Reactive species surface adsorption aid, thin film, semiconductor substrate, and semiconductor device

Abstract

The present invention relates to a reactive species surface adsorption aid, a thin film, a semiconductor substrate, and a semiconductor device. According to the present invention, the reactive species surface adsorption aid is applied prior to the injection of a metal precursor, so that during the exposure of a substrate to the metal precursor, the reactive species surface adsorption aid reduces the adsorption energy of a reactive species to promote the nucleation of the reactive species, leading to an increased initial deposition rate and improved resistivity, thereby enabling the provision of a high-quality thin film.

Description

Reactive species surface adsorption aids, thin films, semiconductor substrates and semiconductor devices

[0001] The present invention relates to a reactive species surface adsorption assistant, a thin film, a semiconductor substrate and a semiconductor device, and more particularly, to a reactive species surface adsorption assistant, a thin film, a semiconductor substrate and a semiconductor device capable of providing a high-quality thin film by improving the initial deposition speed and resistivity by reducing the adsorption energy of the reactive species when exposing the metal precursor to the substrate prior to metal precursor injection and promoting nucleus formation of the reactive species.

[0002] In the conventional thin film formation through ALD (atomic layer deposition), the surface adsorption of reactive species provided by the injected metal precursor is the most important factor in initiating thin film deposition.

[0003] The factor determining the initial nucleation time is influenced by the extent of surface adsorption of the above reactants.

[0004] As the miniaturization of semiconductor devices causes the initial nucleation to occur later when forming a thin film in the horizontal direction, the initial nucleation ALD deposition is required to form the nuclei, which has a negative effect on the UPH (unit per hour) aspect, i.e. productivity, and increases the surface roughness of the thin film, which affects the crystallinity, thereby lowering the density and electrical conductivity of the thin film.

[0005] Therefore, it is necessary to develop a deposition technology that promotes initial nuclei growth for each deposition cycle, thereby enabling the deposition of thicker films relative to the number of cycles without initial nucleation ALD deposition, thereby improving productivity and film quality.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] Korean Patent Publication No. 2021-0077789

[0009] One object of the present invention is to provide a reactive species surface adsorption aid that can improve resistivity while increasing the thickness of a thin film by applying it in a step prior to metal precursor injection.

[0010] Another object of the present invention is to provide a thin film using the aforementioned reactive species surface adsorption aid and a method for manufacturing the same.

[0011] Another object of the present invention is to provide a semiconductor substrate and a semiconductor device including the thin film.

[0012] According to the present invention, a reactive species surface adsorption assistant for a metal precursor for a thin film is provided, wherein the reactive species surface adsorption assistant is characterized in that it is an iodine-containing compound.

[0013] The above-mentioned reactive species surface adsorption assistant may be an iodine-containing compound that promotes nucleation of the reactive species by reducing the adsorption energy of the reactive species when exposing a metal precursor to a substrate.

[0014] The above iodine-containing compound may be at least one selected from hydrogen iodide, hydrogen iodide, and a halide having an alkyl group having 4 to 15 carbon atoms.

[0015] The above hydrogen iodide or hydrogen iodide water is a single hydrogen iodide having a purity of 3N to 15N, a gas mixture of 1 to 99 wt% of hydrogen iodide having a purity of 3N to 15N and the balance of an inert gas so that the total amount becomes 100 wt%, or an aqueous solution mixture of 0.5 to 70 wt% of hydrogen iodide having a purity of 3N to 15N and the balance of water so that the total amount becomes 100 wt%, wherein the inert gas may be nitrogen, helium or argon having a purity of 4N to 9N.

[0016] The above alkyl group having 4 to 15 carbon atoms may be an iodine compound having a secondary benzyl, secondary allyl, tertiary benzyl, tertiary allyl, or tertiary alkyl structure.

[0017] The above metal precursor may be at least one selected from the group represented by the following chemical formulas (1) to (6).

[0018] Chemical formula (1) = M x L y L' z

[0019] (In the above chemical formula (1), x below is an integer of 1 to 3, M below can be selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn, y is an integer of 1 to 6, z is an integer of 0 to 6 (preferably 1 to 6), and L and L' are each independently A ligand composed of one or more combinations of H, C, N, O, F, P, S, Cl, Br or I, or a ligand composed of H, C, N, O, F, P, S, Cl and Br.

[0020]

[0021] Chemical formula (2) =

[0022] (In the above chemical formula (2), M1 below is Zr, Hf, Si, Ge or Ti, X1, X2, X3 below are independently -NR1R2 or -OR3 or -R4, R1 to R4 are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.)

[0023]

[0024] Chemical formula (3) =

[0025] (In the above chemical formula (3), M is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2, -OR'3, or R'4, and R'1 to R'4 are independently an alkyl group having 1 to 6 carbon atoms.)

[0026] Chemical formula (4) = M(O)n(X)m(L)k

[0027] (In the above chemical formula (4), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo; O is oxygen, X is halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 0 to 3.)

[0028] Chemical formula (5) = MXaYbZc

[0029] (In the above chemical formula (5), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo; X is a halogen element; Y is an amine series or an alkoxy series; a is an integer from 0 to 6; b is an integer from 0 to 6; Z is selected from the group consisting of an alkyl cyanide having 1 to 15 carbon atoms, or a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); and c is an integer from 0 to 5.)

[0030] Chemical formula (6) = ML1L2L3L4(L5)h(L6)i

[0031] (In the above chemical formula (6), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo, L1, L2, L3, L4, L5, and L6 are independently H; F; Cl; Br; I; NRaRb; ORc; CO; RdCp; amidinate; guadiinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbons substituted with one or more carbons (C), nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); Cp is cyclopentadienyl, Ra, Rb, Rc, and Rd are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and I are independently 0 or 1, and the overall oxidation number of the compound is an integer of -2 to 6.)

[0032] The above thin film may be at least one laminated film selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At, and Tn.

[0033] The above effect is more preferably expressed when the size of the metal constituting the thin film is small and the metal prefers ionic bonding (hard acid metal).

[0034] For example, it can be Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ti, Zr, Hf, V, Nb, Cr, Al, Ga, Si, Ge, Sn, As, Sb.

[0035] The above thin film may be formed as a nitride film, a metal film, an oxide film, or a selective thin film thereof on the entire substrate or a portion of the substrate.

[0036]

[0037] In addition, the present invention provides a thin film characterized in that it is formed by applying the aforementioned reactive species surface adsorption aid before injection of a metal precursor.

[0038] The above thin film may be a dielectric film, a wiring or a barrier metal.

[0039] The dielectric film may be SiO2, ZrO2, HfO2, TiO2, or Al2O3.

[0040] The above wiring may be made of at least one metal (M) selected from the group consisting of Al, Cu, Au, Mo, Ag, W, Pt, Ag, Ta, Co, Ru, and Ti.

[0041] The barrier metal may be a metal (M), a metal nitride (MN), a metal sulfide (MS2), or a metal carbide (MC), and may be formed of, for example, any one of TiN, TiC / TiN, TiAlN, TiSiN, TaSiN, WN, WC, TaN, and MoN.

[0042] The above thin film exhibits an initial deposition rate of 0.1 to 1.5 Å / cycle, wherein the initial deposition can be 1 to 70 cycles.

[0043] The above wiring and barrier metal thin film may have a resistivity value of 0.1 to 1,000 μΩcm based on a thin film thickness of 50 nm.

[0044] The above wiring and barrier metal thin film may have a resistivity value of 0.1 to 500 μΩcm based on a thin film thickness of 100 nm.

[0045]

[0046] In addition, the present invention

[0047] A step of forming a seed layer by exposing the aforementioned reactive species surface adsorption aid to the substrate;

[0048] A step of loading the substrate into a chamber and exposing the seed layer to a metal precursor to form a surface adsorption layer of a reactive species; and

[0049] A method for forming a thin film is provided, characterized by including a step of forming a reaction species adsorption layer by exposing the reaction species surface adsorption layer to a reaction gas.

[0050] The above thin film forming method may include a step of forming a seed layer by exposing the above-described reactive species surface adsorption assistant to a substrate; a step of forming a reactive species surface adsorption layer on a substrate by injecting a metal precursor into a chamber; a step of first purging the inside of the chamber with a purge gas; a step of forming a reactive species adsorption layer by exposing the reactive species surface adsorption layer to a reaction gas; and a step of secondarily purging the inside of the chamber with a purge gas.

[0051] The chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0052] The substrate loaded into the chamber may be heated to 100 to 800°C.

[0053] The above reaction gas may be a nitriding agent, a reducing agent, or an oxidizing agent.

[0054] The above nitrifying agent may be nitrogen, ammonia, etc.

[0055] The above reducing agent may be hydrogen, etc.

[0056] The above oxidizing agent may be oxygen, ozone, water, N2O, etc.

[0057] In addition, the present invention provides a semiconductor substrate characterized by including the aforementioned thin film.

[0058] The above thin film may have a multilayer structure of two or three layers.

[0059] In addition, the present invention provides a semiconductor device characterized by including the semiconductor substrate described above.

[0060] According to the surface adsorption aid of the reactive species of the present invention, when a metal precursor is exposed to a substrate, the adsorption energy of the reactive species is reduced, thereby promoting the formation of nuclei of the reactive species, thereby providing a semiconductor device having not only a thick film thickness relative to the number of cycles but also a reduced leakage current and excellent resistivity.

[0061] In addition, according to the surface adsorption aid of the reactive species of the present invention, there is an effect of improving the deposition rate to increase productivity, and improving the film density and electrical conductivity of the metal or metal nitride (MN) or metal carbide (MC) forming the wiring or barrier metal, thereby providing a semiconductor device having very excellent performance.

[0062] Figure 1 is a schematic diagram showing the difference in cross-section of thin films formed depending on whether a reactive species surface adsorption aid is used. (a) shows a thin film according to the prior art described below formed using a substrate pretreated using a reactive species surface adsorption aid, and (b) shows a thin film according to Example 1 formed using a substrate pretreated using a reactive species surface adsorption aid.

[0063] Figure 2 is a graph confirming the deposition thickness per cycle of Example 1 of the present invention and Comparative Example 1 according to the prior art.

[0064]

[0065] Hereinafter, the present invention will be described in detail.

[0066] As used herein, the term "reactive species" refers to a substrate adsorbate capable of displacing or separating a ligand from a metal precursor to provide a film, unless otherwise specified.

[0067] In this document, unless otherwise specified, the term “surface adsorption” or “adsorption” means a positive interaction of a substance other than a metal precursor and a reactant on the reaction surface to improve film quality, such as reducing resistivity, increasing density, reducing impurities, and improving step coverage of the deposited thin film.

[0068]

[0069] The inventors of the present invention confirmed that by using a specific halogen compound that can promote the formation of nuclei of reactive species by reducing the adsorption energy of reactive species when exposing a metal precursor to the surface of a substrate loaded inside a chamber, the deposition thickness of the thin film per cycle is increased while improving the film properties such as electrical characteristics, dielectric characteristics, and thin film density, and dedicated themselves to related research to complete the present invention.

[0070] As discussed above, the present invention has the characteristic of improving the deposition thickness of the thin film by the number of cycles and enhancing the resistivity by applying a reactive species surface adsorption aid to the stage before metal precursor injection in order to solve the above-mentioned problems.

[0071] Due to these characteristics, the density of the thin film is improved, and in the case of dielectric films (SiO2, ZrO2, HfO2, TiO2, Al2O3, etc.), the electrostatic capacitance increases and the leakage current decreases, which is very effective in manufacturing semiconductor devices.

[0072] In addition, it has a very excellent effect in manufacturing semiconductor devices by improving the electrical conductivity of metal (M) or metal nitride (MN) or metal carbide (MC) forming wiring or barrier metal.

[0073] Here, the metal may be at least one selected from, for example, Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn, and preferably Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Se, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, It may be at least one selected from the group consisting of Ir, La, Ce, and Nd.

[0074] The aforementioned thin film may have a film composition of, for example, a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum metal film, a hafnium metal film, a zirconium metal film, a tungsten metal film, an aluminum metal film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0075] The above thin film may include the above-described film composition alone or as a selective area, but is not limited thereto, and also includes SiH and SiOH.

[0076] The above thin film can be used in semiconductor devices not only as a diffusion barrier film but also as an etching stop film, electrode film, dielectric film, gate insulating film, block oxide film, or charge trap.

[0077]

[0078] The surface adsorption assistant for the reactive species used in the present invention may use an iodine-containing compound, and is characterized by using at least one selected from, for example, hydrogen iodide, hydrogen iodide, and a halide having an alkyl group of 4 to 15 carbon atoms. In this case, when a metal precursor is exposed to the surface of a substrate, a predetermined halogen compound capable of promoting nucleus formation of the reactive species by reducing the adsorption energy of the reactive species is used, thereby increasing the deposition thickness of the thin film per cycle and improving film properties such as electrical characteristics, dielectric characteristics, and thin film density.

[0079] As a specific example, the above-mentioned reactive species surface adsorption aid may be introduced in various forms, such as a single substance, a gaseous mixture, or an aqueous solution mixture, prior to injection of the metal precursor.

[0080] The above single material can use 100 wt% of HI, for example, 3N to 15N.

[0081] The above single product can use 100% by weight of an iodine compound having a secondary benzyl, secondary allyl, tertiary benzyl, tertiary allyl, or tertiary alkyl structure as the alkyl group having 4 to 15 carbon atoms.

[0082] The above gas mixture may be composed of, for example, 1 to 99 wt% of HI of 3N to 15N and the remainder of an inert gas such that the total amount of the gas mixture becomes 100 wt%. Here, the inert gas may be nitrogen, helium, argon, etc. having a purity of 4N to 9N.

[0083] The above aqueous solution mixture may be composed of, for example, 0.5 to 70 wt% of HI of 3N to 15N and the remainder of H2O such that the total amount of the aqueous solution mixture becomes 100 wt%.

[0084]

[0085] The metal precursor used in the present invention can be a variety of materials known in the art, and examples thereof include materials represented by the following chemical formulas (1) to (6).

[0086] 1) Chemical formula (1)

[0087] Chemical formula (1) = M x L y L' z

[0088] , and the following x is an integer from 1 to 3, and the following M may be selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn, y is an integer from 1 to 6, z is an integer from 0 to 6 (preferably 1 to 6), and the above L and L' are each independently H, A ligand composed of one or more types selected from the group consisting of C, N, O, F, P, S, Cl, Br, or I, or a combination of two or more types selected from the group consisting of H, C, N, O, F, P, S, Cl, and Br.

[0089] For a specific example, the substance represented by the chemical formula (1) may be SiH2Cl2, SiH2I2, etc.

[0090] 2) The following chemical formula (2)

[0091] Chemical formula (2) =

[0092] , and M1 below is Zr, Hf, Si, Ge or Ti, and X1, X2, X3 below are independently -NR1R 2, -OR 3, or R4, wherein R1 to R4 are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.

[0093] 3) Chemical formula (3)

[0094] Chemical formula (3) =

[0095] , and M below is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2, -OR'3, or R'4, and R'1 to R'4 are independently an alkyl group having 1 to 6 carbon atoms.

[0096] 4) Chemical formula (4)

[0097] Chemical formula (4) = M(O)n(X)m(L)k, where Mo is molybdenum, O is oxygen, X is halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 0 to 3.

[0098] 5) Chemical formula (5)

[0099] Chemical formula (5) = MXaYbZc

[0100] (In the above chemical formula (5), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo; X is a halogen element; Y is an amine series or an alkoxy series; a is an integer from 0 to 6; b is an integer from 0 to 6; Z is selected from the group consisting of an alkyl cyanide having 1 to 15 carbon atoms, or a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); and c is an integer from 0 to 5.)

[0101] 6) The following chemical formula (6)

[0102] Chemical formula (6) = ML1L2L3L4(L5)h(L6)i

[0103] , and M below is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru and Mo, L1, L2, L3, L4, L5 and L6 below are independently H; F; Cl; Br; I; NRaRb; ORc; CO; RdCp; amidinate; guadiinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbon substituted with one or more carbon (C), nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); Cp below is cyclopentadienyl, Ra, Rb, Rc and Rd below are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and I below are independently 0 or 1, and the overall oxidation number of the compound is an integer of -2 to 6.

[0104] For example, the ligand may be a thin film metal precursor selected from the group consisting of alkyl cyanides having 1 to 15 carbon atoms in the alkyl; and linear or cyclic saturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S).

[0105] The reaction gas used in the present invention can be selected according to the target thin film to be manufactured, and is connected to the target thin film, for example, as follows.

[0106] As a reaction gas for the oxide film, one or more of O2, O3, H2O, and N2O can be selected.

[0107] Additionally, one or more of H2, NH3, and reducing molecules (such as formic acid) can be selected as the reaction gas for the metal film.

[0108] Additionally, the reaction gas for the nitride film may be NH3 or H2 / N2 gas mixture.

[0109] Additionally, the reaction gas for the carbide metal film may be H2, alkane, or M(CH3)3, where M may be a boron group (group 13 of the periodic table) element.

[0110] Additionally, the reaction gas for the metal sulfide film may be a gaseous or vaporous molecular species containing H2S and S.

[0111] As a specific example, the TiN nitride film of the semiconductor device manufactured through the present invention has an initial GPC of, for example, 0.1 to 1.5 Å / cycle, preferably 0.5 to 1.5 Å / cycle, and more preferably 0.8 to 1.2 Å / cycle up to 70 cycles, and in this case, the speed can be improved at the beginning of the deposition, thereby providing an effect of thickening the film thickness per cycle.

[0112] The TiN nitride film of the semiconductor device manufactured through the present invention may have a resistivity value of, for example, 0.1 to 1,000 μΩcm based on a film thickness of 50 nm, preferably 15 to 590 μΩcm, and more preferably 15 to 290 μΩcm, and excellent thin film properties are effective within this range.

[0113] The above thin film may have a resistivity value of, for example, 0.1 to 500 μΩcm, preferably 15 to 120 μΩcm, based on a thin film thickness of 100 nm, and has excellent thin film properties within this range.

[0114]

[0115] Meanwhile, the above-mentioned reactive species surface adsorption aid can provide a seed layer on the substrate.

[0116] For example, the seed layer may be formed on the entire substrate or a portion of the substrate on which the thin film is formed.

[0117] The above seed layer is characterized in that it does not remain on the thin film.

[0118] At this time, unless otherwise specified, non-residue refers to a case where C element is present at less than 0.1 atom% (atom %), Si element at less than 0.1 atom% (atom %), N element at less than 0.1 atom% (atom %), and halogen element at less than 0.1 atom% (atom %) when analyzed by XPS. More preferably, in the Secondary-ion mass spectrometry (SIMS) measurement method or X-ray Photoelectron Spectroscopy (XPS) measurement method that digs deep into the substrate and measures, when considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using the shielding agent under the same deposition conditions, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element species does not exceed 5%.

[0119] The above thin film may contain, for example, 100 ppm or less of a halogen compound.

[0120] The above thin film can be used as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap, but is not limited thereto.

[0121] The above-mentioned reactive species surface adsorption aid may preferably be a compound having a purity of 99.9% or more, a compound having a purity of 99.95% or more, or a compound having a purity of 99.99% or more. For reference, when using a compound having a purity of less than 99%, impurities may remain in the thin film or cause a side reaction with the precursor or reactant, so it is recommended to use a substance having a purity of 99% or more if possible.

[0122]

[0123] The method for forming a thin film of the present invention comprises the steps of: forming a seed layer by exposing the aforementioned reactive species surface adsorption aid to a substrate; loading the substrate into a chamber and exposing the seed layer to a metal precursor to form a reactive species surface adsorption layer; and exposing the reactive species surface adsorption layer to a reaction gas to form a reactive species adsorption layer; In this case, when exposing the metal precursor to the substrate, the adsorption energy of the reactive species is reduced to promote nucleation of the reactive species, thereby improving the initial deposition speed and improving the resistivity, thereby providing a high-quality thin film.

[0124]

[0125] In addition, the present invention

[0126] i) A step of loading a substrate into a chamber and exposing it to a reactive species surface adsorption aid to form a seed layer on the substrate surface;

[0127] ⅱ) A step of first purging the inside of the chamber with purge gas;

[0128] ⅲ) A step of vaporizing a metal precursor to expose the seed layer to the metal precursor and form a surface adsorption layer of a reactive species;

[0129] ⅳ) A step of secondary purging the inside of the chamber with purge gas;

[0130] ⅴ) a step of supplying a reaction gas into the chamber to expose a surface adsorption layer of the reaction species and form a reaction species adsorption layer; and

[0131] ⅵ) A method for forming a thin film is provided, including a step of purging the inside of the chamber for the third time with a purge gas.

[0132]

[0133] The above metal precursor may be a precursor having a vapor pressure of more than 0.01 mTorr and less than 100 Torr at 25°C, which is a molecule having the above-mentioned metal as a central metal.

[0134] In a preferred example, the method for forming a thin film of the present invention can adsorb the surface adsorption aid of the reactive species of the present invention onto the substrate before the metal precursor within one cycle, and in this case, the energy for the reactive species of the metal precursor to be adsorbed is reduced, thereby promoting the formation of nuclei of the reactive species, thereby improving the initial deposition speed and improving the resistivity, thereby providing a high-quality thin film.

[0135]

[0136] In the above thin film forming method, for example, when the surface adsorption aid of the reactive species is treated before deposition of the metal precursor, the unit cycle can be repeated 1 to 99,999 times as needed, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired thickness of the thin film can be obtained while sufficiently obtaining the effect to be achieved in the present invention.

[0137] The chamber may be an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber.

[0138] The above metal precursor may include a step of vaporizing and then injecting and then performing plasma post-treatment.

[0139] The amount of purge gas injected into the chamber in each of the above steps vi) and vi) may be 10 to 100,000 times the volume of the injected metal precursor and reaction gas.

[0140] The above reaction gas and metal precursor can be transported into the chamber by the VFC method, the DLI method, or the LDS method.

[0141] The substrate loaded in the chamber is heated to 100 to 800°C, and the ratio of the reactant surface adsorption aid and the metal precursor input into the chamber (mg / cycle) can be 1:1 to 1:20 or 20:1.

[0142] The above metal precursor can be preferably transported into the ALD chamber by the VFC method, the DLI method or the LDS method, and more preferably, it is transported into the chamber by the LDS method.

[0143] The substrate loaded in the chamber can be heated, for example, to 100 to 800°C, specifically to 200 to 600°C, and the metal precursor can be injected onto the substrate in an unheated or heated state. Depending on the deposition efficiency, it is possible to first inject the precursor in an unheated state and then adjust the heating conditions during the deposition process. For example, the precursor can be injected onto the substrate at 200 to 600°C for 1 to 20 seconds.

[0144]

[0145] The ratio of the amount (mg / cycle) of the metal precursor and the reactive species surface adsorption aid injected into the chamber may be preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10, and within this range, the effect of improving the film thickness and resistivity by cycle number is large.

[0146] In the present invention, purging is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter 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 or close to a single atomic mono-layer, which is advantageous in terms of film quality.

[0147]

[0148] The above ALD (atomic layer deposition process) is very advantageous in manufacturing integrated circuits (ICs) that require a high aspect ratio, and in particular, has advantages such as excellent conformality, uniformity, and precise thickness control due to a self-limiting thin film growth mechanism.

[0149] The above thin film formation method can be carried out at a deposition temperature in the range of, for example, 50 to 800°C, preferably at a deposition temperature in the range of 200 to 600°C, more preferably at a deposition temperature in the range of 350 to 600°C, even more preferably at a deposition temperature in the range of 400 to 600°C, and even more preferably at a deposition temperature in the range of 450 to 600°C, and within this range, there is an effect of growing a thin film with excellent film quality while implementing ALD process characteristics.

[0150] The above thin film formation method can be performed at a deposition pressure in the range of, for example, 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 1 to 7 Torr, and has the effect of obtaining a thin film of uniform thickness within this range.

[0151] In this description, the deposition temperature and deposition pressure can 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.

[0152] The above thin film formation method may preferably include a step of raising the temperature inside the chamber to a deposition temperature before introducing the metal precursor into the chamber; and / or a step of purging the chamber by injecting an inert gas into the chamber before introducing the metal precursor into the chamber.

[0153] In addition, the present invention may include a thin film manufacturing device capable of implementing the above thin film manufacturing method, which includes an ALD chamber, a first vaporizer for vaporizing a metal precursor, and a first transport means for transporting the vaporized metal precursor into the ALD chamber. Here, the vaporizer and the transport means are not particularly limited as long as they are vaporizers and transport means commonly used in the technical field to which the present invention pertains.

[0154]

[0155] As a specific example, to explain the above thin film formation method, first, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0156] The above substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0157] The above substrate may further have a conductive layer or an insulating layer formed on top thereof.

[0158] In particular, the substrate is pretreated with the aforementioned reactive species surface adsorption aid to form a seed layer.

[0159] In the present invention, the step of forming a seed layer on a substrate using a reactive species surface adsorption aid can be performed by supplying a reactive species surface adsorption aid.

[0160] In order to deposit a reactive species adsorption layer on a substrate positioned in the above deposition chamber, the above-described metal precursor or a mixture thereof with a non-polar solvent is prepared.

[0161] The prepared metal precursor or a mixture thereof with a non-polar solvent (a composition for forming a thin film) is injected into a vaporizer, then changed into a vapor phase and transferred to a deposition chamber to be adsorbed on a substrate, and the unadsorbed metal precursor is purged.

[0162] In this description, the method of delivering the metal precursor, etc. to the deposition chamber may be, for example, a method of delivering volatilized gas using a mass flow controller (MFC) method (Vapor Flow Control; VFC) or a method of delivering liquid using a liquid mass flow controller (LMFC) method (Liquid Delivery System; LDS), and preferably, the LDS method is used.

[0163] At this time, as a transport gas or dilution gas for moving a metal precursor, etc. onto a substrate, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) may be used, but are not limited thereto.

[0164] In the present invention, an inert gas may be used as the purge gas, for example, and preferably, the carrier gas or dilution gas may be used.

[0165]

[0166] Next, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the technical field to which the present invention pertains, and may preferably include a nitriding agent, an oxidizing agent, a reducing agent, etc.

[0167] For example, a nitride film is formed by a reaction between a nitriding agent and a metal precursor adsorbed on a substrate, and the nitriding agent used at this time may be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas.

[0168] Next, the unreacted residual reaction gas is purged using an inert gas. This removes not only the excess reaction gas but also any generated byproducts.

[0169] As described above, the method for forming a thin film comprises, as an example, a step of forming a seed layer by pretreating a substrate with a reactive species surface adsorption aid, a step of loading the substrate into a chamber and adsorbing a metal precursor onto the substrate, a step of purging unadsorbed metal precursor, a step of supplying a reaction gas, and a step of purging residual reaction gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0170] The above thin film forming method, as another example, comprises a step of forming a seed layer by pretreating a substrate with a reactive species surface adsorption aid, a step of loading the substrate into a chamber and purging the inside of the chamber, a step of adsorbing a metal precursor onto the substrate, a step of purging unadsorbed metal precursor, a step of supplying a reaction gas, and a step of purging residual reaction gas, and the unit cycle may be repeated to form a thin film of a desired thickness.

[0171] The above unit cycle may 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, there is an effect of well expressing the desired thin film properties.

[0172]

[0173] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film forming method of the present invention, and in this case, the thickness of the thin film relative to the number of cycles, particularly the initial film forming speed of the thin film, and the density and electrical properties of the thin film are excellent.

[0174] The above-mentioned manufactured thin film preferably has a thickness of 100 nm or less, a resistivity value of 0.1 to 1,000 μΩcm based on a thin film thickness of 50 nm, a resistivity value of 0.1 to 500 μΩcm based on a thin film thickness of 100 nm, a halogen content of 10,000 ppm or less, a step coverage of 90% or more, and within this range, has excellent performance as a diffusion barrier and has an effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0175] The above thin film may have a thickness of, for example, 0.1 to 100 nm, preferably 0.5 to 50 nm, more preferably 1.5 to 10 nm, and even more preferably 2 to 5 nm, and within this range, the thin film has excellent properties.

[0176] The above thin film may have a resistivity value of, for example, 0.1 to 1,000 μΩcm, preferably 0.1 to 560 μΩcm, and more preferably 0.1 to 260 μΩcm based on a thin film thickness of 50 nm, and the thin film has excellent properties within this range.

[0177] The above thin film may have a resistivity value of, for example, 0.1 to 500 μΩcm, preferably 0.1 to 320 μΩcm, and more preferably 0.1 to 120 μΩcm based on a thin film thickness of 100 nm, and the thin film has excellent properties within this range.

[0178] The above thin film may have a halogen content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm, and within this range, the thin film has excellent thin film properties while reducing the thin film growth rate. Here, the halogen remaining in the thin film is, for example, Cl2, Cl, or Cl - It can be, and the lower the halogen residue in the thin film, the better the film quality is, which is desirable.

[0179] The above thin film has a step coverage of, for example, 90% or more, preferably 92% or more, and more preferably 95% or more, and within this range, even a thin film with a complex structure can be easily deposited on a substrate, so it has the advantage of being applicable to next-generation semiconductor devices.

[0180]

[0181] The above thin film may have a multilayer structure of, for example, two or three layers, as needed. The multilayer film having a two-layer structure may have a lower layer-middle layer structure, as a specific example, and the multilayer film having a three-layer structure may have a lower layer-middle layer-upper layer structure, as a specific example.

[0182] The above-mentioned lower layer may be formed by including at least one selected from the group consisting of, for example, Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0183] The above-mentioned multilayer film is, for example, Ti x N y , preferably including TN.

[0184] The above upper layer may be formed by including at least one selected from the group consisting of, for example, W and Mo.

[0185]

[0186] In addition, the present invention provides a semiconductor substrate characterized by being manufactured by the above-described thin film forming method.

[0187] The above thin film may have a multilayer structure of two or three layers.

[0188]

[0189] In addition, the present invention provides a semiconductor device including the semiconductor substrate described above.

[0190] The semiconductor substrate may be a low resistive metal gate interconnect, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D Gate-All-Around (GAA), or a 3D NAND flash memory.

[0191]

[0192] Hereinafter, preferred embodiments and drawings are presented to help understand the present invention, but the following embodiments and drawings are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0193] Example

[0194] Example 1

[0195] A substrate with a 100 nm SiO2 film was prepared as the substrate. 5N HI was prepared as the surface adsorption aid for the reactant, and TiCl4 was prepared as the precursor compound. An ALD deposition process was performed using the substrate, the surface adsorption aid for the reactant, and the precursor compound.

[0196] Specifically, the substrate was placed in the deposition chamber, and then the prepared reactive species surface adsorption aid was supplied onto the substrate at a flow rate of 100 sccm for 5 seconds.

[0197] Next, 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 TiCl4 vaporized in the vaporizer was introduced into the deposition chamber for 2 seconds, and then argon gas was supplied at 5000 sccm for 6 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0198] The temperature inside the chamber was maintained at 500°C during the deposition reaction.

[0199] By repeating this process up to 250 times, a self-limiting atomic layer thin film was formed.

[0200] The manufactured thin film (Ti nitride film) is schematically shown in Fig. 1.

[0201] The following Figure 1 is a schematic diagram showing the difference in cross-section of a thin film formed depending on whether or not a reactive species surface adsorption aid is used. (a) shows a thin film according to the prior art described below formed using a process of pretreatment using a reactive species surface adsorption aid, and (b) shows a thin film according to Example 1 formed using a process of pretreatment using a reactive species surface adsorption aid.

[0202] As shown in Figure 1 below, it can be seen that the promotion of nucleus formation of the reaction species differs depending on whether or not a surface adsorption aid for the reaction species is used, and this difference can be confirmed through the test example below.

[0203]

[0204] Example 2

[0205] A substrate with a TiN (20 nm) / SiO2 (100 nm) film was prepared.

[0206] 5N HI was prepared as a surface adsorption aid for the reactive species.

[0207] Tris(dimethylamido)cyclopentadienyl hafnium (CpHf) and Tris(dimethylamido)cyclopentadienyl zirconium (CpZr) were prepared as precursor compounds, respectively.

[0208] The HfO2 and ZrO2 ALD deposition process was performed using the above substrate, reactive species surface adsorption aid, and precursor compounds. Then, a 300 nm Al electrode was formed as the top electrode using the e-beam evaporation deposition method to fabricate a MIM device.

[0209] Specifically, the substrate was placed in the deposition chamber, and then the prepared reactive species surface adsorption aid was supplied onto the substrate at a flow rate of 100 sccm for 5 seconds.

[0210] Next, the prepared precursor compound CpHf was placed in a separate canister and supplied to a separate vaporizer heated to 170°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. CpHf vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 2000 sccm for 6 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 1.5 Torr.

[0211] The temperature inside the chamber was maintained at 300°C during the deposition reaction.

[0212] The ALD process was performed in this manner until a thickness of 5 nm was formed.

[0213] Next, the prepared precursor compound CpZr was placed in a separate canister and supplied to a separate vaporizer heated to 170°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. The CpZr vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 2000 sccm for 6 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 1.5 Torr.

[0214] A pattern was formed using a photolithography process, and the lower Si was exposed through a dry etching process. The dry etching conditions were as follows: Source / bias power 350 / 100 W, CF4 / Ar gas flow rate 80 / 20 sccm, process pressure 5 mTorr, and etching time 45 s. After forming a 300 nm upper electrode using an E-beam evaporation deposition method (electrode area: 200 um × 200 um), the MIM device is shown in Fig. 3.

[0215] The difference in electrical characteristics depending on the use of a reactive species surface adsorbent was confirmed through IV and CV measurements.

[0216] *IV measurement of MIM devices: The voltage range was measured from 0 to 15 V and the leakage current and breakdown voltage values ​​were compared.

[0217] *CV measurement of MIM devices: The charge capacity and dielectric constant values ​​were compared under the conditions of frequency 1 MHz, voltage amplitude 100 mm, and voltage range -2 to 2 V.

[0218] Based on the above CV measurement results, the charge capacity (electrostatic capacity) and dielectric constant were extracted using the following mathematical formula 1.

[0219] [Mathematical Formula 1]

[0220]

[0221] (In the above equation, εr is the relative permittivity, Cox is the electrostatic capacitance, ε0 is the dielectric constant in vacuum, A is the area of ​​the plates, d is the distance between the plates, and F is the force applied to the conducting plates.)

[0222]

[0223] Example 3

[0224] 5N HI and NH3 were used as surface adsorption aids for the reactive species, and the ALD deposition process was performed using a precursor compound having the following chemical formula, BTBMMo.

[0225] [chemical formula]

[0226]

[0227] First, the substrate was placed in the deposition chamber, and then the prepared reactive species surface adsorption aid was supplied onto the substrate at a flow rate of 100 sccm for 5 seconds.

[0228] Next, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 150°C at a flow rate of 0.1 g / min using a Liquid Mass Flow Controller (LMFC) at room temperature. The BTBMMo precursor vaporized in the vaporizer was introduced into the deposition chamber for 3 seconds, and then argon gas was supplied at 3000 sccm for 10 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 2.5 Torr.

[0229] Then, after supplying NH3 reducing agent to the chamber at a flow rate of 1000 sccm, 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 at 2.5 Torr. The deposition temperature was maintained at 350°C, and this process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0230] The thickness of the thin film (MoN metal film) was measured using an ellipsometer, a device that can measure optical properties such as the thickness or refractive index of a thin film using the polarization characteristics of light. The thickness of the thin film deposited per cycle was calculated by dividing the thickness by the number of cycles, and the result was 10 nm. The thin film component analysis was performed using AES and SIMS. In addition, the sheet resistance was measured using the 4-probe measurement method, and the measured thickness was used to calculate the resistivity value.

[0231]

[0232] Comparative Example 1

[0233] The same process as in Example 1 was repeated, except that a process was used in which the reactive species was not pretreated with a surface adsorption aid.

[0234]

[0235] Comparative Example 2

[0236] A device was manufactured using the same process as in Example 2, except that a process was used in which no pretreatment with a reactive species surface adsorption aid was used.

[0237]

[0238] Comparative Example 3

[0239] The same process as Example 3 was repeated except that a process was used in which the reactive species was not pretreated with a surface adsorption aid.

[0240]

[0241] <Test Example 1: Comparison of film thickness by cycle number>

[0242] For each thin film of Example 1 and Comparative Example 1, the thin film thickness was calculated using the ellipsometry method, which is an optical thickness measurement method.

[0243] Specifically, the thickness of the thin film measured by an ellipsometer, a device that can measure optical properties such as the thickness or refractive index of a thin film using the polarization properties of light, was divided by the number of cycles to calculate the thickness of the thin film deposited per cycle, and the resulting value is shown in Figure 2 below.

[0244] The following Figure 2 is a graph confirming the deposition thickness per cycle of Example 1 of the present invention and Comparative Example 1 according to the prior art.

[0245] As shown in Fig. 2 below, in Example 1, which used a process in which a reactive species surface adsorption aid was pretreated, a result was confirmed in which thin film growth was promoted at the beginning of the 70th cycle of deposition, whereas in Comparative Example 1, which used a process in which a reactive species surface adsorption aid was not pretreated, no thin film thickness was observed even until almost 50 cycles were reached.

[0246] From these results, it was confirmed that the process of pretreatment with a reactive species surface adsorption aid provided the effect of increasing the film thickness by the number of cycles.

[0247]

[0248] <Test Example 2: Resistivity Comparison>

[0249] For each thin film of Example 1 and Comparative Example 1, the resistance was evaluated by converting the results obtained by the 4-probe measurement method into resistivity using the thickness value, and the results obtained are shown in Table 1 below.

[0250] Thickness (Å)Resistivity (μΩ·cm)Example 1Comparative Example 150300256100150100

[0251] As shown in Table 1 above, it was confirmed that the resistivity value was improved by thickness in Example 1, which used a process pretreated with a reactive species surface adsorption aid, compared to Comparative Example 1, which used a process not pretreated with a reactive species surface adsorption aid.

[0252] <Test Example 3: Comparison of Breakdown Voltage and Dielectric Constant>

[0253] The results obtained based on the IV and CV measurement methods for each thin film of Example 2 and Comparative Example 2 are shown in Table 2 below.

[0254] MIM device Average (average, HfZrO210 nm) Classification Mask method Electrode area (um) 2 )Leakage Current at 1 MV / cm(A / cm 2 )Breakdown Voltage(MV / cm)C OX (F) Dielectric constant comparison example 2 Photolithography process 200 × 200 1.00 E-076.38 2.09 E-105.91 Example 2 1.00 E-075.92 2.55 E-107.19

[0255] As shown in Table 2 above, it was confirmed that the dielectric constant was improved by more than 20% and the breakdown voltage was also improved by 0.46 MV / cm in Example 2 using the process utilizing the reactive species surface adsorption aid compared to Comparative Example 2 using the process without pretreatment with the reactive species surface adsorption aid. Consequently, it was confirmed that Example 2 using the process pretreated with the reactive species surface adsorption aid according to the present invention had an improved thin film density and improved crystallinity compared to Comparative Example 2, and thus had excellent electrical improvement characteristics such as the dielectric constant.

[0256]

[0257] <Test Example 4: Impurity Reduction Characteristics>

[0258] Thin film impurities were analyzed using Auger electron spectroscopy (AES).

[0259] Specifically, the type and content of elements constituting the material surface were analyzed by measuring the energy of the Auger electrons emitted by incidenting a focused electron beam onto the material surface.

[0260] Target Comparative Example 3 Example 3 Mo / N (AES) 1.3 0.9 C Impurity (AES) 280 O Impurity (AES) 910 Density (g / cm 3 )6.06.8SIMSC - 467624054CN - 109961177

[0261] As shown in Table 3 above, in Example 3 according to the present invention, it was confirmed through AES analysis that C impurities were reduced to 0% during thin film formation, and according to SIMS results, it was confirmed that the number of C ions detected was reduced by more than 91%. Furthermore, it can be seen that a very high-quality MoN thin film was formed, as the thin film density increased from 6.0 to 6.8.

[0262]

[0263] In conclusion, Example 1, which used a process pretreated with a reactive species surface adsorption aid according to the present invention, showed a significantly improved initial deposition rate compared to Comparative Example 1 that did not undergo the pretreatment, and not only was the film thickness deposited thicker per cycle, but also the resistivity improvement characteristic was excellent. Therefore, it was confirmed that by applying a predetermined reactive species surface adsorption aid as a pretreatment in an ALD process cycle according to the present invention, not only was the film thickness deposited thicker, but also the film quality could be improved, thereby providing a thin film required for a semiconductor device that requires improved resistivity.

Claims

1. As a surface adsorption aid for reactive species for metal precursors for thin films, A reactive species surface adsorption aid characterized in that the above reactive species surface adsorption aid is an iodine-containing compound.

2. In paragraph 1, The above reactive species surface adsorption assistant is an iodine-containing compound that promotes nucleation of reactive species by reducing the adsorption energy of the reactive species when a metal precursor is exposed to a substrate.

3. In paragraph 1, A reactive species surface adsorption aid, characterized in that the iodine-containing compound is at least one selected from hydrogen iodide, hydrogen iodide water, and a halide having an alkyl group having 4 to 15 carbon atoms.

4. In paragraph 3, A reactive species surface adsorption aid characterized in that the alkyl group having 4 to 15 carbon atoms is an iodine compound having a secondary benzyl, secondary allyl, tertiary benzyl, tertiary allyl, or tertiary alkyl structure.

5. In paragraph 1, The metal precursor is a reactive species surface adsorption aid characterized in that it is at least one selected from the group represented by the following chemical formulas (1) to (6): Chemical formula (1) = M x L y L' z (In the above chemical formula (1), x below is an integer of 1 to 3, M below can be selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn, y is an integer of 1 to 6, z is an integer of 0 to 6 (preferably 1 to 6), and L and L' are each independently A ligand composed of one or more combinations of H, C, N, O, F, P, S, Cl, Br or I, or a ligand composed of H, C, N, O, F, P, S, Cl and Br. Chemical formula (2) = (In the above chemical formula (2), M1 below is Zr, Hf, Si, Ge or Ti, and X1, X2, X3 below are independently -NR1R 2, -OR 3, or R4, and R1 to R4 are independently an alkyl group having 1 to 6 carbon atoms, and n is 1 or 2.) Chemical formula (3) = (In the above chemical formula (3), M is Zr, Hf, Si, Ge or Ti, R1 is independently hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 5, X'1, X'2 and X'3 are independently -NR'1R'2, -OR'3, or R'4, and R'1 to R'4 are independently an alkyl group having 1 to 6 carbon atoms.) Chemical formula (4) = M(O)n(X)m(L)k (In the above chemical formula (4), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo; O is oxygen, X is halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 0 to 3.) Chemical formula (5) = MXaY(6-a)Zb (In the above chemical formula (5), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo; X is a halogen element; Y is an amine series or an alkoxy series; a is an integer of 1 to 6; Z is selected from the group consisting of an alkyl cyanide having 1 to 15 carbon atoms, or a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); and b is an integer of 0 to 5.) Chemical formula (6) = ML1L2L3L4(L5)h(L6)i (In the above chemical formula (6), M is at least one selected from the group consisting of Co, Ni, Ru, Ti, Ta, Nb, W, Cu, Ru, and Mo, L1, L2, L3, L4, L5, and L6 are independently H; F; Cl; Br; I; NRaRb; ORc; CO; RdCp; amidinate; guadiinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbons substituted with one or more carbons (C), nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); Cp is cyclopentadienyl, Ra, Rb, Rc, and Rd are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and I are independently 0 or 1, and the overall oxidation number of the compound is an integer of -2 to 6.) 6. In paragraph 1, A reactive species surface adsorption aid characterized in that the above thin film is a laminated film of at least one selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Pt, At and Tn.

7. In paragraph 1, The above thin film is a reactive species surface adsorption aid characterized in that the nitride film, metal film, oxide film or a selective thin film thereof is formed on the entire substrate or a portion of the substrate.

8. A thin film characterized by being formed by applying the surface adsorption aid of the reactive species of clause 1 before injection of the metal precursor.

9. In paragraph 8, A thin film characterized in that the above thin film is a dielectric film, wiring or barrier metal.

10. In paragraph 8, A thin film characterized in that the above thin film exhibits an initial deposition rate of 0.1 to 1.5 Å / cycle, wherein the initial deposition is 1 to 70 cycles.

11. In paragraph 8, The above thin film is characterized in that the resistivity value is 0.1 to 1,000 μΩcm based on a thin film thickness of 50 nm, and the resistivity value is 0.1 to 500 μΩcm based on a thin film thickness of 100 nm.

12. A step of forming a seed layer by exposing the surface adsorption aid of the reactive species of the third clause to the substrate; A step of loading the substrate into a chamber and exposing the seed layer to a metal precursor to form a surface adsorption layer of a reactive species; and A method for forming a thin film, characterized by comprising a step of forming a reaction species adsorption layer by exposing the reaction species surface adsorption layer to a reaction gas.

13. A semiconductor substrate characterized by including the thin film of clause 8.

14. A semiconductor device characterized by including a semiconductor substrate according to claim 13.

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