Low-temperature vapor deposition material, method for forming a low-temperature vapor deposition film, and semiconductor substrate and semiconductor device manufactured thereby.

Abstract

The present invention relates to a low-temperature deposition material, a method for forming a low-temperature deposition film, and semiconductor substrates and semiconductor devices manufactured thereby. By applying a predetermined substance that can act as a strong reducing agent even in low-temperature processes, the present invention not only effectively manufactures thin films and / or metal nitride films with low resistance in low-temperature processes, but also reduces impurities in the film caused by ligands such as carbon, thereby improving physical properties such as resistivity and crystallinity.

Description

Technical Field

[0001] The present invention relates to a low-temperature deposition material, a method for forming a low-temperature deposition film, a semiconductor substrate and a semiconductor device manufactured thereby. More specifically, by applying a predetermined material that can serve as a strong reducing agent even in a low-temperature process, not only can a deposition film with low resistance be effectively manufactured in a low-temperature process, but also impurities in the deposition film caused by ligands such as carbon can be reduced, and physical properties such as roughness and crystallinity can be improved. The present invention relates to a low-temperature deposition material, a method for forming a low-temperature deposition film, a semiconductor substrate and a semiconductor device manufactured thereby.

Background Art

[0002] In recent years, with the increasing demand for higher performance and higher integration of semiconductor devices, the need for materials for electrodes or diffusion prevention films with lower specific resistance has been increasing.

[0003] Such materials are provided in the form of metal films and / or metal nitride films using an atomic layer deposition (ALD) process. At this time, in the reduction process, the use of an extremely strong reducing agent and high thermal energy are currently required.

[0004] However, the binding energy used for the deposition is 467.7 kJ / mol, and high thermal energy is required for reduction to H2. However, if high thermal energy is applied, the precursor compound will be thermally decomposed. Therefore, in a highly integrated substrate or a substrate with a high aspect ratio and complexity, the step coverage may deteriorate, or there may be a risk of cracks (voids) or seams (joints) occurring.

[0005] In addition, impurities (C, Cl - , F -Not only do substances such as these flow in and cause contamination, but they also disrupt the arrangement of crystals and lower the density of the formed film, which may lead to problems with impaired electrical conductivity due to low density.

[0006] Therefore, there is a strong demand for the development of low-temperature deposition materials that can form uniform metal films and / or metal nitride films with complex structures, possess excellent physical properties such as crystallinity, and have low residual film impurities caused by ligands such as carbon, thereby providing deposition films with low resistance even under low-temperature process conditions, as well as methods for forming low-temperature deposition films using these materials and semiconductor substrates.

[0007] [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Republic of Korea Publication Patent No. 2019-0141071 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] To address the problems of conventional technologies as described above, the present invention aims to provide a method for forming a low-temperature vapor-deposited film and a semiconductor substrate manufactured thereby, which can provide a vapor-deposited film with excellent film thickness uniformity and low resistance even in low-temperature processes, by applying a substance with a lower bonding energy than H2 as a low-temperature vapor-deposited material to reduce impurities, improve resistivity, and effectively improve vapor deposition characteristics, even when forming a metal film on a substrate with a complex structure.

[0010] In other words, the present invention aims to provide a method for performing a reduction reaction in a low-temperature process by applying a novel low-temperature vapor deposition material.

[0011] Furthermore, the present invention aims to improve film properties such as electrical characteristics and density, and to provide a vapor-deposited film with low resistance by applying a novel material that undergoes a reduction reaction to form a metal film and / or metal nitride film as a low-temperature vapor deposition material.

[0012] The above-mentioned and other objectives of the present invention can all be achieved by the present invention as described below. [Means for solving the problem]

[0013] To achieve the above objectives, the present invention provides a low-temperature deposition material for wiring metals, metals with a melting point of 350°C or lower, or wiring metal diffusion prevention films, characterized by comprising one or more compounds selected from among compounds having a direct bond between hydrogen (H) and iodine, compounds having a direct bond between carbon (C) and iodine, and compounds having a direct bond between halogen elements (F, Cl, Br) and iodine.

[0014] The aforementioned wiring metal or metal with a melting point of 350°C or less may be selected from Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga.

[0015] The wiring metal diffusion prevention film may be a transition metal nitride film of Ti, Ta, Ni, Mo, Nb, Zr, V, or W, or a nitride film in which a combination of two or more metals is selected.

[0016] The compound having a direct bond between hydrogen (H) and iodine may have a total bond energy in the range of 305 to 325 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen elements: 6-31+G(dp))).

[0017] The compound having a direct bond between carbon (C) and iodine may have a total bond energy in the range of 165 to 242 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen: 6-31+G(dp))).

[0018] Compounds having a direct bond between the halogen element (F, Cl, Br) and iodine may have a total bond energy in the range of 50 to 160 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen: 6-31+G(dp))).

[0019] The low-temperature vapor deposition material may be one or more compounds selected from those represented by the following chemical formulas 1-1 to 1-11.

[0020] [Chemical formula 1-1~1-11]

[0021] [ka]

[0022] Furthermore, the present invention may provide a method for forming a low-temperature vapor-deposited film, characterized by including the step of depositing the aforementioned low-temperature vapor-deposited material as a vapor-deposited film.

[0023] The deposited film may be a metal film and / or a metal nitride film.

[0024] The method for forming the low-temperature deposited film may include the step of injecting a precursor compound and the low-temperature deposited material into a chamber and forming a deposited film using a reduction reaction while adsorbing them onto the surface of a substrate.

[0025] The aforementioned low-temperature deposition film formation method may omit the step of injecting hydrogen as a reaction gas to carry out a reduction reaction.

[0026] The method for forming the low-temperature deposited film may include a post-treatment step of purging the inside of the chamber with a purge gas.

[0027] The chamber may be an atomic layer deposition (ALD) chamber, a vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced vapor deposition (PECVD) chamber.

[0028] The low-temperature deposited film may be a multilayer film of one or more materials selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga.

[0029] The metal nitride film may be a transition metal nitride film of Ti, Ta, Ni, Mo, Nb, Zr, V, or W, or a nitride film in which a combination of two or more metals is selected.

[0030] The low-temperature deposited film may be a wiring metal film, a wiring diffusion prevention film, or a low-resistance metal film.

[0031] The wiring metal film may be a metal film of Mo, W, Ru, Cu, or Rh.

[0032] The wiring metal diffusion prevention film may be a transition metal nitride film of Ti, Ta, Ni, Mo, Nb, Zr, V, or W, or a nitride film in which a combination of two or more metals is selected.

[0033] The low-resistance metal film may be a metal film having a melting point of 350°C or lower.

[0034] The low-resistance metal film may be a metal film of Pb, Cd, Sn, Bi, In, or Ga.

[0035] The low-temperature deposited film can be formed using a precursor compound for low-resistance metal films.

[0036] The precursor compound for the low-resistance metal film is a molecule having one or more elements selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M), and one or more ligands consisting of C, N, O, H, and X (halogens). In order to reduce the central metal atom at a low process temperature of 400°C or less, the compound may have a bond dissociation energy between the central metal atom and the ligand of 350 kJ / mol or less, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(dp))).

[0037] The precursor compound is a molecule composed of one or more elements selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M), and may be a compound having a vapor pressure at 25°C greater than 0.01 mTorr and less than or equal to 100 Torr.

[0038] The substrates brought into the chamber may be heated to temperatures of 100 to 700°C.

[0039] In the present invention, not only can reaction gases such as ammonia, hydrogen, and oxygen, which are commonly used in this art, be omitted, but the step of separately injecting a reaction gas and performing a reduction treatment can also be omitted.

[0040] The low-temperature deposited film may be a metal film such as a molybdenum metal film, a tungsten metal film, a ruthenium metal film, a copper metal film, a rhodium metal film, a lead metal film, a cadmium metal film, a tin metal film, a bismuth metal film, an indium metal film, or a gallium metal film.

[0041] The low-temperature deposited film may be a titanium nitride film, tantalum nitride film, vanadium nitride film, tungsten nitride film, nickel nitride film, zirconium nitride film, molybdenum nitride film, etc., or a metal nitride film in which two or more types are combined for diffusion prevention film applications, such as a titanium niobium nitride film or a titanium nickel nitride film.

[0042] The aforementioned metal film and / or metal nitride film is characterized by having a low resistivity of 5 μΩ·cm to 1000 μΩ·cm.

[0043] The aforementioned metal film and / or metal nitride film is characterized in that, when measured by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS), the content of ligand-derived impurities, such as carbon, is 1% or less.

[0044] The aforementioned metal film and / or metal nitride film is characterized in that its crystallinity, as measured by X-ray diffraction (XRD), is improved by the effect of reducing impurities inside the thin film using a stronger reduction of the metal precursor.

[0045] Furthermore, the present invention provides a semiconductor substrate characterized by being manufactured by the low-temperature deposition film formation method described above.

[0046] The low-temperature deposited film may be a metal film and / or a metal nitride film.

[0047] The low-temperature deposited film may have a multilayer structure of two or three layers.

[0048]

[0049] Furthermore, the present invention provides a semiconductor device characterized by comprising the aforementioned semiconductor substrate. [Effects of the Invention]

[0050] According to the present invention, by applying a predetermined substance that can act as a strong reducing agent even in low-temperature processes, a reduction reaction (reduction of the activation energy of the reaction with the reaction gas) can be achieved at a process temperature in which the precursor is not thermally decomposed. This provides a method for forming a uniform metal film and / or metal nitride film, even when forming a metal film and / or metal nitride film on a highly integrated substrate or a substrate with a complex structure.

[0051] Furthermore, this method has the effect of improving the electrical properties of metal films and / or metal nitride films by more effectively reducing impurities and process by-products in the metal film and / or metal nitride film that are caused by ligands such as carbon, which lead to deterioration of film properties such as crystallinity and electrical properties during the formation of the metal film and / or metal nitride film, thereby improving the crystallinity and resistivity of the metal film and / or metal nitride film.

[0052] Furthermore, it has the effect of improving impurities and film quality to provide a method for forming high-quality low-temperature deposited films and semiconductor substrates manufactured thereby. [Brief explanation of the drawing]

[0053] [Figure 1] This graph shows the analysis results obtained by Auger electron spectroscopy (AES) at different temperatures for Example 5 according to the present invention.

[0054] [Figure 2] This is an X-ray diffraction (XRD) analysis graph for each process temperature of Example 5 according to the present invention and Comparative Example 3 of the conventional method.

[0055] [Figure 3] This is an XRD analysis graph of Example 6 according to the present invention and a conventional comparative example 4.

[0056] [Figure 4]This figure shows the reaction activation energies required to reduce the CO ligand and NO ligand of the Mo(CO)6 precursor and (EtCp)Mo(CO)2(NO) precursor, respectively, in Example 8, comparing them with respect to H2 and HI. [Figure 5] This figure shows a comparison of the reaction activation energies required for the reduction of the CO ligand and NO ligand in the Mo(CO)6 precursor and (EtCp)Mo(CO)2(NO) precursor, respectively, in comparative example 5, using H2 and HI. [Modes for carrying out the invention]

[0057]

[0058] The following describes in detail the method for forming the low-temperature vapor-deposited film described herein and the semiconductor substrate manufactured thereby.

[0059] In this description, the term "low-temperature vapor deposition material" refers, for example, to a novel material capable of forming a metal film and / or metal nitride film by vapor deposition via a reduction reaction in a low-temperature process at 600°C or below, preferably 550°C or below, and more preferably 500°C or below.

[0060] In this description, the term "reduction reaction" refers, unless otherwise specified, to a reaction that not only substitutes the ligand of a precursor compound but also reduces it to such an extent that it eliminates the need for a conventional reduction reaction using a reaction gas.

[0061] In this description, the term "modification" refers, unless otherwise specified, to the positive interaction between substances other than precursors and reactants at the reaction surface, resulting in improvements to the film quality, such as a decrease in resistivity, an increase in density, or a reduction in impurities.

[0062] Unless otherwise noted or mentioned in this document, % refers to weight percentage.

[0063] The inventors of this invention have discovered that when using a predetermined low-temperature deposition material that can carry out a reduction reaction at a relatively low process temperature such that the precursor compound adsorbed on the surface of a substrate introduced into the chamber does not undergo thermal decomposition, it is possible to improve the film quality, such as electrical properties and crystallinity, while preventing the inflow of film impurities caused by ligands such as carbon. After conducting research on this, the inventors have completed the present invention.

[0064] The low-temperature deposited film can, for example, be formed from one or more precursors selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga to provide a metal film, in which case the effects to be achieved in the present invention can be fully obtained.

[0065] The aforementioned wiring metal diffusion prevention film can be formed, for example, from one or more precursors selected from the group consisting of Ti, Ta, Ni, Mo, Nb, Zr, V, and W, and can provide a metal nitride film, in which case the effects to be achieved in the present invention can be fully obtained.

[0066] The low-temperature deposited film may have, as specific examples, a film composition such as a molybdenum metal film, a tungsten metal film, a ruthenium metal film, a copper metal film, a rhodium metal film, a lead metal film, a cadmium metal film, a tin metal film, a bismuth metal film, an indium metal film, or a gallium metal film.

[0067] The aforementioned low-temperature deposited film may include the aforementioned film composition alone or as a selective area, but is not limited thereto, and may also include SiH, SiOH, etc.

[0068] The low-temperature deposited film may be a multilayer film of one or more materials selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga.

[0069] The metal nitride film may be a laminated film of one or more elements selected from the group consisting of Ti, Ta, Ni, Mo, Nb, Zr, V, and W.

[0070] The aforementioned low-temperature deposited film can be used in semiconductor devices as a wiring metal film or a metal film with low resistance, which are commonly used applications.

[0071] The aforementioned metal nitride film can be used in semiconductor devices as a wiring metal diffusion prevention film or for low-resistance applications.

[0072] The resistivity of the metal film and / or metal nitride film may be in the range of 5 μΩ·cm to 1000 μΩ·cm.

[0073] The wiring metal film may be a metal film of Mo, W, Ru, Cu, or Rh.

[0074] The low-resistance metal film may be a metal film having a melting point of 350°C or lower.

[0075] The low-resistance metal film may be a metal film of Pb, Cd, Sn, Bi, In, or Ga.

[0076] The low-temperature deposited film can be formed using a precursor compound for low-resistance metal films.

[0077] The aforementioned precursor compound may, for example, use Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as the central metal atom (M) and the ligand (L). 1 , L 2 , L 3 , L 4 , L 5 and L 6 It may have a structure in which elements such as are combined.

[0078] As specific examples, the precursor compound is a molecule having one or more ligands composed of C, N, O, H, and X (halogen) with Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, or Ga as a central metal atom (M). When the vapor pressure at 25 °C is 0.01 mTorr to 100 Torr, the effect of using the low-temperature deposition material can be maximized.

[0079] As other specific examples, the precursor compound is a molecule having one or more ligands composed of C, N, O, H, and X (halogen) with one or more selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, Ti, Ta, Ni, Mo, Nb, Zr, V, and Ga as a central metal atom (M). In order to reduce the central metal atom at a low process temperature of 400 °C or lower, it may be a compound in which the bond dissociation energy between the central metal atom and the ligand calculated using the Gaussian 16 program (basis function system of DFT-D3 / B3LYP (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(d,p))) is within 350 kJ / mol.

[0080] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as ligands. When the central metal is hexavalent, L 1 、L 2 、L 3 、L 4 、L 5 、L 6 can be attached to the central metal, and the ligands corresponding to L 1 to L 6 may be the same as or different from each other.

[0081] As an example, L 1 、L 2 、L 3 、L 4 、L 5 and L 6-H or -R, which may be the same or different from each other, where -R is C1~C 10 Alkyl, C1~C 10 Alkenes or C1-C 10 an alkane which may be linear or cyclic, and the L 1 , L 2 , L 3 and L 4 Depending on the oxidation value of the central metal, the n number of L can be formed from 2 to 6.

[0082] For example, if the central metal is divalent, L 1 and L 2 It can attach to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 It can be attached to the central metal, L 1 ~L 6 The ligands corresponding to these may be the same or different from each other.

[0083] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 -H, -OR, or -NR2, which may be the same or different from each other, where -R is H, C1~C 10 Alkyl, C1~C 10 Alkenes, C1~C 10 This can be an alkane, iPr, or TBu, which in this case has a reaction energy suitable for substitution with the reaction gas described later.

[0084] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6-H or -X, which may be the same or different from each other, where -X may be F, Cl, Br, or I, and in this case, has a reaction energy suitable for substitution with the reaction gas described later.

[0085] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 -H or -R, which may be the same or different from each other, where -R is C1~C 10 Alkyl, C1~C 10 Alkenes or C1-C 10 It is an alkane, which may have a linear or cyclic structure, and in this case, has a reaction energy suitable for substitution with the reaction gas described later.

[0086] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 -H, -OR, or -NR2, which may be the same or different from each other, where -R is H, C1~C 10 Alkyl, C1~C 10 Alkenes, C1~C 10 This can be an alkane, iPr, or tBu, which in this case has a reaction energy suitable for substitution with the reaction gas described later.

[0087] As a specific example, L 1 , L 2 , L 3 , L 4 , L 5 and L 6 -H or -X, which may be the same or different from each other, where -X may be F, Cl, Br, or I, and in this case, it has a reaction energy suitable for substitution with the reaction gas described later.

[0088]

[0089] For example, a precursor compound with molybdenum (Mo) as the central metal may be one or more compounds selected from those having the structure shown in the following chemical formulas 2-3, and may include trimethylene methane ligands and their derivatives, but the present invention is not limited thereto.

[0090] [Chemical formula 2]

[0091] [ka]

[0092]

[0093] (In the above chemical formula 2, R1 to R5 are independently selected from hydrogen, an amino group, a silyl group, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 8 carbon atoms. Cases where R1 to R5 are simultaneously hydrogen are not included.)

[0094] [Chemical formula 3]

[0095] [ka]

[0096] (In the above chemical formula 3, X is a linear or branched cyclic, saturated or unsaturated hydrocarbon substituted with H, F, Cl, Br, I, NO, CN, amidinate, guazininate, ethylenediamine, propylenediamine, -NR6R7, -OR8, R9Cp, and one or more carbon (C), nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); R6, R7, R8, and R9 are independently selected from hydrogen, a C1-C12 alkyl group, and a C6-C12 aryl group; and n is an integer from 0 to 2.)

[0097] The derivatives of the trimethylenemethane ligand may include, for example, structures having trimenzylidenemethane ligand, dibenzylidenemethane ligand, and the like.

[0098] Precursor compounds with molybdenum (Mo) as the central metal include, for example, hexacarbonylmolybdenum (Mo(CO)6), bis(ethylbenzene)molybdenum ((Ethylbenzene)2Mo), tricarbonyl(2,6-diisopropylaniline)molybdenum ((2,6-diisopropylaniline)Mo(CO)3), carbonyl(1,4-diisopropyl-1,4-diazabutadiene)molybdenum ((1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)), pentacarbonyl(dichloromethylphosphine)molybdenum (Mo(CO)5PCl2Me), and molybdenum acetate dimers. Dimer), bis(allyl)(ethylbenzene)molybdenum ((Ethylbenzene)Mo(allyl)2), dicarbonyl(allyl)(methylcyclopentadienyl)molybdenum (MeCpMo(CO)2(allyl)), dicarbonyl(allyl)(isopropylcyclopentadienyl)molybdenum (iprCpMo(CO)2(allyl)), tris(tetramethylheptanedionato)molybdenum (Mo(thd)3), tris(ethyl methacrylate)(methylcyclopentadienyl)molybdenum ((MeCp)Mo(EMA)3), bis(methylcyclopentadienyl)(tert-butylimido)molybdenum ((tert-butylimido)Mo(MeCp)2), tetrakis(dimethylamide)molybdenum Molybdenum (TDMAMo), dihydridobis(cyclopentadienyl)molybdenum (Cp2MoH2), tetrakis(dithiocarbamate)molybdenum (Mo(Dithiocarbamate)4), chlorobis(tert-butylimido)(aminothiolate)molybdenum ((tert-butylimido)2MoCl(aminothiolate)), (aminothiolate)bis(tert-butylimido)(tert-butylthiol)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), bis(aminothiolate)bis(tert-butylimido)2Mo(aminothiolate)2,Bis(tert-butylthiol)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)2), Bis(tert-butylamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butylamine)2), (cyclopentadienylethyl methacrylate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(CpEMA)), dioxobis(isopropylamidinato)molybdenum ( MoO2(ipr-amidinate)2), bis(isopropylamidinate)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(ipr-amidinate)2), bis(tert-butoxy)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butoxy)2), (N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylene These may include triamine, chloro(hydrazido)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(hydrazido)Cl), dioxobis(dithiocarbamate)molybdenum (MoO2(Dithiocarbamate)2), bis(tert-butylimido)(1,4-di-tert-butyl-1,4-diazabutadiene)molybdenum ((1,4-ditert-butyl-1,4,diazabutadiene)Mo(tert-butylimido)2), dichlorodioxomolybdenum (MoO2Cl2), etc.

[0099] Here, dichlorodioxomolybdenum (MoO2Cl2), bis(ethylbenzene)molybdenum ((Ethylbenzene)2Mo), tricarbonyl(2,6-diisopropylaniline)molybdenum ((2,6-diisopropylaniline)Mo(CO)3), tricarbonyl(benzene)molybdenum ((benzene)Mo(CO)3), and tricarbonyl(1,4-diisopropyl-1,4-diazabutadiene)molybdenum (1,4-diisopropyl-1,4-diazabutadiene)Mo(CO)3 may each be compounds represented by the following chemical formulas 4-1 to 4-5.

[0100] [Chemical formula 4-1~4-5]

[0101] [ka]

[0102] Here, the aforementioned pentacarbonyl(dichloromethylphosphine)molybdenum (Mo(CO)5PCl2Me), molybdenum acetate dimer, bis(allyl)(ethylbenzene)molybdenum ((Ethylbenzene)Mo(allyl)2), dicarbonyl(allyl)(methylcyclopentadienyl)molybdenum (MeCpMo(CO)2(allyl)), and dicarbonyl(allyl)(isopropylcyclopentadienyl)molybdenum (iprCpMo(CO)2(allyl)) may each be compounds represented by the following chemical formulas 4-6 to 4-10.

[0103] [Chemical formula 4-6~4-10]

[0104] [ka]

[0105] Here, the tris(tetramethylheptanedionato)molybdenum (Mo(thd)3), tris(ethyl methacrylate)(methylcyclopentadienyl)molybdenum ((MeCp)Mo(EMA)3), bis(methylcyclopentadienyl)(tert-butylimido)molybdenum ((tert-butylimido)Mo(MeCp)2), tetrakis(dimethylamide)molybdenum (TDMAMo), and dihydridebis(cyclopentadienyl)molybdenum (Cp2MoH2) may each be compounds represented by the following chemical formulas 4-11 to 4-15.

[0106] [Chemical formula 4-11~4-15]

[0107] [ka]

[0108] Here, the tetrakis(dithiocarbamate)molybdenum (Mo(Dithiocarbamate)4), chlorobis(tert-butylimido)(aminothiolate)molybdenum ((tert-butylimido)2MoCl(aminothiolate)), (aminothiolate)bis(tert-butylimido)(tert-butylthiol)molybdenum ((tert-butylimido)2Mo(tert-butylthiol)(aminothiolate)), bis(aminothiolate)bis(tert-butylimido)2Mo(aminothiolate)2, and bis(tert-butylthiol)bis(tert-butylimido)2Mo(tert-butylthiol)2 may each be a compound represented by the following chemical formulas 4-16 to 4-20.

[0109] [Chemical formula 4-16~4-20]

[0110] [ka]

[0111] Here, the bis(tert-butylamine)bis(tert-butylimide)molybdenum ((tert-butylimido)2Mo(tert-butylamine)2), (cyclopentadienylethyl methacrylate)bis(tert-butylimide)molybdenum ((tert-butylimido)2Mo(CpEMA)), dioxobis(isopropylamidinate)molybdenum (MoO2(ipr-amidinate)2), and bis(isopropylamidinate)bis(tert-butylimide)molybdenum ((tert-butylimido)2Mo(ipr-amidinate)2) may each be a compound represented by the following chemical formulas 4-21 to 4-24.

[0112] [Chemical formula 4-21~4-24]

[0113] [ka]

[0114] Here, the bis(tert-butoxy)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(tert-butoxy)2), (N,N-dimethyldiethylenetriamine)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(N,N-dimethyldiethylene Triamine, chloro(hydrazide)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(hydrazido)Cl), dioxobis(dithiocarbamate)molybdenum (MoO2(Dithiocarbamate)2), bis(tert-butylimido)(1,4-di-tert-butyl-1,4-diazabutadiene)molybdenum ((1,4-ditert-butyl-1,4,diazabutadiene)Mo(tert-butylimido)2), dichlorodioxomolybdenum (MoO2Cl2), bis(dimethylamide)bis(tert-butylimido)molybdenum ((tert-butylimido)2Mo(dimethylamide)2), and bis(methylbenzene)molybdenum ((Methylbenzene)2Mo) may each be compounds represented by the following chemical formulas 4-25 to 4-31.

[0115] [Chemical formula 4-25~4-31]

[0116] [ka]

[0117] The aforementioned precursor compound can be used, for example, by mixing it with a nonpolar solvent, which has the advantage of making it easier to adjust the viscosity and vapor pressure of the precursor compound.

[0118]

[0119] The low-temperature deposition material of the present invention not only lowers the activation energy of precursor compounds adsorbed on a substrate and effectively replaces ligands, but also possesses reducing power to carry out reduction reactions, thereby eliminating the reduction step using reaction gases required in the process.

[0120] The substitution of the ligand can, for example, be formed on the entire substrate or a portion of the substrate on which the low-temperature deposited film is formed.

[0121] The low-temperature vapor deposition material is characterized by including, as an example, one or more compounds selected from among compounds having a direct bond between hydrogen (H) and iodine, compounds having a direct bond between carbon (C) and iodine, and compounds having a direct bond between a halogen element (F, Cl, Br) and iodine.

[0122] The aforementioned low-temperature deposition material can spontaneously undergo a reduction reaction to form a film without the need for a separate reaction gas such as H2.

[0123] The compound having a direct bond between hydrogen (H) and iodine may have a total bond energy of 165-242 kJ / mol or less, or 290 kJ / mol or more, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen: 6-31+G(dp))). In this case, the content of film impurities caused by ligands such as carbon can be reduced, and a thin film with low resistance can be effectively provided.

[0124] The compound having a direct bond between carbon (C) and iodine may have a total bond energy of 165-242 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen: 6-31+G(dp))). In this case, the content of film impurities caused by ligands such as carbon can be reduced, effectively providing a thin film with low resistance.

[0125] Compounds having a direct bond between the halogen elements (F, Cl, Br) and iodine may have a total bond energy of 50-160 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen elements: 6-31+G(dp))), and in this case, a thin film with low resistance can be effectively provided.

[0126] The low-temperature deposition material, specifically the compound having a direct bond between hydrogen (H) and iodine, may have a total bond energy of 305-325 kJ / mol, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(dp))). In this case, the content of impurities in the film caused by ligands such as carbon can be reduced, effectively providing a thin film with low resistance.

[0127] The low-temperature vapor deposition material may be one or more compounds selected from those represented by the following chemical formulas 1-1 to 1-11.

[0128] [Chemical formula 1-1~1-11]

[0129] [ka]

[0130] The low-temperature deposition material is, for example, elemental hydrogen iodide of 3N to 15N purity, a gas mixture of 1 to 99% by weight of hydrogen iodide of 3N to 15N purity and an amount of inert gas remaining to make up 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of hydrogen iodide of 3N to 15N purity and an amount of water remaining to make up 100% by weight. Here, the inert gas may be nitrogen, helium, or argon with a purity of 4N to 9N. In this case, a reduction reaction is performed to reduce impurities, and a thin film or metal nitride film with low resistance can be effectively formed.

[0131] The low-temperature deposition material is preferably a mixture of 5N to 6N elemental hydrogen iodide, 1 to 99% by weight of 5N to 6N hydrogen iodide and an inert gas residue so that the total amount is 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 5N to 6N hydrogen iodide and an inert gas residue so that the total amount is 100% by weight, where the inert gas may be nitrogen, helium, or argon having a purity of 4N to 9N. In this case, side reactions are suppressed during the formation of the low-temperature deposition film, the film growth rate is adjusted, process by-products in the low-temperature deposition film are reduced, corrosion and degradation are reduced, and the film quality is improved, such as improved crystallinity of the film. Furthermore, even when forming a thin film on a highly integrated substrate or a substrate with a complex structure, the uniformity of the film thickness can be greatly improved.

[0132] In such cases, by providing sufficient reduction reaction effects to precursor compounds adsorbed on the substrate at relatively low process temperatures where the precursors do not undergo thermal decomposition, it is possible to significantly improve film thickness uniformity even when forming thin films on highly integrated substrates or substrates with complex structures. Furthermore, it has the advantage of effectively protecting the substrate surface by preventing the adsorption of not only precursors but also process by-products, reducing the reaction rate, and effectively removing process by-products.

[0133] The low-temperature deposition material is preferably a compound with a purity of 99.9% or higher, a compound with a purity of 99.95% or higher, or a compound with a purity of 99.99% or higher. For reference, if a compound with a purity of less than 99% is used, there is a risk that impurities may remain in the thin film or cause side reactions with precursors or reactants. Therefore, it is preferable to use a substance with a purity of 99% or higher whenever possible.

[0134] The aforementioned low-temperature vapor-deposited film may, for example, contain a halogen compound at a concentration of 100 ppm or less. For reference, if an excess of halogen remains, for example, when using a nitride agent described later under temperature conditions of 200-300°C, chlorides such as NH4Cl are formed and remain in the low-temperature vapor-deposited film, which is undesirable.

[0135] The aforementioned low-temperature deposited film can be used for applications such as wiring metal films or low-resistance metal films, and the present invention is not limited thereto.

[0136] In particular, it forms a relatively rough film, significantly reduces the growth rate of the formed film, ensures uniformity even when applied to substrates with complex structures, and allows for deposition on thin walls. Furthermore, it offers the effect of improving the amount of residual O, Si, metals, metal oxides, and even carbon, which were previously difficult to reduce, as by-products of the process.

[0137]

[0138] A method for forming a low-temperature vapor-deposited film according to one embodiment of the present invention is characterized by including a step of injecting a precursor compound and the low-temperature vapor-deposited material into a chamber and adsorbing them onto the surface of a substrate while forming a vapor-deposited film using a reduction reaction. In this case, the reduction of the precursor adsorbed on the substrate can be effectively carried out at a relatively low process temperature such that the precursor does not undergo thermal decomposition, thereby appropriately lowering the film growth rate and significantly improving the uniformity of the film, even when vapor-deposited on a highly integrated substrate or a substrate with a complex structure, and providing a vapor-deposited film with low resistance.

[0139] The low-temperature deposition material and precursor compound can be transported into the chamber by a vapor flow control (VFC) system, a direct liquid injection (DLI) system, or a liquid supply system (LDS) system.

[0140] The ratio of the amount (mg / cycle) of the precursor compound to the low-temperature deposition material introduced into the chamber can be 1:1 to 1:20.

[0141] The step of injecting the low-temperature deposition material onto the surface of the substrate is performed such that the feeding time (seconds) of the low-temperature deposition material onto the surface of the substrate is preferably 0.01 to 10 seconds, more preferably 0.02 to 8 seconds, even more preferably 0.04 to 6 seconds, and even more preferably 0.05 to 4 seconds per cycle. Within this range, there is an advantage that the film growth rate is low, and that the step coverage and cost-effectiveness are excellent.

[0142] In this description, the feeding time for the low-temperature deposition material is based on a flow rate of 0.1 to 8,000 mg / cycle, with a chamber volume of approximately 15 to 20 L as a guideline, and more specifically, a flow rate of 10 to 5,000 mg / cycle, with a chamber volume of approximately 18 L as a guideline.

[0143]

[0144] As a specific example, the method for forming the low-temperature vapor-deposited film may include the steps of: injecting a precursor compound and the low-temperature vapor-deposited material into a chamber and forming a vapor-deposited film using a reduction reaction while adsorbing them onto the surface of a substrate; and purging the inside of the chamber with a purge gas.

[0145] The aforementioned overall steps can be considered a unit cycle, and this cycle can be repeated until a low-temperature deposited film of the desired thickness is obtained. When the low-temperature deposited material is introduced simultaneously with the precursor compound within one cycle to improve the film quality, the resulting process by-products are effectively removed, reducing resistivity and significantly improving step coverage. In addition, uniformity is improved, and film quality such as electrical properties, dielectric properties, and density is improved, resulting in a low-resistivity deposited film.

[0146] The chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0147] The substrates brought into the chamber may be heated to temperatures of 100 to 700°C.

[0148] The low-temperature deposition material or precursor compound may be vaporized and injected, followed by a plasma post-treatment step, in which case the film growth rate can be improved while reducing process by-products.

[0149] In the purging step, 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 compound. For example, it may be 10 to 10,000 times the volume of the precursor compound introduced into the ALD chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed precursor compound can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of purge gas and precursor compound introduced are based on one cycle, and the volume of the precursor compound refers to the volume of vaporized precursor compound vapor.

[0150]

[0151] The low-temperature deposition material and precursor compound can preferably be transported into the ALD chamber by a vapor flow control (VFC) system, a direct liquid injection (DLI) system, or a liquid supply system (LDS) system, and more preferably by a VFC system.

[0152] The substrate brought into the chamber may be heated to, for example, 100-700°C, and more specifically, 300-600°C. The low-temperature deposition material or precursor compound may be injected onto the substrate either unheated or heated. Depending on the deposition efficiency, the material may be injected unheated first, and then the heating conditions may be adjusted during the deposition process. For example, it may be injected onto the substrate for 1-20 seconds under temperature conditions of 50-400°C.

[0153]

[0154] The ratio of the amount (mg / cycle) of the precursor compound to the low-temperature deposition material introduced into the chamber is preferably 1:1 to 1:400, more preferably 1:2 to 1:350, even more preferably 1:2 to 1:300, and even more preferably 1:2.5 to 1:200. Within this range, the effect of improving step coverage and reducing process by-products is significant.

[0155]

[0156] The low-temperature deposition film formation method described above can be carried out, for example, at a deposition temperature in the range of 100 to 600°C, preferably in the range of 300 to 500°C, and more preferably in the range of 300 to 400°C. Within this range, it has the effect of growing a film with excellent quality while providing ALD process characteristics.

[0157] The method for forming the low-temperature deposited film described above can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably in the range of 0.1 to 20 Torr, more preferably in the range of 0.1 to 10 Torr, and most preferably in the range of 0.3 to 7 Torr. Within this range, a low-temperature deposited film with a uniform thickness can be obtained.

[0158] In this description, the deposition temperature and deposition pressure may be measured as the temperature and pressure formed within the deposition chamber, or as the temperature and pressure applied to the substrate within the deposition chamber.

[0159] The method for forming the low-temperature deposited film may preferably include the steps of raising the temperature inside the chamber to the deposition temperature before introducing the precursor compound into the chamber, and / or purging the chamber by injecting an inert gas before introducing the precursor compound into the chamber.

[0160]

[0161] The method for forming the low-temperature deposited film described above has the remarkable effect of preventing deterioration of crystallinity and electrical properties within a given range. This is achieved by measuring the strength (c / s) of residual impurities (carbon or halogen elements) in the low-temperature deposited film based on SIMS, with a film thickness of 100 Å as a guideline. Preferably, the strength (c / s) is 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred embodiment, the strength may be 5,000 or less, more preferably 10 to 4,000, and even more preferably 10 to 3,000.

[0162] In this description, the purging is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeters per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the film growth rate per cycle is appropriately controlled, and deposition is performed as an atomic mono-layer or approximately thereof, which has the advantage of being advantageous in terms of film quality.

[0163]

[0164] Furthermore, the present invention may include, as a manufacturing apparatus capable of providing the method for manufacturing the low-temperature vapor-deposited film, an ALD chamber, a first vaporizer for vaporizing a precursor compound, a first transport means for transporting the vaporized precursor compound into the ALD chamber, a second vaporizer for vaporizing a low-temperature vapor-deposited material, and a second transport means for transporting the vaporized low-temperature vapor-deposited material into the ALD chamber. Here, the vaporizer and transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the art to which the present invention belongs.

[0165] As a specific example, the method for forming the low-temperature deposited film described above is first placed in a deposition chamber capable of depositing atomic layers, on which the substrate on which the deposited film is to be formed is positioned.

[0166] The aforementioned substrate can encompass semiconductor substrates such as silicon substrates and silicon oxide.

[0167] The aforementioned substrate may have a conductive layer or an insulating layer further formed on its upper surface.

[0168] To deposit a vapor-deposited film onto a substrate positioned within the aforementioned deposition chamber, the above-mentioned low-temperature deposition material, precursor compound, or mixture thereof with a non-polar solvent is prepared.

[0169] Next, the prepared low-temperature deposition material, precursor compound, or mixture thereof with a nonpolar solvent (hereinafter referred to as "composition for deposition film formation") is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber where it is adsorbed onto the substrate. Any unadsorbed material or mixture thereof with a nonpolar solvent is then purged.

[0170] The nonpolar solvent is preferably one or more selected from the group consisting of alkanes and cycloalkanes. In this case, while containing an organic solvent with very low reactivity and solubility, which makes it easy to control moisture content, it has the advantage of improving step coverage even when the deposition temperature increases during the formation of low-temperature deposited films.

[0171] As a more preferred example, the nonpolar solvent is C1-C 10 Alkanes or C3~C 10 It may contain cycloalkanes, preferably C3-C3. 10 This is a cycloalkane, which has the advantage of being very reactive and soluble, making it easy to manage moisture levels.

[0172] In this description, C1, C3, etc., refer to the number of carbon atoms.

[0173] The cycloalkane is preferably C3-C 10It may be a monocycloalkane, and among the said monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, making it suitable for the vapor deposition process, but it is not limited to this.

[0174] The aforementioned nonpolar solvent, for example, has a solubility in water (at 25°C) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, it has the advantage of low reactivity with the precursor compound and easy moisture control.

[0175] In this description, solubility is not particularly limited to measurement methods or standards commonly used in the art to which the present invention pertains. For example, a saturated solution can be measured by high-performance liquid chromatography (HPLC).

[0176] The nonpolar solvent may preferably be present in an amount of 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, relative to the total weight of the precursor compound and the nonpolar solvent combined.

[0177] If the amount of the nonpolar solvent added exceeds the upper limit, it will cause impurities, increasing the resistance and film impurity values. Conversely, if the amount of the organic solvent added is below the lower limit, there is a drawback in that the effect of improving step coverage due to solvent addition and the effect of reducing impurities such as chloride (Cl) ions are not obtained to a great extent.

[0178]

[0179] As described above, in the method for forming the low-temperature vapor-deposited film, for example, a unit cycle may consist of the steps of injecting a precursor compound and the low-temperature vapor-deposited material into a chamber and adsorbing them onto the surface of a substrate, and purging the unadsorbed material. This unit cycle can be repeated to form a low-temperature vapor-deposited film of a desired thickness.

[0180] The aforementioned unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired film properties are successfully expressed.

[0181]

[0182] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the low-temperature deposition film formation method described herein, and in such a case, the uniformity of film thickness is remarkably excellent, and the density and electrical properties are excellent.

[0183]

[0184] Preferably, the low-temperature deposited film has a film thickness of 30 nm or less, a resistivity of 5 to 2,000 μΩ·cm based on a film thickness of 10 nm, an impurity content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within this range, it exhibits outstanding performance as a diffusion-blocking film and has outstanding effectiveness as a metal wiring material, but is not limited thereto.

[0185] The aforementioned low-temperature deposited film may have a film thickness of, for example, 0.1 to 30 nm, preferably 1 to 20 nm, and more preferably 2 to 10 nm, and within this range, it has the effect of exhibiting excellent film properties.

[0186] As an example, the low-temperature deposited film may have a resistivity of 0.1 to 200 μΩ·cm, preferably 0.1 to 20 μΩ·cm, based on a film thickness of 10 nm, and within this range, it has the effect of exhibiting excellent film properties.

[0187] The low-temperature deposited film has an impurity content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 1 to 8,500 ppm, and even more preferably 1 to 1,000 ppm. Within this range, the film exhibits excellent crystallinity while also improving resistivity. The impurities remaining in the low-temperature deposited film are those resulting from insufficient reduction of the metal precursor ligand. Examples include carbon, nitrogen, oxygen, and halogen elements. The lower the amount of impurities remaining in the low-temperature deposited film, the better the film quality, and therefore preferable.

[0188] The low-temperature deposited film is characterized in that, when the content of ligand-derived impurities in the film is measured by XPS, the amount of impurities such as carbon is reduced to 1% or less.

[0189] In this document, unless otherwise specified, percentages refer to weight-based units.

[0190] The aforementioned low-temperature deposited film has, for example, a step coverage ratio of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even if the structure is complex, it can be easily deposited onto a substrate, which has the advantage of being applicable to next-generation semiconductor devices.

[0191] The low-temperature deposited film produced has preferably a film thickness of 20 nm or less, an impurity content of carbon, nitrogen, oxygen, halogens, etc. based on a film thickness of 10 nm of the low-temperature deposited film being 10,000 ppm or less, and a step coverage ratio of 90% or more. Within this range, it has the effect of having outstanding performance as a dielectric film or blocking film, but is not limited thereto.

[0192] The low-temperature deposited film is characterized by improved crystallinity as measured by XRD.

[0193] The low-temperature deposited film is characterized by improved resistivity.

[0194]

[0195] The following examples and drawings are provided to further the understanding of the present invention. However, these examples and drawings are merely illustrative of the present invention, and it will be obvious to those skilled in the art that a wide variety of changes and modifications can be made within the scope of the present invention and the technical concept. It goes without saying that such modifications and changes also fall within the scope of the attached claims.

[0196]

[0197] [Examples]

[0198] Example 1

[0199] 5N HI was used as the low-temperature deposition material, and the ALD process was carried out using the BTBMMo precursor compound with the following chemical formula.

[0200] [ka]

[0201] First, the prepared precursor compound was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC). After the BTBMMo precursor vaporized into a vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0202] Next, the prepared low-temperature deposition material was placed in a canister and supplied to the chamber at room temperature using a liquid mass flow controller (LMFC) at a flow rate of 1000 sccm. The low-temperature deposition material, vaporized into a vapor phase in a vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0203] The thickness of the metal film deposited per cycle was calculated by dividing the measured thickness of the manufactured low-temperature deposited film (MoN metal film) using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light, by the number of cycles, and the result was 10 nm. The components of the metal film were further analyzed by Auger electron spectroscopy (AES) and SIMS. Then, after measuring the surface resistance using the 4-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0204]

[0205] Example 2

[0206] The ALD process was carried out using 5N HI as the low-temperature deposition material, NH3 as the reaction gas, and the BTBMMo precursor compound with the following chemical formula as the precursor compound.

[0207] [ka]

[0208] First, the prepared precursor compound was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC). After the BTBMMo precursor vaporized into a vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0209] Next, the prepared HI low-temperature deposition material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The low-temperature deposition material, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a catalytic reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. Then, NH3 reaction gas was supplied to the chamber at a flow rate of 1000 sccm, followed by another argon purge at 5000 sccm for 10 seconds. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer metal film with a thickness of 10 nm.

[0210] The thickness of the metal film deposited per cycle was calculated by dividing the measured thickness of the manufactured low-temperature deposited film (MoN metal film) using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light, by the number of cycles, and the result was 10 nm. The components of the metal film were analyzed by performing analysis using AES and SIMS. Then, after measuring the surface resistance using the 4-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0211]

[0212] Example 3

[0213] 5N HI was used as the low-temperature deposition material, and the ALD process was carried out using the BTBTBMo precursor compound with the following chemical formula.

[0214] [ka]

[0215] First, the prepared precursor compound was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC). After the BTBTBMo precursor vaporized into a vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0216] Next, the prepared low-temperature deposition material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The low-temperature deposition material, vaporized into a vapor phase in a vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer metal film with a thickness of 10 nm.

[0217] The thickness of the metal film deposited per cycle was calculated by dividing the measured thickness of the manufactured low-temperature deposited film (MoN metal film) using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light, by the number of cycles, and the result was 10 nm. The components of the metal film were analyzed by performing analysis using AES and SIMS. Then, after measuring the surface resistance using the 4-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0218]

[0219] Example 4

[0220] The ALD process was carried out using 5N HI as the low-temperature deposition material, NH3 as the reaction gas, and the BTBTBMo precursor compound with the following chemical formula as the precursor compound.

[0221] [ka]

[0222] First, the prepared precursor compound was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC). After the BTBTBMo precursor vaporized into a vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0223] Next, the prepared HI low-temperature deposition material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The low-temperature deposition material, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a catalytic reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. Then, NH3 reaction gas was supplied to the chamber at a flow rate of 1000 sccm, followed by another argon purge at 5000 sccm for 10 seconds. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer metal film with a thickness of 10 nm.

[0224] The thickness of the metal film deposited per cycle was calculated by dividing the measured thickness of the manufactured low-temperature deposited film (MoN metal film) using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light, by the number of cycles, and the result was 10 nm. The components of the metal film were analyzed by performing analysis using AES and SIMS. Then, after measuring the surface resistance using the 4-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0225]

[0226] Example 5

[0227] 5N HI was used as the low-temperature deposition material, and the ALD process was carried out using the Mo(CO)6 precursor compound with the following chemical formula.

[0228] [ka]

[0229] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While flowing Ar gas as a carrier gas at 50 sccm, the Mo(CO)6 precursor was introduced into the deposition chamber for 3 seconds. Then, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0230] Next, the prepared low-temperature deposition material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The low-temperature deposition material, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 375°C, and this process was repeated 50 to 200 times to form a self-limiting atomic layer metal film with a thickness of 10 nm.

[0231] The thickness of the metal film deposited per cycle was calculated by dividing the measured thickness of the manufactured low-temperature deposited film (Mo metal film) using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light, by the number of cycles, and the result was 10 nm. After measuring the surface resistance using the 4-probe measurement method, the resistivity was calculated using the measured film thickness. The crystallinity of the Mo metal film was confirmed using XRD analysis.

[0232]

[0233] Example 6

[0234] 5N HI was used as the low-temperature deposition material, and the ALD process was carried out using the Mo(tol)2 precursor compound with the following chemical formula.

[0235] [ka]

[0236] First, the prepared precursor compound was placed in a separate canister and heated to 130°C. While flowing Ar gas as a carrier gas at 50 sccm, the Mo(tol)2 precursor was introduced into the deposition chamber for 10 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0237] Next, the prepared low-temperature deposition material was placed in a canister and supplied to the chamber at a flow rate of 1000 sccm using a mass flow controller (MFC) at room temperature. The low-temperature deposition material vaporized into the vapor phase in the vaporizer was introduced into the deposition chamber where the substrate was carried in for 2 seconds to perform a reduction reaction, and then argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 250°C, and such a process was repeated 30 to 300 times to form a self-limiting atomic layer metal film with a film thickness of 10 nm.

[0238] For the manufactured low-temperature deposition film (Mo metal film), the film thickness of the metal film measured by an ellipsometer, which is a device capable of measuring optical properties such as the film thickness and refractive index of the metal film using the polarization characteristics of light, was divided by the number of cycles to calculate the film thickness of the metal film deposited per cycle, and it was 10 nm. After measuring the surface resistance using the four-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0239]

[0240] Example 7

[0241] As the low-temperature deposition material, 5N HI was used. As the precursor compound, a TiCl4 precursor was used. As the nitride film reducing agent, NH3 was used to perform an ALD deposition process.

[0242] First, the prepared precursor compound was placed in a separate canister and heated to 30°C. While flowing Ar gas as a carrier gas at 100 sccm, the TiCl4 precursor was introduced into the deposition chamber for 3 seconds, followed by purging with argon gas at 3000 sccm for 5 seconds. Next, the prepared low-temperature deposition material was placed in a canister and supplied into the chamber at room temperature using a Liquid Mass Flow Controller (MFC) at a flow rate of 1000 sccm for 5 seconds. Then, argon gas was supplied at 3000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.0 Torr. Next, 1000 sccm of NH3 was supplied for 5 seconds to reduce the material and form a nitride thin film, followed by argon purging.

[0243] By maintaining the deposition temperature at 500°C and repeatedly performing this process, a self-limiting atomic layer metal nitride film with a thickness of 10 nm was formed.

[0244]

[0245] Example 8

[0246] The ALD deposition process was carried out using 5N HI as the low-temperature deposition material, NbF5 precursor as the precursor compound, and NH3 as the nitride film reducing agent.

[0247] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While flowing Ar gas as a carrier gas at 100 sccm, the NbF5 precursor was introduced into the deposition chamber for 3 seconds, followed by purging with argon gas at 1000 sccm for 6 seconds. Next, the prepared low-temperature deposition material was placed in a canister and supplied into the chamber at room temperature using a Liquid Mass Flow Controller (MFC) at a flow rate of 1000 sccm for 5 seconds. Then, argon gas was supplied at 1000 sccm for 10 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.0 Torr. Next, NH3 was supplied at 1000 sccm for 5 seconds to reduce the material and form a nitride thin film, followed by argon purging.

[0248] By maintaining the deposition temperature at 450°C and repeating this process, a self-limiting atomic layer metal nitride film with a thickness of 10 nm was formed.

[0249]

[0250] Example 9

[0251] ALD deposition was performed using 3N tertiary butyliodide as the low-temperature deposition material, MoO2Cl2 precursor as the precursor compound, and NH3 as the nitride film reducing agent.

[0252] First, the prepared precursor compound was placed in a separate canister and heated to 120°C. While flowing Ar gas as a carrier gas at 200 sccm, the MoO2Cl2 precursor was introduced into the deposition chamber for 5 seconds, followed by purging with argon gas at 1000 sccm for 5 seconds. Next, the prepared low-temperature deposition material was placed in a canister and supplied into the chamber at room temperature using a Liquid Mass Flow Controller (MFC) at a flow rate of 1000 sccm for 5 seconds. Then, argon gas was supplied at 1000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 3.0 Torr. Next, NH3 was supplied at 1000 sccm for 5 seconds to reduce the material and form a nitride thin film, followed by argon purging.

[0253] By maintaining the deposition temperature at 400°C and repeating this process, a self-limiting atomic layer metal nitride film with a thickness of 10 nm was formed.

[0254]

[0255] [Comparative Example]

[0256] Comparative Example 1

[0257] NH3 was used as the thin film-forming material, and the ALD process was carried out using the BTBMMo precursor compound with the following chemical formula.

[0258] [ka]

[0259] First, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150 °C at a flow rate of 0.1 g / min using a liquid mass flow controller (LMFC) at room temperature. The BTBMMo precursor vaporized into the vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0260] Next, NH3 as the prepared thin film forming substance was supplied to the chamber at a flow rate of 1,000 sccm. The thin film forming substance vaporized into the vapor phase in the vaporizer was introduced into the deposition chamber where the substrate was carried in for 2 seconds to perform a reduction reaction, and then argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350 °C, and such a process was repeated 200 - 400 times to form a self-limiting atomic layer thin film with a film thickness of 10 nm.

[0261] For the manufactured thin film (MoN nitride film), the film thickness of the thin film measured by an ellipsometer, which is a device capable of measuring optical properties such as the film thickness and refractive index of the thin film using the polarization characteristics of light, was divided by the number of cycles to calculate the film thickness of the thin film deposited per cycle, and it was 10 nm. The analysis of the thin film components was advanced by performing analysis using AES and SIMS. Then, after measuring the surface resistance using the four-probe measurement method, the resistivity value was calculated using the measured film thickness.

[0262]

[0263] Comparative Example 2

[0264] As the reaction gas, NH3 was used, and as the precursor compound, the BTB TBMo precursor of the following chemical formula was used to perform an ALD process.

[0265]

Chemical formula

[0266] First, the prepared precursor compound was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC). After the BTBTBMo precursor vaporized into a vapor phase in the vaporizer was introduced into the deposition chamber for 3 seconds, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure in the reaction chamber was controlled to 2.5 Torr.

[0267] Next, the prepared reaction gas NH3 was supplied to the chamber at a flow rate of 1,000 sccm. The reaction gas, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Then, argon gas was supplied at 5,000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0268] The film thickness of the manufactured thin film (MoN nitride film) was measured using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light. By dividing the measured film thickness by the number of cycles, the film thickness deposited per cycle was calculated to be 10 nm. The components of the thin film were analyzed using AES and SIMS. Then, after measuring the surface resistance using the 4-probe measurement method, the resistivity was calculated using the measured film thickness.

[0269]

[0270] Comparative Example 3

[0271] The ALD process was carried out using NH3 as the reaction gas and the Mo(CO)6 precursor compound with the following chemical formula as the precursor compound.

[0272] [ka]

[0273] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While flowing Ar gas as a carrier gas at 50 sccm, the Mo(CO)6 precursor was introduced into the deposition chamber for 3 seconds. Then, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0274] Next, NH3, the prepared reaction gas, was supplied to the chamber at a flow rate of 1,000 sccm. The reaction gas, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Then, argon gas was supplied at 5,000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 375°C, and this process was repeated 50 to 200 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0275] The film thickness of the fabricated thin film (Mo nitride film) was measured using an ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index using the polarization characteristics of light. The film thickness deposited per cycle was calculated by dividing the measured thickness by the number of cycles, and it was found to be 10 nm. After measuring the surface resistance using the 4-probe measurement method, the resistivity was calculated using the measured film thickness. The crystallinity of the Mo thin film was confirmed by XRD analysis.

[0276]

[0277] Comparative Example 4

[0278] The ALD process was carried out using NH3 as the reaction gas and the Mo(tol)2 precursor compound with the following chemical formula as the precursor compound.

[0279] [ka]

[0280] First, the prepared precursor compound was placed in a separate canister and heated to 130°C. While flowing Ar gas as a carrier gas at 50 sccm, the Mo(tol)2 precursor was introduced into the deposition chamber for 10 seconds. Then, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0281] Next, NH3, the prepared reaction gas, was supplied to the chamber at a flow rate of 1,000 sccm. The reaction gas, vaporized into a vapor phase in the vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. Then, argon gas was supplied at 5,000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 2.5 Torr. The deposition temperature was maintained at 250°C and 300°C, respectively, and this process was repeated 30 to 300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0282] An ellipsometer, a device capable of measuring optical properties such as film thickness and refractive index of a manufactured thin film (Mo nitride film) using the polarization characteristics of light, was used to measure the film thickness of the thin film. By dividing the measured film thickness by the number of cycles, the film thickness deposited per cycle was calculated to be 10 nm. After measuring the surface resistance using the 4-probe measurement method, the resistivity was calculated using the measured film thickness.

[0283]

[0284] Comparative Example 5

[0285] The bond dissociation energy of the thin-film forming material and metal precursor of the present invention is an important factor in reducing the precursor at low temperatures. The computer simulation program used to calculate the bond dissociation energy was Gaussian 16, and the computer simulation method used was DFT-D3 / B3LYP. The basis set was LanL2DZ for iodine and the central metal (e.g., Mo), and 6-31+G(d,p) for the other elements.

[0286] Furthermore, the activation energy of the reaction between the Mo(CO)6 and (EtCp)Mo(CO)2(NO) precursors and H2 was calculated using the same method as described above. In this case, the method used to search for the transition state was the DFT / TS-Berny method, and the intrinsic reaction coordinate (IRC) was 40 points.

[0287]

[0288] Comparative Example 6

[0289] The ALD process was carried out using 99% CH3I as the thin-film forming material and a MoCl5 precursor with the following chemical formula as the precursor compound.

[0290] [ka]

[0291] First, the prepared precursor compound was placed in a separate canister and heated to 140°C. While flowing Ar gas as a carrier gas at 100 sccm, the MoCl5 precursor was introduced into the deposition chamber for 5 seconds. Then, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 5.0 Torr.

[0292] Next, the prepared thin-film forming material was placed in a canister and supplied to the chamber at room temperature using a mass flow controller (MFC) at a flow rate of 1000 sccm. The thin-film forming material, vaporized into a vapor phase in a vaporizer, was introduced into the deposition chamber containing the substrate for 2 seconds to carry out a reduction reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. At this time, the pressure inside the reaction chamber was controlled to 5.0 Torr. The deposition temperature was maintained at 400-600°C, and this process was repeated 30-300 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0293]

[0294] Comparative Example 7

[0295] NH3 was used as the reactant for the nitriding process, and a TiCl4 precursor was used as the precursor compound for the ALD process.

[0296] First, the prepared precursor compound was placed in a separate canister and heated to 50°C. While flowing Ar gas as a carrier gas at 100 sccm, the TiCl4 precursor was introduced into the deposition chamber for 3 seconds. Then, argon gas was supplied at 3000 sccm for 5 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.0 Torr.

[0297] Next, NH3 was supplied to the chamber at 1000 sccm to inject the reaction gas. The deposition temperature was set to 500-550°C, and this process was repeated 50-150 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0298]

[0299] Comparative Example 8

[0300] The ALD deposition process was carried out using NH3 as the reactant for the nitriding process and NbF5 precursor as the precursor compound. The procedure was carried out in the same manner as in Example 8, except that the low-temperature deposition material was supplied.

[0301]

[0302] Comparative Example 9

[0303] The ALD deposition process was carried out using NH3 as the reactant for the nitriding process and a MoO2Cl2 precursor as the precursor compound. The procedure was carried out in the same manner as in Example 9, except that the low-temperature deposition material was supplied.

[0304]

[0305] Comparative Example 10

[0306] The ALD deposition process was carried out using H2 as the reactant and the following chemical formula MoCl5 precursor compound as the precursor compound. [ka]

[0307]

[0308] First, the prepared precursor compound was placed in a separate canister and heated to 140°C. While flowing Ar gas as a carrier gas at 100 sccm, the MoCl5 precursor was introduced into the deposition chamber for 5 seconds. Then, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 5.0 Torr.

[0309] Next, H2 was used as the reactant and supplied at 1000 sccm for 5 seconds to carry out the reduction reaction. After that, argon gas was supplied at 5000 sccm for 10 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 5.0 Torr. The deposition temperature was maintained at 400°C.

[0310]

[0311] [Example Test]

[0312] For each of the thin films obtained in Examples 1-9 and Comparative Examples 1-10, the impurity content, the types and content of elements constituting the material surface, the deposition rate, the crystal structure, and orientation were confirmed using the following methods.

[0313] * Analysis of carbon impurities by secondary-ion mass spectrometry (SIMS): While ion sputtering was applied axially to the thin film, the sputtering time reached 50 seconds, when it was considered that there was little contamination in the surface layer of the substrate. The carbon impurity content (count) was then taken into consideration and the value of carbon impurities was confirmed from the SIMS graph.

[0314] * Auger electron spectroscopy (AES): A focused electron beam is incident on the surface of a material, and the energy of the emitted Auger electrons is measured to analyze the types and content of elements that make up the surface of the material.

[0315] * Measurement of deposition rate (GPC: Growth Per Cycle): The deposition rate (GPC) was measured for each of the thin films obtained in Examples 1-9 and Comparative Examples 1-9 using the following method. Specifically, the deposition rate of thin films with thicknesses of 3-30 nm was measured using an ellipsometer, and the unit used was Å / cycle.

[0316] * Glazing incident X-ray diffraction (incident angle (θ) = 3°): Surface diffraction analysis was performed using Cu-Kα X-rays to confirm information such as the crystal structure and orientation.

[0317] [Table 1]

[0318] As shown in Table 1 above, it can be confirmed that by utilizing either the HI thin film forming material alone or the combined process of the HI thin film forming material and NH3 reaction gas according to the present invention, the amount of carbon impurities generated when the NH3 reaction gas is used alone is drastically reduced.

[0319] Furthermore, as is clear from Examples 1 and 2, AES analysis confirmed that the amount of C impurities was reduced to 0% during thin film formation, and SIMS analysis confirmed that the number of C ions detected by 91% or more was reduced.

[0320] Furthermore, the increase in thin film density from 6.0 to 6.8 indicates that an extremely high-quality MoN thin film was formed.

[0321]

[0322] [Table 2]

[0323] As shown in Table 2 above, when using either the HI thin film forming material alone or the combined process of the HI thin film forming material and NH3 reaction gas according to the present invention, the resistivity of the formed thin film decreases sharply compared to when the NH3 reaction gas is used alone. Furthermore, the amount of C impurities is in the order of Comparative Example 2 > Example 4 > Example 3, suggesting that the HI thin film forming material alone was also used to achieve the most effective reduction.

[0324]

[0325] [Table 3]

[0326] As shown in Table 3 above, when the HI thin film forming material is used according to the present invention, the resistivity of the formed thin film decreases sharply and the deposition rate increases by more than three times compared to when NH3 reaction gas is used alone.

[0327] In particular, XRD analysis was performed for each process temperature, and the results are shown in Figure 2 below. Figure 2 is an XRD analysis graph for each process temperature of Example 5 and Comparative Example 3 of the present invention.

[0328] As is clear from Figure 2 below, in Example 5, a pure Mo metal thin film was formed.

[0329] Furthermore, the AES analysis results for each temperature in Example 5 are shown in Figure 1 below.

[0330] Figure 1 is a graph showing the AES analysis results for each temperature in Example 5 according to the present invention. As is clear from Figure 1 below, the changes in the types and contents of constituent elements for each process temperature were confirmed.

[0331]

[0332] [Table 4]

[0333] As shown in Table 4 above, when the HI thin film forming material is used according to the present invention, the resistivity of the formed thin film decreases sharply and the deposition rate increases by more than double compared to when only NH3 reaction gas is used.

[0334] In particular, XRD analysis was performed, and the results are shown in Figure 3 below. Figure 3 is the XRD analysis graph for Example 6 and Comparative Example 4 of the present invention.

[0335] As is clear from Figure 3 below, a partially pure Mo metal thin film was formed in Example 6.

[0336]

[0337] [Table 5]

[0338] As shown in Table 5 above, when using the HI thin film forming material according to the present invention, a Mo metal thin film with low resistivity was formed at a low temperature of 400°C. Furthermore, in the case of iodine bonded to carbon, it can be seen that a Mo thin film is formed without carbon impurities when using I-1, which has a low bond dissociation energy. However, in the case of CH3I, which has a strong carbon-iodine bond of 250 kJ / mol, not only did the resistivity increase by more than 10 times, but carbon impurities were also found to be present in the thin film. This is because carbon is a factor in the increase in resistivity and acts as an impurity inside the thin film.

[0339] In the mechanism of residual impurities in thin films, if the bond dissociation energy between carbon and iodine is large, the iodine bond will not dissociate, or the dissociated carbon molecules will strongly bond to the substrate surface and will not detach.

[0340] On the other hand, in Comparative Example 10, which used H2 with a high bond energy, a Mo thin film was not formed at the low temperature of 400°C.

[0341]

[0342] Furthermore, in Example 8, the results of calculating the bond dissociation energy of the carbon or hydrogen compound bonded with iodine are shown in Table 6 below.

[0343] [Table 6]

[0344] On the other hand, the CH3I used in Comparative Example 6 had a bond dissociation energy of 250.15 kJ / mol.

[0345] In Example 8 and Comparative Example 5, the reaction activation energies required to reduce the CO ligand and NO ligand of the Mo(CO)6 precursor and (EtCp)Mo(CO)2(NO) precursor, respectively, are shown in comparison with H2 and HI in Figures 4 and 5 below.

[0346] As is clear from Figures 4 and 5 below, the energy required to reduce the CO ligand using H2 in the Mo(CO)6 precursor is 341.67 kJ / mol, but when HI is used, the activation energy is extremely low at 157.12 kJ / mol. This result suggests that reduction is possible at even lower process temperatures without C and O impurities.

[0347] While the energy required to reduce the NO ligand using H2 in the (EtCp)Mo(CO)2(NO) precursor is 323.77 kJ / mol, it can be confirmed that the activation energy is extremely low at 82.91 kJ / mol when using HI. This result suggests that reduction can be achieved even at lower process temperatures without N and O impurities.

[0348] The bond dissociation energies of Mo precursors applicable to low-temperature processes are shown in Table 7 below.

[0349]

[0350] [Table 7]

[0351] As is clear from Table 7 above, it can be confirmed that reduction occurs at temperatures of 400°C or lower when the binding dissociation energy with the ligand bound to Mo is 350 kJ / mol or less.

[0352]

[0353] Table 8 below shows the resistivity values ​​corresponding to the bond dissociation energy of the inventive materials used to reduce the reaction activation energy between TiCl4 and NH3 reaction gas during the formation of TiN thin films.

[0354]

[0355] [Table 8]

[0356] As is clear from Table 8 above, with the exception of CH3I2, which does not have a carbon-iodine bond, we confirmed that for iodine bonded to carbon, not only is the deposition rate improved, but the resistivity is also improved, limited to substances with a concentration of 242 kJ / mol or less.

[0357] In particular, we were able to confirm that the greater the bond dissociation energy between carbon and iodine, the wider the degradation range of resistivity.

[0358] [Table 9]

[0359] As is clear from Table 9 above, when forming metal nitride films in each low-temperature process, it was confirmed that using low-temperature deposition materials not only improves the deposition rate and resistivity, but also reduces impurities remaining in the thin film due to insufficient reduction of the precursor ligand in the low-temperature process.

[0360] As a result, it was confirmed that using a predetermined low-temperature deposition material that can perform catalytic or reduction reactions at a relatively low process temperature so that the precursor compound adsorbed on the surface of the substrate introduced into the chamber does not undergo thermal decomposition is suitable for improving the film quality of the low-temperature deposited film, such as its electrical properties and crystallinity, while preventing the inflow of thin-film impurities caused by ligands such as carbon.

Claims

1. A low-temperature deposition material for wiring metals, metals with a melting point of 350°C or lower, or a diffusion-preventing film for wiring metals, A low-temperature vapor deposition material characterized by containing one or more compounds selected from among compounds having a direct bond between hydrogen (H) and iodine, compounds having a direct bond between carbon (C) and iodine, and compounds having a direct bond between a halogen element (F, Cl, Br) and iodine.

2. The aforementioned wiring metal or metal with a melting point of 350°C or less is selected from Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga. The low-temperature deposition material according to claim 1, characterized in that the wiring metal diffusion prevention film is a transition metal nitride film of Ti, Ta, Ni, Mo, Nb, Zr, V, W, or a nitride film in which a combination of two or more metals is selected.

3. The low-temperature vapor deposition material according to claim 1, characterized in that the compound having a direct bond between hydrogen (H) and iodine has a total bond energy of 305 to 325 kJ / mol calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(d.p))).

4. The low-temperature vapor deposition material according to claim 1, characterized in that the compound having a direct bond between carbon (C) and iodine has a total bond energy of 165 to 242 kJ / mol calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(d.p))).

5. The low-temperature vapor deposition material according to claim 1, characterized in that the compound having a direct bond between the halogen element (F, Cl, Br) and iodine has a total bond energy of 50 to 160 kJ / mol calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (iodine: LanL2DZ, carbon, hydrogen element: 6-31+G(d.p))).

6. The low-temperature vapor deposition material according to claim 1, characterized in that the low-temperature vapor deposition material is one or more compounds selected from the compounds represented by the following chemical formulas 1-1 to 1-11. [Chemical formulas 1-1 to 1-11] 【Chemistry 1】

7. A method for forming a low-temperature vapor-deposited film, characterized by comprising the step of depositing a low-temperature vapor-deposited material as a vapor-deposited film using any one of claims 1 to 6.

8. The method for forming a low-temperature deposited film according to claim 7, characterized in that the deposited film is a metal film and / or a metal nitride film.

9. The method for forming a low-temperature vapor-deposited film according to claim 7, characterized in that it includes the step of injecting a precursor compound and the low-temperature vapor-deposited material into a chamber and forming a vapor-deposited film using a reduction reaction while adsorbing them onto the surface of a substrate.

10. The method for forming a low-temperature deposited film according to claim 7, characterized in that the step of injecting hydrogen as a reaction gas to carry out a reduction reaction is omitted.

11. The method for forming a low-temperature vapor-deposited film according to claim 7, characterized in that the method includes a post-treatment step of purging the inside of a chamber with a purge gas.

12. The method for forming a low-temperature deposited film according to claim 9 or 11, characterized in that the chamber is an atomic layer deposition (ALD) chamber, a vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced vapor deposition (PECVD) chamber.

13. The method for forming a low-temperature deposited film according to claim 7, characterized in that the low-temperature deposited film is a laminated film of one or more metals selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga.

14. The method for forming a low-temperature deposited film according to claim 7, characterized in that the low-temperature deposited film has a resistivity in the range of 5 μΩ·cm to 1000 μΩ·cm.

15. The method for forming a low-temperature deposited film according to claim 9, characterized in that the precursor compound is a molecule having one or more elements selected from the group consisting of Mo, W, Ru, Cu, Rh, Pb, Cd, Sn, Bi, In, and Ga as a central metal atom (M), and one or more ligands consisting of C, N, O, H, and X (halogen), and in order to reduce the central metal atom at a low process temperature of 400°C or less, the compound is such that the bond dissociation energy between the central metal atom and the ligand, calculated using the Gaussian 16 program (DFT-D3 / B3LYP basis set (central metal, iodine: LanL2DZ, C, N, O, H, X: 6-31+G(d.p)) is 350 kJ / mol or less.

16. The method for forming a low-temperature deposited film according to claim 9, characterized in that the substrate is heated to 100 to 700°C.

17. A semiconductor substrate comprising a low-temperature deposited film manufactured by the low-temperature deposited film formation method described in claim 7.

18. A semiconductor element characterized by comprising the semiconductor substrate described in claim 17.

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