a low-resistance film.

[0130] The chamber may 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.

[0131] The substrate loaded in the chamber may be heated to 100 to 800°C.

[0132] The method may include performing a plasma post-treatment after the thin film forming substance or precursor compound is vaporized and injected, thereby improving the growth rate of the thin film while reducing process byproducts.

[0133] According to another example of the present invention, a thin film forming method is characterized by the steps of injecting a precursor compound into a chamber so that it is adsorbed on the surface of a substrate; injecting a thin film forming substance into the chamber and forming a deposited film through a catalytic reaction; and injecting a reaction gas into the chamber to form a nitride film. In this case, the thin film growth rate is appropriately reduced by effectively reducing the precursor adsorbed on the substrate, thereby having the effect of greatly improving the film quality such as electrical properties and film density even when a thin film is formed on a highly integrated substrate or a substrate with a complex structure.

[0134] As a specific example, the thin film forming method may include: a step of injecting a precursor compound into the chamber so that it is adsorbed on the surface of the substrate; a step of purging the interior of the chamber for the first time using a purge gas; a step of injecting the above-mentioned thin film forming substance into the chamber and forming a deposited film through a catalytic reaction; a step of purging the interior of the chamber for a second time using a purge gas; a step of injecting a reaction gas into the chamber to form a thin film; and a step of purging the interior of the chamber for a third time using a purge gas.

[0135] All the above steps can be taken as a unit cycle and the cycle can be repeated until a film of desired thickness is obtained. When the film-forming material is sequentially added after the precursor compound in one cycle in this way to improve the film quality, the following advantages can be achieved: process by-products can be significantly reduced and step coverage can be greatly improved, the resistivity of the film can be reduced by increasing the crystallinity of the film, and even when applied to high aspect ratio semiconductor devices, the thickness uniformity of the film can be greatly improved, thereby not only ensuring the reliability of the semiconductor device, but also improving the film quality such as electrical properties and film density, and providing a low-resistance film.

[0136] The chamber may 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.

[0137] The substrate loaded in the chamber may be heated to 100 to 800°C.

[0138] The reaction gas is not limited as long as it is a gas used to manufacture a metal thin film or a metal nitride thin film, and as an example, it may be nitrogen, ammonia, hydrogen, or the like.

[0139] In this specification, the feeding time of the reaction gas is based on a flow rate of 0.1 mg / cycle to 8000 mg / cycle when the volume of the chamber is 15 L to 20 L. More specifically, in a chamber volume of 18 L, the flow rate is based on a flow rate of 10 mg / cycle to 5000 mg / cycle.

[0140] In the step of purging the unadsorbed precursor compounds, the amount of purge gas introduced into the ALD chamber is not particularly limited as long as it is sufficient to remove the unadsorbed precursor compounds. As an example, the amount of purge gas introduced into the ALD chamber can be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, based on the volume of the precursor compound introduced into the ALD chamber. Within this range, the unadsorbed precursor compounds can be sufficiently removed to achieve uniform thin film formation and prevent film quality degradation. The amounts of purge gas and precursor compound introduced are based on one cycle, and the volume of the precursor compound represents the volume of the vaporized precursor compound vapor.

[0141] Furthermore, in the purge step performed immediately after the reactive gas supply step, as an example, the amount of purge gas introduced into the ALD chamber may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, based on the volume of the reactive gas introduced into the ALD chamber. Within this range, the desired effect can be fully achieved. The amounts of purge gas and reactive gas introduced are each based on one cycle.

[0142] Preferably, the thin film forming materials, precursor compounds, and reaction gases can be delivered into the atomic layer deposition (ALD) chamber by vapor flow control (VFC), direct liquid injection (DLI), or liquid delivery system (LDS), more preferably, by vapor flow control (VFC).

[0143] As an example, the substrate loaded into the chamber can be heated to 100°C to 800°C, and as a specific example, can be heated to 300°C to 600°C. The thin film forming substance or precursor compound can be injected onto the substrate in an unheated state or a heated state. Furthermore, the heating conditions can be adjusted during the deposition process after injection in an unheated state based on deposition efficiency. As an example, the injection can be performed at 50°C to 400°C for 1 second to 20 seconds.

[0144] Preferably, the ratio of the amount of the precursor compound to the amount of the thin film forming substance input into the chamber (mg / cycle (mg / cycle)) can be 1:1 to 1:400, more preferably 1:2 to 1:350, more preferably 1:2 to 1:300, and further preferably 1:2.5 to 1:200. Within this range, the effect of improving step coverage and reducing process by-products is significant.

[0145] As an example, the thin film forming method can be implemented at a deposition temperature in the range of 100°C to 800°C, preferably in the range of 300°C to 600°C, more preferably in the range of 300°C to 500°C, and even more preferably in the range of 300°C to 400°C. Within this range, it has the effect of providing the process characteristics of atomic layer deposition (ALD) while growing it into a thin film with excellent film quality.

[0146] As an example, the thin film forming method can be implemented at a deposition pressure in the range of 0.01 Torr to 20 Torr, preferably in the range of 0.1 Torr to 20 Torr, more preferably in the range of 0.1 Torr to 10 Torr, and most preferably in the range of 0.3 Torr to 7 Torr. Within this range, a thin film with uniform thickness can be obtained.

[0147] In this specification, the deposition temperature and the deposition pressure may be measured by the temperature and pressure formed in the deposition chamber, or by the temperature and pressure applied to the substrate in the deposition chamber.

[0148] Preferably, the thin film forming method may include a step of raising the temperature in the chamber to a deposition temperature before the precursor compound is introduced into the chamber; and / or a step of injecting an inert gas into the chamber for purging before the precursor compound is introduced into the chamber.

[0149] In the thin film forming method, the film thickness is measured by secondary ion mass spectrometry (SIMS). The intensity (c / s) of impurities (carbon or halogen elements) remaining in the film based on the reference can be preferably less than 100,000, more preferably less than 70,000, more preferably less than 50,000, and further preferably less than 10,000. As a preferred embodiment, it can be less than 5,000, more preferably 10 to 4,000, and even more preferably 10 to 3,000. Within this range, the effect of preventing degradation of crystallinity and electrical properties is excellent.

[0150] In this specification, the purge is preferably 1000 sccm to 50000 sccm (Standard Cubic Centimeter per Minute), more preferably 2000 sccm to 30000 sccm, and even more preferably 2500 sccm to 15000 sccm. Within this range, the film growth rate per cycle is properly controlled, and deposition is performed in an atomic mono-layer or close thereto, which has advantages in terms of film quality.

[0151] Furthermore, the present invention, as a thin film manufacturing apparatus capable of providing the thin film manufacturing method, may include a thin film manufacturing apparatus comprising: an atomic layer deposition (ALD) chamber; a first vaporizer for vaporizing a precursor compound; a first delivery device for delivering the vaporized precursor compound into the atomic layer deposition (ALD) chamber; a second vaporizer for vaporizing a thin film forming substance; a second delivery device for delivering the vaporized thin film forming substance into the atomic layer deposition (ALD) chamber; and a third delivery device for delivering a reaction gas into the atomic layer deposition (ALD) chamber. The vaporizer and delivery device may be any of those commonly used in the technical field to which the present invention pertains, and are not particularly limited.

[0152] As a specific example, the thin film forming method is described. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of performing atomic layer deposition.

[0153] The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0154] The substrate may further have a conductive layer or an insulating layer formed on its upper portion.

[0155] In order to deposit a thin film on the substrate in the deposition chamber, the thin film forming material, the precursor compound or a mixture thereof and the non-polar solvent are prepared.

[0156] Subsequently, the prepared precursor compound or its mixture with a non-polar solvent (hereinafter referred to as the "thin film forming composition") is injected into a vaporizer, converted into a vapor phase, and transported to a deposition chamber so that it is adsorbed on the substrate, and the unadsorbed precursor compound or its mixture with a non-polar solvent is purged.

[0157] Preferably, the non-polar solvent may be one or more selected from the group consisting of alkanes and cycloalkanes. In this case, there are the following advantages: the organic solvent includes an organic solvent with low reactivity and solubility and is easy to manage moisture, and at the same time, during the film formation process, when the deposition temperature increases, the step coverage can also be improved.

[0158] As a more preferred example, the non-polar solvent may include C1 to C10 alkane or C3 to C10 cycloalkane, preferably C3 to C10 cycloalkane, in which case it has the advantages of low reactivity and solubility and easy moisture management.

[0159] In this specification, C1, C3, etc. represent the number of carbon atoms.

[0160] Preferably, the cycloalkane may be a C3 to C10 monocycloalkane. Among the monocycloalkane, cyclopentane is liquid at room temperature and has the highest vapor pressure, and is therefore preferred in the vapor deposition process, but is not limited thereto.

[0161] As an example, the solubility of the non-polar solvent in water (25°C) is less than 200 mg / L, preferably 50 mg / L to 400 mg / L, and more preferably 135 mg / L to 175 mg / L. Within this range, it has the advantages of low reactivity to precursor compounds and easy moisture management.

[0162] In this specification, solubility is not particularly limited as long as it is based on a measurement method or standard commonly used in the technical field to which the present invention belongs. As an example, a saturated solution can be measured according to High Performance Liquid Chromatography (HPLC).

[0163] Preferably, based on the total weight of the precursor compound and the non-polar solvent, the content of the non-polar solvent can be 5 wt % to 95 wt %, more preferably 10 wt % to 90 wt %, even more preferably 40 wt % to 90 wt %, most preferably 70 wt % to 90 wt %.

[0164] When the content of the non-polar solvent input exceeds the upper limit value, impurities will be induced, thereby increasing the resistance and the value of impurities in the film. When the content of the organic solvent input is less than the lower limit value, there are disadvantages that the effect of improving the step coverage due to the addition of the solvent and the effect of reducing impurities such as chloride (Cl) ions are not significant.

[0165] Next, the prepared film-forming material is injected into a vaporizer, converted into a vapor phase, and transported to a deposition chamber to be adsorbed, and the unadsorbed film-forming material is purged.

[0166] In this specification, as an example, the method for delivering thin film forming materials and precursor compounds to the deposition chamber can use VFC that uses a mass flow controller (MFC) to deliver volatile gases or LDS that uses a liquid mass flow controller (LMFC) to deliver liquids. Preferably, the VFC method is used.

[0167] At this time, as a carrier gas (transport gas) or dilution gas for moving thin film forming materials and precursor compounds to the substrate, one or a mixed gas of two or more selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) can be used, but is not limited to this.

[0168] In this specification, as an example, an inert gas may be used as the purge gas. Preferably, the transport gas or the dilution gas may be used.

[0169] 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 belongs. Preferably, the reaction gas may include a nitriding gas such as nitrogen (N2), hydrazine gas (N2H4), or a mixture of nitrogen and hydrogen, or a reducing gas such as hydrogen (H2).

[0170] The nitriding gas reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0171] The reducing gas reacts with the precursor compound adsorbed on the substrate to form a metal film.

[0172] Next, the unreacted residual reaction gas is purged with inert gas, thereby removing not only the excess reaction gas but also the generated by-products.

[0173] As described above, as an example, the thin film forming method can take the following steps as a unit cycle, repeating the unit cycle to form a thin film of a desired thickness, the steps including: a step of adsorbing a precursor compound on a substrate; a step of purging unadsorbed precursor compounds; a step of adsorbing a thin film forming substance on a substrate; a step of purging unadsorbed thin film forming substances; a step of supplying a reaction gas as needed; and a step of purging residual reaction gas as needed.

[0174] As an example, the unit cycle can be repeated 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 film properties are well expressed.

[0175] Furthermore, the present invention provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured using the thin film forming method of this specification. In this case, the thickness uniformity of the thin film is very excellent and the density and electrical characteristics of the thin film are excellent.

[0176] Preferably, the thickness of the film manufactured above is less than 30nm, and based on the film thickness of 10nm, the resistivity value is 5μΩ·cm to 2000μΩ·cm, the impurity content is less than 10000ppm, and the step coverage is more than 90%. Within this range, it has excellent performance as an anti-diffusion film and has excellent effects as a metal wiring material, but is not limited to this.

[0177] As an example, the film thickness may be 0.1 nm to 30 nm, preferably 1 nm to 20 nm, and more preferably 2 nm to 10 nm. Within this range, the film has excellent properties.

[0178] As an example, based on a film thickness of 10 nm, the resistivity value of the film can be 0.1 μΩ·cm to 400 μΩ·cm, preferably 0.1 μΩ·cm to 200 μΩ·cm, and more preferably 0.1 μΩ·cm to 20 μΩ·cm. Within this range, the film has excellent properties.

[0179] Preferably, the impurity content of the film can be 10,000 ppm or less, or 1 ppm to 9,000 ppm, more preferably 1 ppm to 8,500 ppm, and even more preferably 1 ppm to 1,000 ppm. Within this range, the film exhibits excellent crystallinity and improved resistivity. Impurities remaining in the film are impurities remaining in the film due to insufficient reduction of the metal precursor ligands. Examples include nitrogen, oxygen, and halogen elements. Lower amounts of residual impurities in the film indicate better film quality, and are therefore preferred.

[0180] The thin film is characterized in that the content of impurities (carbon, etc.) in the thin film caused by the ligand is reduced to 1% or less when measured by X-ray photoelectron spectroscopy (XPS).

[0181] As an example, the step coverage of the film is above 90%, preferably above 92%, and more preferably above 95%. Within this range, even a film with a complex structure can be easily deposited on the substrate. Therefore, it has the advantage of being applicable to the next generation of semiconductor devices.

[0182] Preferably, the thickness of the film manufactured above is less than 20 nm. Taking the film thickness of 10 nm as the benchmark, the impurity content of carbon, nitrogen, oxygen, halogen, etc. is less than 10,000 ppm, and the step coverage is more than 90%. Within this range, it has excellent performance as a dielectric film or barrier film, but is not limited to this.

[0183] The films are characterized by improved crystallinity as measured by X-ray diffraction (XRD).

[0184] The thin film is characterized by improved resistivity.

[0185] Below, preferred embodiments and drawings are presented to help understand the present invention. Those skilled in the art will appreciate that the following embodiments and drawings are only used to illustrate the present invention, and that various changes and modifications may be made within the scope of the scope of the present invention and the technical concept. Of course, these variations and modifications also fall within the scope of protection of the attached patent claims.

[0186] [Example]

[0187] Example 1

[0188] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a thin film forming substance and a precursor having the following chemical formula BTBMMo as a precursor compound.

[0189]

[0190] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBMMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds, followed by an argon purge at 5000 sccm for 10 seconds. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0191] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds, and then a reduction reaction is carried out. Then, argon gas is supplied at a flow rate of 5000 sccm for 10 seconds to implement argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 350°C, and the process described above is repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0192] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0193] Example 2

[0194] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a film forming substance, NH 3 as a reaction gas, and a precursor having the following chemical formula BTBMMo as a precursor compound.

[0195]

[0196] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBMMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds, followed by an argon purge at 5000 sccm for 10 seconds. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0197] Next, the prepared HI film-forming material is loaded into a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The film-forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a catalytic reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to implement an argon purge. In addition, the reaction gas NH3 is supplied into the chamber at a flow rate of 1000 sccm, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to implement an argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 350°C, and the process as described above is repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0198] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0199] Example 3

[0200] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a film-forming substance and a precursor having the following chemical formula BTBTBMo as a precursor compound.

[0201]

[0202] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBTBMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to purge the chamber. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0203] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a reduction reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 350°C, and the above process is repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0204] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0205] Example 4

[0206] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a film forming substance, NH 3 as a reaction gas, and a precursor having the following chemical formula BTBTBMo as a precursor compound.

[0207]

[0208] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBTBMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to purge the chamber. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0209] Next, the prepared HI film-forming material is loaded into a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The film-forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a catalytic reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to implement an argon purge. In addition, the reaction gas NH3 is supplied into the chamber at a flow rate of 1000 sccm, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to implement an argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 350°C, and the process as described above is repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0210] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0211] Example 5

[0212] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a film forming substance and a Mo(CO)6 precursor having the following chemical formula as a precursor compound.

[0213]

[0214] First, the prepared precursor compounds were placed in a separate tank and heated to 50°C. Argon was used as a carrier gas and the Mo(CO)6 precursor was introduced into the deposition chamber at a flow rate of 50 sccm for 3 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was controlled at 2.5 Torr.

[0215] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a reduction reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 375°C, and the above process is repeated 50 to 200 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0216] The thickness of the produced thin film (molybdenum metal film) was measured using an ellipsometer (a device that uses the polarization properties of light to measure optical properties such as film thickness or refractive index). The thickness of the film deposited per cycle was calculated to be 10 nm, divided by the number of cycles. The surface resistivity was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness. The crystallinity of the Mo film was confirmed by X-ray diffraction (XRD) analysis.

[0217] Example 6

[0218] An atomic layer deposition (ALD) deposition process was performed using 5N HI as a thin film forming substance and a precursor having the following chemical formula Mo(tol)2 as a precursor compound.

[0219]

[0220] First, the prepared precursor compounds were placed in a separate tank and heated to 130°C. The Mo(tol)2 precursor was then introduced into the deposition chamber using argon as a carrier gas at a flow rate of 50 sccm for 10 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 2.5 Torr.

[0221] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a reduction reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber is controlled to 2.5 Torr. The deposition temperature is maintained at 250°C, and the above process is repeated 30 to 300 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0222] The thickness of the fabricated thin film (molybdenum metal film) was measured using an ellipsometer (a device that uses the polarization properties of light to measure optical properties such as film thickness or refractive index). Dividing the thickness by the number of cycles, the thickness of the film deposited per cycle was calculated to be 10 nm. Surface resistance was measured using a four-probe method, and the resistivity value was calculated using the measured thickness.

[0223] Example 7

[0224] An atomic layer deposition (ALD) deposition process was performed using 5N HI and 99% I-7 as thin film forming substances and a MoCl5 precursor having the following chemical formula as a precursor compound.

[0225]

[0226] First, the prepared precursor compounds were placed in a separate canister and heated to 140°C. Argon was used as a carrier gas and the MoCl5 precursor was introduced into the deposition chamber at a flow rate of 100 sccm for 5 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 5.0 Torr.

[0227] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a reduction reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber is controlled to 5.0 Torr. The deposition temperature is maintained at 400-600°C, and the process described above is repeated 30 to 300 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0228] Example 8

[0229] The bond dissociation energy between the thin film-forming material and the metal precursor is an important factor in reducing the precursor at low temperatures. The calculation of the bond dissociation energy was performed using Gaussian 16, using the DFT-D3 / B3LYP method with a basis set of LanL2DZ for iodine and the central metal (e.g., Mo) and 6-31+G(d,p) for other elements.

[0230] In addition, the same method was used to calculate the activation energies of the reactions of molybdenum hexacarbonyl (Mo(CO)6) and (EtCp)Mo(CO)2(NO) precursors with the film-forming substances. In this case, the transition state calculation method was DFT / TS-Berny, and the intrinsic reaction coordinate (IRC) was 40 pts.

[0231] Example 9

[0232] Using 5N HI as a thin film-forming substance, the following chemical formulas of molybdenum dioxide dichloride (MoO2Cl2), molybdenum pentachloride (MoCl5), BTBMMo, molybdenum hexacarbonyl (Mo(CO)6), molybdenum (Tol)2 (Mo(Tol)2), (CP) molybdenum (NO)(CO)2 ((CP)Mo(NO)(CO)2), and tricarbonyl cycloheptatrienyl molybdenum ((Cycloheptatriene)Mo(CO)3) precursors were used as precursor compounds, and an ALD deposition process was carried out at 250-400°C to compare the effects of the low-temperature reduction process based on the ligand bond dissociation energy.

[0233] First, the prepared precursor compounds were placed in separate canisters and introduced into the deposition chamber at a vapor pressure of 0.1 to 1 Torr. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was then controlled at 5.0 Torr.

[0234] Next, the prepared thin film-forming material is placed in a tank 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, is then introduced into the deposition chamber loaded with the substrate for 3 seconds to initiate a reduction reaction. Argon gas is then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber is then controlled at 5.0 Torr. This process is repeated 30 to 300 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0235] Example 10

[0236] An atomic layer deposition (ALD) deposition process was performed using I-1, I-3, I-5, I-7, I-8, I-10, and I-12 with a purity of more than 99% from the substances whose bond dissociation energies were calculated in Table 5 as thin film forming materials, NH3 as a reactant for the nitridation process, and a TiCl4 precursor as a precursor compound.

[0237] First, the prepared precursor compounds were placed in a separate tank and heated to 50°C. Argon was used as a carrier gas and the TiCl4 precursor was introduced into the deposition chamber at a flow rate of 100 sccm for 3 seconds. Argon was then supplied at a flow rate of 3000 sccm for 5 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 2.0 Torr.

[0238] 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 introduced into the deposition chamber, loaded with a substrate, for 3 seconds to initiate a reduction reaction. Argon gas was then supplied at a flow rate of 3000 sccm for 10 seconds to perform an argon purge. The pressure within the reaction chamber was maintained at 2.0 Torr.

[0239] Next, NH3 was supplied to the chamber at a flow rate of 1000 sccm to inject the reaction gas. The deposition temperature was maintained at 550°C, and the above process was repeated 50 to 150 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0240] [Comparative Example]

[0241] Comparative Example 1

[0242] An atomic layer deposition (ALD) deposition process was performed using NH 3 as a film forming substance and a precursor having the following chemical formula BTBMMo as a precursor compound.

[0243]

[0244] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBMMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds, followed by an argon purge at 5000 sccm for 10 seconds. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0245] Next, the prepared thin-film-forming substance, NH3, was supplied to the chamber at a flow rate of 1000 sccm. The thin-film-forming substance, vaporized in the vaporizer, was introduced into the deposition chamber loaded with the substrate for 2 seconds to initiate a reduction reaction. Argon gas was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure within the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and the above process was repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0246] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0247] Comparative Example 2

[0248] An atomic layer deposition (ALD) deposition process was performed using NH 3 as a reaction gas and a precursor having the following chemical formula BTBTBMo as a precursor compound.

[0249]

[0250] First, the prepared precursor compounds were placed in separate canisters and supplied at room temperature to a separate vaporizer heated to 150°C using a liquid mass flow controller (LMFC) at a flow rate of 0.1 g / min. The BTBTBMo precursor, vaporized in the vaporizer, was introduced into the deposition chamber for 3 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to purge the chamber. The pressure within the reaction chamber was maintained at 2.5 Torr.

[0251] Next, the prepared NH3 reactant gas was supplied to the chamber at a flow rate of 1000 sccm. The reactant gas, vaporized in the vaporizer, was introduced into the deposition chamber with the substrate loaded for 2 seconds to initiate a reduction reaction. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure within the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 350°C, and the above process was repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0252] For the manufactured thin film (MoN metal film), the thickness of the film was measured using an ellipsometer (a device that can use the polarization properties of light to measure optical properties such as the thickness or refractive index of a thin film) and divided by the number of cycles to calculate the thickness of the film deposited per cycle to be 10nm. The film composition was analyzed by Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). In addition, the surface resistance was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness.

[0253] Comparative Example 3

[0254] An atomic layer deposition (ALD) deposition process was performed using NH 3 as a reaction gas and a precursor of the following chemical formula Mo(CO) 6 as a precursor compound.

[0255]

[0256] First, the prepared precursor compounds were placed in a separate tank and heated to 50°C. Argon was used as a carrier gas and the Mo(CO)6 precursor was introduced into the deposition chamber at a flow rate of 50 sccm for 3 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was controlled at 2.5 Torr.

[0257] Next, the prepared NH3 reactant gas was supplied to the chamber at a flow rate of 1000 sccm. The reactant gas, vaporized in the vaporizer, was introduced into the deposition chamber loaded with the substrate for 2 seconds to initiate a reduction reaction. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure within the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 375°C, and the above process was repeated 50 to 200 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0258] The thickness of the produced thin film (molybdenum metal film) was measured using an ellipsometer (a device that uses the polarization properties of light to measure optical properties such as film thickness or refractive index). The thickness of the film deposited per cycle was calculated to be 10 nm, divided by the number of cycles. The surface resistivity was measured using a four-probe measurement method, and the resistivity value was calculated using the measured thickness. The crystallinity of the Mo film was confirmed by X-ray diffraction (XRD) analysis.

[0259] Comparative Example 4

[0260] An atomic layer deposition (ALD) deposition process was performed using NH 3 as a reaction gas and a precursor of the following chemical formula Mo(tol) 2 as a precursor compound.

[0261]

[0262] First, the prepared precursor compounds were placed in a separate tank and heated to 130°C. The Mo(tol)2 precursor was then introduced into the deposition chamber using argon as a carrier gas at a flow rate of 50 sccm for 10 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 2.5 Torr.

[0263] Next, the prepared NH3 reactant gas was supplied to the chamber at a flow rate of 1000 sccm. The reactant gas, vaporized in the vaporizer, was introduced into the deposition chamber loaded with the substrate for 2 seconds to initiate a reduction reaction. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure within the reaction chamber was controlled at 2.5 Torr. The deposition temperature was maintained at 250°C and 300°C, respectively, and the above process was repeated 30 to 300 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0264] The thickness of the fabricated thin film (molybdenum metal film) was measured using an ellipsometer (a device that uses the polarization properties of light to measure optical properties such as film thickness or refractive index). Dividing the thickness by the number of cycles, the thickness of the film deposited per cycle was calculated to be 10 nm. Surface resistance was measured using a four-probe method, and the resistivity value was calculated using the measured thickness.

[0265] Comparative Example 5

[0266] The bond dissociation energy between the thin film-forming material and the metal precursor is an important factor in reducing the precursor at low temperatures. The calculation of the bond dissociation energy was performed using Gaussian 16, using the DFT-D3 / B3LYP method with a basis set of LanL2DZ for iodine and the central metal (e.g., Mo) and 6-31+G(d,p) for other elements.

[0267] In addition, the same method was used to calculate the activation energies of the reactions of molybdenum hexacarbonyl (Mo(CO)6) and (EtCp)Mo(CO)2(NO) precursors with H2. In this case, the transition state calculation method was DFT / TS-Berny, and the intrinsic reaction coordinate (IRC) was 40 pts.

[0268] Comparative Example 6

[0269] An atomic layer deposition (ALD) deposition process was performed using 99% of I-1 as a thin film forming substance and a MoCl5 precursor having the following chemical formula as a precursor compound.

[0270]

[0271] First, the prepared precursor compounds were placed in a separate canister and heated to 140°C. Argon was used as a carrier gas and the MoCl5 precursor was introduced into the deposition chamber at a flow rate of 100 sccm for 5 seconds. Argon was then supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 5.0 Torr.

[0272] Next, the prepared thin film forming material is placed in a tank and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The thin film forming material vaporized into a vapor phase in the vaporizer is added to the deposition chamber loaded with the substrate for 2 seconds to perform a reduction reaction, and then argon is supplied at a flow rate of 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber is controlled to 5.0 Torr. The deposition temperature is maintained at 400-600°C, and the process as described above is repeated 30 to 300 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0273] Comparative Example 7

[0274] An atomic layer deposition (ALD) deposition process was performed using NH 3 as a reactant for the nitridation process and a TiCl 4 precursor as a precursor compound.

[0275] First, the prepared precursor compounds were placed in a separate tank and heated to 50°C. Argon was used as a carrier gas and the TiCl4 precursor was introduced into the deposition chamber at a flow rate of 100 sccm for 3 seconds. Argon was then supplied at a flow rate of 3000 sccm for 5 seconds to perform an argon purge. The pressure in the reaction chamber was maintained at 2.0 Torr.

[0276] Next, NH3 was supplied to the chamber at a flow rate of 1000 sccm to inject the reaction gas. The deposition temperature was maintained at 550°C, and the above process was repeated 50 to 150 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0277] [Test Example]

[0278] The obtained thin films of Examples 1 to 10 and Comparative Examples 1 to 7 were examined for impurity content, type and content analysis of elements constituting the material surface, deposition rate measurement, crystal structure, orientation, etc., by the following methods.

[0279] *Secondary ion mass spectrometry (SIMS) carbon impurities: ion sputtering was performed along the axial direction into the film. The carbon impurity content (counts) was confirmed in the SIMS graph, considering that the sputtering time was 50 seconds with less contamination in the substrate surface layer.

[0280] *Auger Electron Spectroscopy (AES): This technique measures the energy of Auger electrons emitted when a focused electron beam is incident on a material surface to analyze the types and contents of elements on the material surface.

[0281] *Deposition rate (GPC) measurement: For each of the films obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the deposition rate (GPC) was measured as follows. Specifically, the deposition rate of films with a thickness of 3 nm to 30 nm was measured using an ellipsometer, using the unit:

[0282] *Grazing-incidence angle (incident angle, θ = 3°) X-ray diffraction: Surface diffraction analysis using Cu-Kα X-rays (Cu-Kα X-rays) confirms information such as crystal structure and orientation.

[0283]

Table 1

[0284]

[0285] As shown in Table 1, it was confirmed that when using the thin film-forming substance HI alone or in combination with the reactive gas NH3 according to the present invention, the amount of carbon impurities generated was significantly reduced compared to when using the reactive gas NH3 alone. Furthermore, as shown in Examples 1 and 2, AES analysis confirmed that carbon impurities were reduced to 0% during thin film formation, and SIMS results confirmed a reduction of over 91% in the number of detected carbon ions.

[0286] In addition, the increase in film density from 6.0 to 6.8 indicates that a very high-quality MoN film has been formed.

[0287]

Table 2

[0288]

[0289] As shown in Table 2 above, it can be confirmed that when a process using only the thin film forming substance HI according to the present invention or a process using the thin film forming substance HI and the reaction gas NH3 in combination is used, the resistivity of the formed thin film is drastically reduced compared to the case where the reaction gas NH3 is used alone. In addition, the reduction of C impurities is most significant in the order of Comparative Example 2 > Example 4 > Example 3.

[0290]

Table 3

[0291]

[0292] As shown in Table 3 above, when the thin film forming material HI according to the present invention is used, the resistivity of the formed thin film is drastically reduced, and the deposition rate is increased by more than three times compared to when the reaction gas NH3 is used alone. In particular, X-ray diffraction (XRD) analysis was conducted at different process temperatures, and the results are shown below. Figure 2 middle. Figure 2 1 is an X-ray diffraction (XRD) analysis diagram of different process temperatures according to Example 5 of the present invention and Comparative Example 3.

[0293] as follows Figure 2 As shown, it can be seen that a pure Mo metal thin film is formed in Example 5.

[0294] In addition, the AES analysis results of Example 5 at different temperatures are shown below. Figure 1 middle.

[0295] Figure 1 : is a graph of the AES analysis results at different temperatures according to Example 5 of the present invention. Figure 1 As shown in FIG, it is confirmed that the types and contents of the elements formed vary according to the process temperature.

[0296]

Table 4

[0297]

[0298] As shown in Table 4 above, when the thin film forming material HI according to the present invention is used, the resistivity of the formed thin film is drastically reduced and the deposition rate is increased by more than 2 times compared to the case where only the reaction gas NH3 is used. In particular, X-ray diffraction (XRD) analysis was conducted, and the results are shown below. Figure 3 middle. Figure 3 1 is an X-ray diffraction (XRD) analysis diagram between Example 6 according to the present invention and Comparative Example 4.

[0299] as follows Figure 3 As shown, it can be seen that a pure Mo metal film is partially formed in Example 6.

[0300]

Table 5

[0301]

[0302]

[0303] As shown in Table 5 above, it can be seen that when the film-forming material HI according to the present invention is used, a Mo metal film with low resistivity is formed even at a low temperature of 400 degrees. In addition, it can be seen that even when iodine is combined with carbon, when I-7 with a low bond dissociation energy is used, a Mo film without carbon impurities is formed. However, in the case of I-1 with a strong carbon-iodine bond of 250 kJ / mol, it was confirmed that not only the resistivity increased by more than 10 times, but also carbon impurities were present in the film. The reason for the increase in resistivity is carbon, because it constitutes an impurity inside the film. According to the residual action mechanism of film impurities, when the bond dissociation energy of the carbon-iodine bond is large, the iodine bond will not dissociate, or the dissociated carbon molecules will be strongly bound to the substrate surface and will not detach.

[0304] In Example 8, the bond dissociation energy of carbon or hydrogen compounds bonded to iodine was calculated, and the results are shown in Table 6 below.

[0305]

Table 6

[0306]

[0307] On the other hand, in Example 8 and Comparative Example 5, the activation energy required for the reduction of the CO ligand and NO ligand of the Mo(CO)6 precursor and the (EtCp)Mo(CO)2(NO) precursor, respectively, was compared with that of H2 and HI and is shown below. Figure 4 and Figure 5 middle.

[0308] as follows Figure 4 and Figure 5 As shown in the figure, it can be confirmed that when using H2, the energy required to reduce the CO ligand in the Mo(CO)6 precursor is 341.67 kJ / mol, while when using HI, it is 157.12 kJ / mol, that is, the required activation energy is much lower. This result shows that reduction can be achieved even at lower process temperatures without generating C and O impurities.

[0309] It was confirmed that the energy required for reducing the NO ligand in the (EtCp)Mo(CO)2(NO) precursor using H2 was 323.77 kJ / mol, whereas the energy required using HI was 82.91 kJ / mol, indicating a significantly lower activation energy. This result demonstrates that reduction can be achieved even at lower process temperatures without generating N and O impurities.

[0310] The bond dissociation energies of Mo precursors suitable for low temperature processes are shown in Table 7 below.

[0311]

Table 7

[0312]

[0313]

[0314] As shown in Table 7 above, it was confirmed that when the bond dissociation energy of the ligand bound to Mo is 350 kJ / mol or less, reduction can occur at 400° C. or less.

[0315] Table 8 below shows the resistivity results according to bond dissociation energy for a plurality of inventive substances used to reduce the activation energy of the reaction of TiCl 4 with the reaction gas NH 3 when forming a TiN thin film.

[0316]

Table 8

[0317]

[0318] As shown in Table 8 above, except for I-12 which does not contain a carbon-iodine bond, in the case of iodine bonded to carbon, only in the substances whose bond energy is 242 kJ / mol or less, it was confirmed that not only the deposition rate but also the resistivity was improved.

[0319] In particular, it was confirmed that the greater the bond dissociation energy between carbon and iodine, the greater the decrease in resistivity.

[0320] The results show that by using a specified thin film forming substance that can undergo a catalytic reaction or reduction reaction at a lower process temperature (a temperature at which the precursor does not undergo thermal decomposition) for the precursor compound adsorbed on the surface of the substrate loaded inside the chamber, it is suitable for preventing and preventing the influx of impurities into the thin film caused by ligands such as carbon, while improving the film quality such as electrical properties and crystallinity.

Claims

1. A thin film forming substance, characterized in that The bond dissociation energy between iodine and hydrogen, carbon, or halogen elements such as F, Cl, and Br calculated using the Gaussian 16 software program is less than 242 kJ / mol or greater than 290 kJ / mol, wherein the Gaussian 16 software program adopts DFT-D3 / B3LYP, and for iodine, the basis set is LanL2DZ, and for carbon and hydrogen elements, the basis set is 6-31+G(d,p).

2. The thin film forming material according to claim 1, wherein The thin film forming substance is a substance that forms a metal thin film or a metal nitride film through a reduction or catalytic reaction, and the thin film forming substance includes a compound of iodine combined with hydrogen, carbon, or halogen elements such as F, Cl, and Br.

3. The thin film forming material according to claim 1, wherein The thin film forming substance is one or more compounds selected from the group consisting of the compounds represented by the following chemical formulas 1-1 to 1-11: [Chemical Formula 1-1] to [Chemical Formula 1-11] H-I, ICl,IBr,ICl3。 4. The thin film forming material according to claim 1, wherein The thin film forming substance is pure 3N to 15N hydrogen iodide, or a gas mixture of 1 weight percent to 99 weight percent of 3N to 15N hydrogen iodide and an inert gas as a remainder to make the total amount reach 100 weight percent, or an aqueous solution mixture of 0.5 weight percent to 70 weight percent of 3N to 15N hydrogen iodide and water as a remainder to make the total amount reach 100 weight percent, wherein the inert gas is nitrogen, helium or argon with a purity of 4N to 9N.

5. A thin film forming method, characterized in that: The thin film-forming substance according to any one of claims 1 to 4 is used.

6. The thin film forming method according to claim 5, wherein The thin film forming method comprises: injecting a precursor compound into the chamber to allow it to adsorb on the surface of the substrate, and The step of injecting the above-mentioned thin film forming material into the chamber and forming a metal thin film or a metal nitride film through a reduction reaction.

7. The thin film forming method according to claim 5, wherein The thin film forming method comprises: The step of injecting the precursor compound into the chamber so that it is adsorbed on the surface of the substrate, injecting the thin film forming material into the chamber to reduce the activation energy of the reaction with the reaction gas, and The step of supplying a reaction gas into the chamber and forming a metal thin film or a metal nitride film through a reduction reaction.

8. The thin film forming method according to claim 6 or 7, wherein: Each of the steps includes: The step of purging the interior of the chamber with a purge gas.

9. The thin film forming method according to claim 6 or 7, wherein: The chamber is an atomic layer deposition chamber, a chemical vapor deposition chamber, a plasma enhanced atomic layer deposition chamber or a plasma enhanced chemical vapor deposition chamber.

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

11. The thin film forming method according to claim 5, wherein The film is a metal film or a metal nitride film with a resistivity ranging from 5 μΩ·cm to 1000 μΩ·cm.

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

13. The thin film forming method according to claim 6 or 7, characterized in that: The substrate loaded in the chamber is heated to 100° C. to 800° C.

14. 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, characterized in that: The invention comprises a thin film produced by the thin film forming method according to claim 6 or 7.

16. A semiconductor device, characterized in that: Comprising the semiconductor substrate according to claim 15.

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