Method for forming thin film

Abstract

This invention relates to an activator, a thin film formation method using the same, a semiconductor substrate and a semiconductor device manufactured therefrom. By providing a compound with a predetermined structure as an activator, the activator effectively replaces the ligand in the adsorbed precursor to improve the reaction rate and appropriately reduce the thin film growth rate. Thus, even when forming a thin film on a substrate with a complex structure, it can significantly improve the step coverage and the thickness uniformity of the thin film, and also has the effect of reducing impurities.

Description

Technical Field

[0001] This invention relates to an activator, a thin film formation method using the same, a semiconductor substrate and a semiconductor device manufactured therefrom. Specifically, it utilizes a compound with a predetermined structure as an activator to effectively replace ligands in a precursor adsorbed on a substrate, thereby improving the reaction rate and appropriately reducing the thin film growth rate. This allows for significant improvement in step coverage and film thickness uniformity, and substantial reduction in impurities, even when forming thin films on substrates with complex structures. Prior Technology

[0002] Thin films formed by the atomic layer deposition (ALD) process in the prior art cannot be adequately removed during the deposition process, leaving ligands in the precursor compound that remain in the grown film. As a result, contamination occurs when impurities flow into the film.

[0003] That is, when a thin film is formed in the horizontal direction due to the refinement of semiconductor devices, impurities from ligands (C, Cl-, F-, etc.) in the thin film can disrupt the crystal arrangement, thereby reducing the density of the formed thin film.

[0004] This low density may cause problems with reduced conductivity, and due to the refinement and stacking of semiconductor devices, the use of substrates including deeper via holes or trenches is increasing.

[0005] When a thin film is formed by filling a cylindrical hole pattern or groove or along the inner wall in the vertical direction, there is a step coverage that makes it difficult to make the thickness of the film formed on the upper part of the pattern uniform with the thickness of the film formed on the lower part of the groove, which is close to 100%.

[0006] As a specific example, referring to the prior literature J. Vac. Sci. Technol. A 37, 060904 (2019), it is disclosed that aminosilane precursors cannot be nitrided by NH3, therefore, a technique for nitriding using NH3 plasma and N2 plasma is employed.

[0007] However, even when plasma is applied to substrates with narrow and deep hole patterns, the plasma can only reach the upper part of the substrate to form a nitride film. The plasma-generated N free radicals have a short lifetime and therefore cannot reach the interior of the holes, thus failing to form a nitride film.

[0008] Therefore, there is a need to develop a method for forming thin films that can effectively remove ligands from precursor compounds injected during deposition, form complex thin films with low impurity residues, and significantly improve step coverage and film thickness uniformity, as well as semiconductor substrates manufactured thereby. Summary of the Invention

[0009] [Technical Issues] In order to solve the technical problems in the prior art as described above, the object of the present invention is to provide an activator, a thin film formation method thereon, and a semiconductor substrate thereby manufactured, which effectively replaces the ligand in the adsorbed precursor by providing a compound with a predetermined structure as an activator to improve the reaction rate and appropriately reduce the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when forming a thin film on a substrate with a complex structure.

[0010] The purpose of this invention is to improve the crystallinity and oxidation content of thin films, thereby improving the density, electrical properties and dielectric properties of the thin films.

[0011] The above-mentioned objectives and other objectives of the present invention can all be achieved by the present invention as described below. [Technical Solution]

[0012] To achieve the above objectives, an activator is provided comprising a halogen compound, wherein the halogen compound is used to replace a ligand contained in a precursor compound represented by chemical formula 1.

[0013] [Chemical Formula 1] In the aforementioned chemical formula 1, M is selected from one or more of 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, Ir, La, Ce, and Nd. L1, L2, L3, and L4 can be -H, -X, -R, -OR, or -NR2 and may be the same as or different from each other. Among them, -X is F, Cl, Br, or I, and -R can be a C1-C10 alkyl, C2-C10 alkenyl, or C2-C10 alkynyl and may be linear or cyclic. The aforementioned L1, L2, L3, and L4 may be formed with n values ​​of 2 to 6 depending on the oxidation valence of the central metal.

[0014] As an example, when the central metal is divalent, L1 and L2 can bind to the central metal as ligands. When the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 can bind to the central metal. The ligands corresponding to L1 to L6 can be the same or different from each other.

[0015] In the aforementioned chemical formula 1, L1, L2, L3 and L4 can be -H or -R and can be the same as or different from each other. Among them, -R can be a C1~C10 alkyl, C2~C10 alkenyl or C2~C10 alkynyl and can be linear or cyclic.

[0016] In the aforementioned chemical formula 1, L1, L2, L3 and L4 can be -H, -OR or -NR2 and may be the same as or different from each other, wherein -R can be H, C1~C10 alkyl, C2~C10 alkenyl, C2~C10 alkynyl, iPr or tBu.

[0017] In the aforementioned chemical formula 1, L1, L2, L3, and L4 can be -H or -X and may be the same as or different from each other, wherein -X can be F, Cl, Br, or I.

[0018] The aforementioned halogen compound may be selected from one or more of hydrogen iodide, hydrogen iodide water, iodomethane, iodoethane, iodopropane, iodobutane, iodoisopropane, and iodotert-butane.

[0019] The aforementioned activator may be a pure hydrogen iodide of 3N to 15N, or a gaseous mixture of 1 to 99% by weight of hydrogen iodide of 3N to 15N and an inert gas with a balance of 100% by weight, or an aqueous mixture of 0.5 to 70% by weight of hydrogen iodide of 3N to 15N and water with a balance of 100% by weight, wherein the inert gas is nitrogen, helium, or argon with a purity of 4N to 9N.

[0020] The deposition rate increase of the aforementioned activator, as represented by mathematical formula 1, can be more than 10%.

[0021] [Mathematical Expression 1] The rate of increase in deposition rate (DR) = [{(DRi) - (DRf)} / (DRi)] × 100 In this formula, DR (Deposition rate, Å / cycle) is the deposition rate of the thin film. When depositing a thin film formed from precursors and reactants, DRi (initial deposition rate) is the deposition rate of the film without the addition of an activator. DRf (final deposition rate) is the deposition rate of the film with the addition of an activator during the above process. The deposition rate (DR) is the value of a 3-30 nm thick film measured using an ellipsometer under ambient temperature and pressure conditions, and the unit is Å / cycle.

[0022] In the aforementioned mathematical formula 1, with or without the use of an activator, the film growth rate per cycle represents the film deposition thickness (Å / cycle) per cycle, i.e., the deposition rate. For example, the aforementioned deposition rate can be obtained by dividing the final thickness of a film with a thickness of 3 to 30 nm measured by an ellipsometry under normal temperature and pressure conditions by the total number of cycles.

[0023] The refractive index of the aforementioned activator can be above 1.40, 1.42 to 1.50, 1.43 to 1.48, or 1.44 to 1.48.

[0024] The aforementioned activator can provide replacement regions for oxide films, nitride films, metal films, or selective films thereof.

[0025] The aforementioned replacement region can be formed on the entire substrate or a portion of the substrate on which the aforementioned oxide film, nitride film, metal film or selective thin film thereof is to be formed.

[0026] When the total area of ​​the entire substrate or a portion of the substrate is set to 100%, the ligand adsorption region can occupy 10% to 95% of the area, and the ligand-unadsorbed region can occupy the remaining area.

[0027] When the total area of ​​the entire substrate or a portion of the substrate is set to 100%, the first ligand adsorption region can occupy 10% to 95% of the area, the second ligand adsorption region can occupy 10% to 95% of the remaining area, and the ligand-unadsorbed region can occupy the remaining area.

[0028] The aforementioned activator activates a laminated film formed from one or more precursor compounds selected from 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, Ir, La, Ce, and Nd.

[0029] The aforementioned activator can be used for the formation of anti-diffusion films, etch stop films, electrode films, dielectric films, gate insulating films, bulk oxide films, or thin films for charge trapping.

[0030] In addition, the present invention provides a thin film forming method, which includes the following steps: injecting the above-mentioned activator into a chamber to replace the ligand in the precursor compound adsorbed on the surface of the loaded substrate.

[0031] In addition, the present invention provides a thin film forming method, which includes the following steps: Step (1-i) involves vaporizing the aforementioned activator to replace the ligand in the precursor compound, wherein the precursor compound is adsorbed onto the surface of the substrate loaded within the chamber; Step (1-ii) involves first purging the interior of the aforementioned chamber using purging gas; Step (1-iii) vaporizes the precursor compound and causes it to adsorb onto the region where the substitution region has been removed; Step (1-iv) involves a second purging of the interior of the aforementioned chamber using purging gas; Step (1-v) involves supplying the reactant gas into the aforementioned chamber; and Step (1-vi) involves a third purging of the interior of the aforementioned chamber using purging gas.

[0032] In addition, the present invention provides a thin film forming method, which includes the following steps: Step (2-i) vaporizes the precursor compound and adsorbs it onto the surface of the substrate loaded in the chamber; Step (2-ii) involves first purging the interior of the aforementioned chamber using purging gas; Step (2-iii) involves vaporizing the aforementioned activator to replace the ligand in the precursor compound, wherein the aforementioned precursor compound is adsorbed onto the surface of the substrate loaded within the chamber; Step (2-iv) involves a second purging of the interior of the aforementioned chamber using purging gas; Step (2-v) involves supplying the reactant gas into the aforementioned chamber; and Step (2-vi) involves a third purging of the interior of the aforementioned chamber using purging gas.

[0033] The aforementioned precursor compound, as a molecule formed from one or more of 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, Ir, La, Ce, and Nd, can be a precursor with a vapor pressure greater than 0.01 mTorr and less than or equal to 100 Torr at 25 °C.

[0034] The aforementioned chamber can be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

[0035] The process may include the following steps: after vaporizing and injecting the aforementioned activator or precursor compound, performing plasma post-treatment.

[0036] The amount of purge gas introduced into the chamber in steps (1-ii) and (1-iv) as well as steps (2-ii) and (2-iv) can be 10 to 100,000 times the volume of the activator introduced.

[0037] The aforementioned reactant gas is an oxidizing agent, nitriding agent, or reducing agent. The aforementioned reactant gas, activator, and precursor compound can be delivered into the chamber by gas flow control (VFC), direct liquid injection (DLI), or liquid transfer system (LDS).

[0038] The aforementioned thin film may be a molybdenum film, tungsten film, silicon nitride film, silicon oxide film, titanium nitride film, titanium oxide film, tungsten nitride film, molybdenum nitride film, hafnium oxide film, zirconium oxide film, tungsten oxide film, or aluminum oxide film.

[0039] The substrate loaded in the chamber is heated to 100°C to 800°C, and the ratio of the amount of the activator to the amount of the precursor compound added in the chamber (mg / cycle) can be 1:1 to 1:20.

[0040] In addition, the present invention provides a semiconductor substrate manufactured by the above-described thin film formation method.

[0041] The aforementioned film can be a multilayer structure with two or three layers.

[0042] In addition, the present invention provides a semiconductor device comprising the semiconductor substrate described above.

[0043] The aforementioned semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal capacitors, DRAM trench capacitors, 3D gate-all-around (GAA) or 3D NAND flash memory. [Beneficial Effects]

[0044] According to the present invention, an activator is provided that effectively replaces ligands in precursors adsorbed on a substrate to improve reaction rate and appropriately increase film growth rate, thereby improving film productivity.

[0045] In addition, during film formation, process byproducts are reduced more effectively to prevent corrosion and degradation, and the crystallinity of the film is improved, thereby improving the film's roughness, dielectric constant, and electrical properties.

[0046] Furthermore, it can improve the step coverage and density of thin films, and further provides a thin film formation method using it and a semiconductor substrate manufactured therefrom. Simple Explanation of the Diagram

[0047] Figure 1 is a diagram that schematically illustrates the deposition process sequence of the present invention in one cycle.

[0048] Figure 2 is a graph comparing the deposition rate increase rate in Examples 1 to 3 using the activator of the present invention with that in Comparative Examples 1 to 3 of the prior art without the activator. Implementation

[0049] The activator of the present invention, the thin film formation method thereunder, and the semiconductor substrate therefrom shall be described in detail below.

[0050] The inventors of this invention have identified a compound capable of replacing the ligand in the precursor compound as an activator. This activator improves the reaction rate based on its activation energy reduction mechanism and ensures film uniformity even when applied to substrates with complex structures, thereby significantly improving step coverage. In particular, it enables deposition at a thinner thickness and reduces the amount of residual O, Si, metals, metal oxides, and previously difficult-to-reduce residual carbon, which are process byproducts. The aforementioned precursor compound is adsorbed onto the surface of the substrate loaded inside the chamber to form a film. Based on this, the activator was studied, leading to the completion of this invention.

[0051] As an example, the aforementioned thin film can be provided by one or more precursors selected from 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, Ir, La, Ce, and Nd, which can provide an oxide film, a nitride film, or a metal film. In this case, the effects to be achieved by the present invention can be fully obtained.

[0052] As a specific example, the aforementioned thin film may have a film composition of molybdenum film, tungsten film, silicon nitride film, silicon oxide film, titanium nitride film, titanium oxide film, tungsten nitride film, molybdenum nitride film, hafnium oxide film, zirconium oxide film, tungsten oxide film, or aluminum oxide film.

[0053] The aforementioned thin film may contain the above-described film composition in the form of a single or selective area, but is not limited thereto, and also indicates the inclusion of SiH and SiOH.

[0054] The aforementioned thin film can be used not only as a commonly used anti-diffusion film, but also as an etch stop film, electrode film, dielectric film, gate insulating film, bulk oxide film, or charge trap in semiconductor devices.

[0055] In this invention, the precursor compound used to form the thin film is a molecule with 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, Ir, La, Ce, and Nd as the central metal atom (M) and having one or more ligands composed of C, N, O, H, and X (halogens). When it is a precursor with a vapor pressure of 1 mTorr to 100 Torr at 25°C, the effect of being replaced by the activator described later can be maximized.

[0056] As an example, the aforementioned precursor compound may be a compound represented by chemical formula 1.

[0057] [Chemical Formula 1] In the aforementioned chemical formula 1, M is selected from one or more of 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, Ir, La, Ce, and Nd. L1, L2, L3, and L4 can be -H, -X, -R, -OR, or -NR2 and may be the same as or different from each other. Among them, -X is F, Cl, Br, or I, and -R can be a C1-C10 alkyl, C2-C10 alkenyl, or C2-C10 alkynyl and may be linear or cyclic. The aforementioned L1, L2, L3, and L4 may be formed with n values ​​of 2 to 6 depending on the oxidation valence of the central metal (M).

[0058] As an example, when the central metal is divalent, L1 and L2 can bind to the central metal as ligands. When the central metal is hexavalent, L1, L2, L3, L4, L5, and L6 can bind to the central metal. The ligands corresponding to L1 to L6 can be the same or different from each other.

[0059] In the aforementioned chemical formula 1, M is hafnium (Hf), silicon (Si), zirconium (Zr) or aluminum (Al), preferably hafnium (Hf) or silicon (Si). In this case, the reduction of process by-products is significant, the step coverage is excellent, and it has the advantages of improved film density, better electrical properties, insulation and dielectric properties of the film.

[0060] The aforementioned L1, L2, L3, and L4 can be -H or -R and may be the same as or different from each other. Among them, -R can be a C1~C10 alkyl, C2~C10 alkenyl, or C2~C10 alkynyl and have a linear or cyclic structure, in which case it has a suitable reaction energy to be substituted by the activator described later.

[0061] In addition, the aforementioned L1, L2, L3 and L4 can be -H, -OR or -NR2 and may be the same as or different from each other. Among them, -R can be H, C1~C10 alkyl, C2~C10 alkenyl, C2~C10 alkynyl, iPr or tBu, in which case it has a suitable reaction energy to be substituted by the activator described later.

[0062] In addition, in the aforementioned chemical formula 1, L1, L2, L3 and L4 can be -H or -X and can be the same as or different from each other, wherein -X can be F, Cl, Br or I, in which case there is a suitable reaction energy to be substituted by an activator described later.

[0063] Specifically, the silicon precursor compound can be selected from, for example, SiH4, SiHCl3, SiH2Cl2, SiCl4, Si2Cl6, Si3Cl8, Si4Cl10, SiH2[NH(C4H9)]2, Si2(NHC2H5)4, Si3NH4(CH3)3, SiH3[N(CH3)2], SiH2[N(CH3)2]2, SiH[N(CH3)2]3, Si[N(CH3)2]4, tetraethyl orthosilicate (TEOS; Si(OC2H5)4), diisopropylamino silane ([Di-isopropylamino... Silane;DIPAS;H3Si[N{(CH)(CH3)2}]), BTBAS, (NH2)Si(NHMe)3, (NH2)Si(NHEt)3, (NH2)Si(NHnPr)3, (NH2)Si( NHiPr)3, (NH2)Si(NHnBu)3, (NH2)Si(NHiBu)3, (NH2)Si(NHtBu)3, (NMe2)Si(NHMe)3, (NMe2)Si(NHEt)3, (NMe2)S i(NHnPr)3, (NMe2)Si(NHiPr)3, (NMe2)Si(NHnBu)3, (NMe2)Si(NHiBu)3, (NMe2)Si(NHtBu)3, (NEt2)Si(NHMe)3, (NEt2)Si(NHEt)3, (NEt2)Si(NHnPr)3, (NEt2)Si(NHiPr)3, (NEt2)Si(NHnBu)3, (NEt2)Si(NHiBu)3, (NEt2)Si(NH tBu)3, (NnPr2)Si(NHMe)3, (NnPr2)Si(NHEt)3, (NnPr2)Si(NHnPr)3, (NnPr2)Si(NHiPr)3, (NnPr2)Si(NHnBu)3, (NnPr2)Si(NHiBu)3, (NnPr2)Si(NHtBu)3, (NiPr2)Si(NHMe)3, (NiPr2)Si(NHEt)3, (NiPr2)Si(NHnPr)3, (NiPr2) Si(NHiPr)3, (NiPr2)Si(NHnBu)3, (NiPr2)Si(NHiBu)3, (NiPr2)Si(NHtBu)3, (NnBu2)Si(NHMe)3, (NnBu2)Si(NH Et)3, (NnBu2)Si(NHnPr)3, (NnBu2)Si(NHiPr)3, (NnBu2)Si(NHnBu)3, (NnBu2)Si(NHiBu)3, (NnBu2)Si(NHtBu)3,(NiBu2)Si(NHMe)3、(NiBu2)Si(NHEt)3、(NiBu2)Si(NHnPr)3、(NiBu2)Si(NHiPr)3、(NiBu2)Si(NHnBu)3、(NiBu2)Si(NHiBu)3、(NiBu2)Si(NHtBu)3、(NtBu2)Si(NHMe)3、(NtBu2)Si(NHEt)3、(NtBu2)Si(NHnPr)3、(NtBu2)Si(NHiPr)3、(NtBu2)Si(NHnBu)3、(NtBu2)Si(NHiBu)3、(NtBu2)Si(NHtBu) 3, (NH2)2Si(NHMe)2, (NH2)2Si(NHEt)2, (NH2)2Si(NHnPr)2, (NH2)2Si(NHiPr)2, (NH2)2Si(NHnBu)2, (NH2)2Si(NHiBu)2, (NH2)2Si(NHtBu)2, (NMe2)2Si(NHMe)2, (NMe2)2Si(NHEt)2, (NMe2)2Si(NHnPr)2, (NMe2)2Si(NHiPr)2, (NMe2)2Si(NHnBu)2, (NMe2)2Si(NHiBu)2, (NMe2)2Si(NHtBu)2, (NEt 2)2Si(NHMe)2,(NEt2)2Si(NHEt)2,(NEt2)2Si(NHnPr)2,(NEt2)2Si(NHiPr)2,(NEt2)2Si(NHnBu)2,(NEt2)2Si(NHiBu)2,(NEt2)2Si(NHtBu)2,(NnPr2)2Si(NHMe)2,(NnPr2)2Si(NHEt)2,(NnPr2)2Si(NHnPr)2,(NnPr2)2Si(NHnPr)2,(NnPr2)2Si(NHiPr)2,(NnPr2)2Si(NHiBu)2,(NnPr2)2Si(NHtB u)2,(NiPr2)2Si(NHMe)2,(NiPr2)2Si(NHEt)2,(NiPr2)2Si(NHnPr)2,(NiPr2)2Si(NHiPr)2,(NiPr2)2Si(NHnBu)2,(NiPr2)2Si(NHiBu)2,(NiPr2)2Si(NHtBu)2,(NnBu2)2Si(NHMe)2,(NnBu2)2Si(NHEt)2,(NnBu2)2Si(NHnPr)2,(NnBu2)2Si(NHiPr)2,(NnBu2)2Si(NHnBu)2,(NnBu2)2Si(NHiBu)2,(NnBu2)2Si(NHiBu)2,(NnBu2)2Si(NHtBu)2、(NiBu2)2Si(NHMe)2、(NiBu2)2Si(NHEt)2、(NiBu2)2Si(NHnPr)2、(NiBu2)2Si(NHiPr)2、(NiBu2)2Si(NHnBu)2、(NiBu2)2Si(NHiBu)2、(NiBu2)2Si(NHtBu)2、(NtBu2)2Si(NHMe)2、(NtBu2)2Si(NHEt)2、(NtBu2)2Si(NHnPr)2、(NtBu2)2Si(NHiPr)2、(NtBu2)2Si(NHnBu)2、(NtBu2 )2Si(NHiBu)2、(NtBu2)2Si(NHtBu)2、Si(HNCH2CH2NH)2、Si(MeNCH2CH2NMe)2、Si(EtNCH2CH2NEt)2、Si(nPrNCH2CH2NnPr)2、Si(iPrNCH2CH2NiPr)2、S i(nBuNCH2CH2NnBu)2、Si(iBuNCH2CH2NiBu)2、Si(tBuNCH2CH2NtBu)2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNCHCHNEt)2、Si(nPrNCHCHNnPr)2、Si (iPrNCHCHNiPr)2、Si(nBuNCHCHNnBu)2、Si(iBuNCHCHNiBu)2、Si(tBuNCHCHNtBu)2、(HNCHCHNH)Si(HNCH2CH2NH)、(MeNCHCHNMe)Si(MeNCH2CH2NMe)、 (EtNCHCHNEt)Si(EtNCH2CH2NEt)、(nPrNCHCHNnPr)Si(nPrNCH2CH2NnPr)、(iPrNCHCHNiPr)Si(iPrNCH2CH2NiPr)、(nBuNCHCHNnBu)Si(nBuNCH2CH2NnB u)、(iBuNCHCHNiBu)Si(iBuNCH2CH2NiBu)、(tBuNCHCHNtBu)Si(tBuNCH2CH2NtBu)、(NHtBu)2Si(HNCH2CH2NH)、(NHtBu)2Si(MeNCH2CH2NMe)、(NHtBu)2 Si(EtNCH2CH2NEt)、(NHtBu)2Si(nPrNCH2CH2NnPr)、(NHtBu)2Si(iPrNCH2CH2NiPr)、(NHtBu)2Si(nBuNCH2CH2NnBu)、(NHtBu)2Si(iBuNCH2CH2NiBu)、(NHtBu)2Si(tBuNCH2CH2NtBu), (NHtBu)2Si(HNCHCHNH), (NHtBu)2Si(MeNCHCHNMe), (NHtBu)2Si(EtNCHCHNEt), (NHtBu)2Si(nPrNCHCHNnPr), (NHtBu)2Si(iPrNCHCHNiPr), (NHtBu)2 Si(nBuNCHCHNnBu), (NHtBu)2Si(iBuNCHCHNiBu), (NHtBu)2Si(tBuNCHCHNtBu), (iPrNCH2CH2NiPr)Si(NHMe)2, (iPrNCH2CH2NiPr)Si(NHEt)2, (iPrNCH2CH2NiPr)Si(NHnPr)2, (iPrNC One or more of the following reactions are given: H₂CH₂NiPr)Si(NHiPr)₂, (iPrNCH₂CH₂NiPr)Si(NHnBu)₂, (iPrNCH₂CH₂NiPr)Si(NHiBu)₂, (iPrNCH₂CH₂NiPr)Si(NHtBu)₂, (iPrNCHCHNiPr)Si(NHMe)₂, (iPrNCHCHNiPr)Si(NHEt)₂, (iPrNCHCHNiPr)Si(NHnPr)₂, (iPrNCHCHNiPr)Si(NHiPr)₂, (iPrNCHCHNiPr)Si(NHnBu)₂, (iPrNCHCHNiPr)Si(NHiBu)₂, and (iPrNCHCHNiPr)Si(NHtBu)₂, wherein a suitable reaction energy is available for substitution by an activator described later.

[0064] Alternatively, tris(dimethylamino)cyclopentadienyl tigrin (CpHf(NMe2)3) and (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino) tigrin (Cp(CH2)3NM3Hf(NMe2)2) can be used as precursor compounds, which have suitable reaction energies for substitution by the activator described later.

[0065] The activator of this invention can reduce the activation energy of the precursor compound adsorbed on the substrate, thereby effectively replacing the ligands in the precursor compound. That is, it is preferable to use a compound that can provide substitution regions for the ligands in the precursor compound adsorbed on the substrate.

[0066] As an example, the aforementioned replacement regions can be formed on the entire substrate or a portion of the substrate on which the aforementioned thin film is to be formed.

[0067] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate is set to 100%, for example, the aforementioned replaced area can occupy 10% to 95% of the area, for a specific example, it can occupy 15% to 90% of the area, more preferably, it can occupy 20% to 85% of the area, more preferably, it can occupy 30% to 80% of the area, even more preferably, it can occupy 40% to 75% of the area, and even more preferably, it can occupy 40% to 70% of the area, while the unreplaced area can occupy the remaining area.

[0068] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate is set to 100%, the first substituted region can occupy 10% to 95% of the area, specifically, 15% to 90% of the area, more preferably, 20% to 85% of the area, more preferably, 30% to 80% of the area, even more preferably, 40% to 75% of the area, and even more preferably, 40% to 70% of the area. The second substituted region can occupy 10% to 95% of the remaining area, specifically, 15% to 90% of the area, more preferably, 20% to 85% of the area, more preferably, 30% to 80% of the area, even more preferably, 40% to 75% of the area, and even more preferably, 40% to 70% of the area. The unsubstituted region can occupy the remaining area.

[0069] The aforementioned activator is selected from hydrogen iodide, hydrogen iodide water, iodomethane, iodoethane, iodopropane, iodobutane, iodoisopropane, and iodotert-butane. At this time, by forming ligand substitution regions that do not remain in the film during film formation, side reactions can be suppressed while forming a relatively sparse film, and the film growth rate can be adjusted to reduce process by-products in the film, thereby reducing corrosion and degradation and improving the crystallinity of the film. When forming a metal oxide film, a stoichiometric oxidation state is achieved. Even when forming a film on a substrate with a complex structure, the step coverage and film thickness uniformity can be significantly improved.

[0070] As a specific example, the aforementioned activator is a pure hydrogen iodide of 3N to 15N, or a gas mixture of 1 to 99 wt% hydrogen iodide of 3N to 15N and an inert gas with the balance of 100 wt%, or an aqueous mixture of 0.5 to 70 wt% hydrogen iodide of 3N to 15N and water with the balance of 100 wt%. When the inert gas is nitrogen, helium, or argon with a purity of 4N to 9N, the reduction of process byproducts is significant, the step coverage is excellent, and the film density improvement and the electrical properties of the film are even better.

[0071] Preferably, the aforementioned activator can be a pure 5N-6N hydrogen iodide, or a gas mixture of 1-99 wt% 5N-6N hydrogen iodide and an inert gas with a total balance of 100 wt%, or an aqueous mixture of 0.5-70 wt% 5N-6N hydrogen iodide and water with a total balance of 100 wt%. The inert gas can be nitrogen, helium, or argon with a purity of 4N-9N. In this case, by forming substitution regions that do not remain in the film during film formation, side reactions can be suppressed while forming a relatively sparse film, and the film growth rate can be adjusted to reduce process by-products in the film, thereby reducing corrosion and degradation, improving the crystallinity of the film, and significantly improving step coverage and film thickness uniformity even when forming films on substrates with complex structures.

[0072] The aforementioned activator is preferably a pure 5N-6N hydrogen iodide, a gaseous mixture of 1-99 wt% 5N-6N hydrogen iodide and an inert gas with a balance of 100 wt%, or an aqueous mixture of 0.5-70 wt% 5N-6N hydrogen iodide and water with a balance of 100 wt%. The inert gas can be a compound of nitrogen, helium, or argon with a purity of 4N-9N, and its deposition rate increase, as expressed by Formula 1, can be 9% or more (deposition rate (DR) of 0.09 Å / cycle or more). Specifically, it can be 9%-25% (DR of 0.09 Å / cycle). The concentration of 9% to 0.25 Å / cycle is preferably 9% to 15% (DR is 0.09 to 0.15 Å / cycle). In this case, a uniformly thick deposited layer is formed based on the activator with the above structure as a replacement region that does not remain on the film. This results in a relatively sparse film while significantly reducing the growth rate of the film. Therefore, even when applied to substrates with complex structures, the uniformity of the film can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of residual O, Si, metal, metal oxides, and residual carbon that is difficult to reduce in the past, which are process byproducts.

[0073] [Mathematical Expression 1] The rate of increase in deposition rate (DR) = [{(DRi) - (DRf)} / (DRi)] × 100 In this formula, DR (Deposition rate, Å / cycle) is the deposition rate of the thin film. When depositing a thin film formed from precursors and reactants, DRi (initial deposition rate) is the deposition rate of the film without the addition of an activator. DRf (final deposition rate) is the deposition rate of the film with the addition of an activator during the above process. The deposition rate (DR) is the value of a 3-30 nm thick film measured using an ellipsometer under ambient temperature and pressure conditions, and the unit is Å / cycle.

[0074] In the aforementioned mathematical formula 1, with or without the use of an activator, the film growth rate per cycle represents the film deposition thickness (Å / cycle) per cycle, i.e., the deposition rate. For example, the aforementioned deposition rate can be obtained by dividing the final thickness of a film with a thickness of 3 to 30 nm measured by an ellipsometry under normal temperature and pressure conditions by the total number of cycles.

[0075] In the aforementioned mathematical formula 1, "when no activator is used" means that the thin film is manufactured in the thin film deposition process by adsorbing only the precursor compound on the substrate. As a specific example, it refers to the case in which the step of adsorbing the activator and the step of purging the unadsorbed activator are omitted in the aforementioned thin film formation method.

[0076] As an example, when the aforementioned activator is a hydrogen iodide compound, it can be a compound with a refractive index in the range of 1.4 to 1.42 or 1.43 to 1.5. As a specific example, it is 1.41 to 1.417 or 1.43 to 1.47, and preferably a compound in the range of 1.413 to 1.417 or 1.450 to 1.452.

[0077] At this point, the activation energy required for the ligand substitution reaction of the activator having the above-mentioned structure on the substrate is reduced. Appropriately substituting the ligands in the precursor compounds adsorbed on the substrate improves the reaction rate. Even when forming a thin film on a substrate with a complex structure, it can significantly improve step coverage and film thickness uniformity. Moreover, it prevents the adsorption of film precursors and process byproducts, thereby effectively protecting the surface of the substrate and effectively removing process byproducts.

[0078] In particular, while forming relatively sparse films, the growth rate of the formed films is greatly reduced. Therefore, even when applied to substrates with complex structures, the uniformity of the films can be ensured, thereby greatly improving the step coverage. In particular, it can be deposited with a thinner thickness and improve the amount of residual O, Si, metals, metal oxides, and carbon that were previously difficult to reduce as process byproducts.

[0079] The aforementioned film is replaced by a region that does not remain on the aforementioned film.

[0080] At this point, unless otherwise defined, "no residue" means that when analyzing the components by XPS, the carbon content is 0.1 atomic percent (A%), the silicon content is less than 0.1 A%), the nitrogen content is less than 0.1 A%), and the halogen content is less than 0.1 A%). More preferably, in secondary-ion mass spectrometry (SIMS) or X-ray photoelectron spectroscopy (XPS) measurements performed by digging into the substrate along the depth direction, when considering the increase or decrease rates of C, N, Si, and halogen impurities before and after using the activator under the same deposition conditions, the increase or decrease rate of the signal intensity of each element species is preferably less than 5%.

[0081] As an example, the content of halogen compounds in the aforementioned film can be less than 100 ppm.

[0082] The aforementioned thin film can be used as an etch stop film, electrode film, dielectric film, gate insulating film, bulk oxide film, or charge trap, but is not limited thereto.

[0083] Preferably, the aforementioned activator can be a compound with a purity of 99.9% or higher, a purity of 99.95% or higher, or a purity of 99.99% or higher. For reference, when using a compound with a purity of less than 99%, impurities may remain in the film or cause side reactions with precursors or reactants. Therefore, substances with a purity of 99% or higher should be used whenever possible.

[0084] Preferably, the aforementioned activator is used in the atomic layer deposition (ALD) process. In this case, while not hindering the adsorption of precursor compounds, it effectively protects the surface of the substrate as an activator and has the advantage of effectively removing process byproducts.

[0085] Preferably, the density of the aforementioned activator can be 0.8~2.5 g / cm3 or 0.8~1.5 g / cm3, and the vapor pressure (20°C) can be 0.1~300 mmHg or 1~300 mmHg. Within this range, it has the effect of effectively forming substitution regions and improving the step coverage, film thickness uniformity, and film quality.

[0086] More preferably, the density of the aforementioned activator can be 0.75~2.0 g / cm3 or 0.8~1.3 g / cm3, and the vapor pressure (20°C) can be 1~260 mmHg. Within this range, it has the effect of effectively forming substitution regions and improving the step coverage, film thickness uniformity, and film quality.

[0087] The thin film formation method of the present invention includes the following steps: injecting the above-mentioned activator into a chamber to replace the ligand in the precursor compound, wherein the aforementioned precursor compound is adsorbed on the surface of the loaded substrate. At this time, the ligand in the precursor adsorbed on the substrate is effectively replaced to improve the reaction rate and appropriately reduce the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when forming a thin film on a substrate with a complex structure.

[0088] In the step of adsorbing the aforementioned activator onto the surface of the substrate, the feeding time (sec) of the activator on the substrate surface per cycle is preferably 0.01 to 5 seconds, more preferably 0.02 to 3 seconds, even more preferably 0.04 to 2 seconds, and even more preferably 0.05 to 1 second. Within this range, it has the advantages of low film growth rate, excellent step coverage, and good economy.

[0089] In this invention, the feeding time of the precursor compound is based on a flow rate of 0.1 to 50 mg / cycle, with a chamber volume of 15 to 20 L. More specifically, it is based on a flow rate of 0.8 to 20 mg / cycle with a chamber volume of 18 L.

[0090] As a preferred embodiment, the aforementioned thin film formation method may include the following steps: step (1-i) vaporizing the aforementioned activator to replace the ligand in the precursor compound, wherein the aforementioned precursor compound is adsorbed onto the surface of the substrate loaded in the chamber; step (1-ii) performing a first purging of the interior of the aforementioned chamber using a purge gas; step (1-iii) vaporizing the precursor compound and adsorbing it onto the surface of the substrate loaded in the chamber; step (1-iv) performing a second purging of the interior of the aforementioned chamber using a purge gas; step (1-v) supplying a reaction gas to the interior of the aforementioned chamber; and step (1-vi) performing a third purging of the interior of the aforementioned chamber using a purge gas. At this point, steps (1-i) to (1-vi) can be taken as a unit cycle and the aforementioned cycle can be repeated until a film of the desired thickness is obtained. When the activator of the present invention is added to the substrate in a cycle in this manner before the precursor compound, the film growth rate can be appropriately reduced even when deposition is performed at high temperature. The generated process byproducts can be effectively removed to reduce the resistivity of the film and the step coverage can be greatly improved.

[0091] In another preferred embodiment, the aforementioned thin film formation method may include the following steps: step (2-i) vaporizing the precursor compound and adsorbing it onto the surface of a substrate loaded in the chamber; step (2-ii) performing a first purging of the interior of the chamber using a purge gas; step (2-iii) vaporizing the aforementioned activator to replace the ligand in the precursor compound, wherein the aforementioned precursor compound is adsorbed onto the surface of a substrate loaded in the chamber; step (2-iv) performing a second purging of the interior of the chamber using a purge gas; step (2-v) supplying a reaction gas to the interior of the chamber; and step (2-vi) performing a third purging of the interior of the chamber using a purge gas. At this point, steps (2-i) to (2-vi) can be used as a unit cycle, and the aforementioned cycle can be repeated until a film of the desired thickness is obtained. When the activator of the present invention is added after the precursor compound in this manner and adsorbed onto the substrate in one cycle, the aforementioned activator can act as a growth activator for film formation. At this time, the film growth rate is increased, and the density and crystallinity of the film are increased. Therefore, it has the advantages of reducing the resistivity of the film and significantly improving the electrical properties.

[0092] As a preferred example, in the thin film formation method of the present invention, the activator of the present invention can be added to the precursor compound and adsorbed onto the substrate in one cycle. At this time, even when depositing the thin film at high temperature, the thin film growth rate can be appropriately reduced, thereby significantly reducing process by-products and significantly improving step coverage. Moreover, the crystallinity of the thin film is increased to reduce the resistivity of the thin film. Furthermore, even when applied to semiconductor devices with large aspect ratios, the thickness uniformity of the thin film can be significantly improved to ensure the reliability of the semiconductor device.

[0093] As an example, in the aforementioned thin film formation method, when the aforementioned activator is deposited before or after the deposition of the precursor compound, the number of repetitions per unit cycle can be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, within which the desired thin film thickness can be obtained and the effects to be achieved by the present invention can be fully obtained.

[0094] As an example, in this invention, the aforementioned chamber may be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma-enhanced atomic layer deposition (PEALD) chamber, or a plasma-enhanced chemical vapor deposition (PECVD) chamber.

[0095] In this invention, the following steps may be included: after vaporizing and injecting the aforementioned activator or precursor compound, a plasma post-treatment is performed, which can improve the growth rate of the thin film and reduce process by-products.

[0096] When the aforementioned activator is adsorbed first on the substrate, followed by the aforementioned precursor compound, or vice versa, the amount of purge gas introduced into the chamber during the step of purging the unadsorbed activator is sufficient to remove the unadsorbed activator. For example, this can be 10 to 100,000 times, more preferably 50 to 50,000 times, and even more preferably 100 to 10,000 times. Within this range, the unadsorbed activator can be sufficiently removed to form a uniform film and prevent film degradation. The amounts of purge gas and activator introduced are calculated over one cycle, and the volume of the activator represents the volume of the vaporized activator vapor.

[0097] As a specific example, when the aforementioned activator is injected (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and when purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec in the step of purging the unadsorbed activator, the amount of purge gas injected is 602 times the amount of activator injected.

[0098] Furthermore, in the aforementioned step of purging the unadsorbed precursor compounds, the amount of purge gas introduced into the chamber is sufficient to remove the unadsorbed precursor compounds. For example, it can be 10 to 100,000 times the volume of the precursor compounds introduced into the chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed precursor compounds can be sufficiently removed to form a uniform film and prevent film degradation. The amounts of purge gas and precursor compounds introduced are based on one cycle, and the volume of the precursor compounds represents the volume of the vaporized precursor compound vapor.

[0099] Furthermore, in the purging step immediately following the aforementioned reactant gas supply step, as an example, the amount of purging gas introduced into the aforementioned chamber can be 10 to 100,000 times the volume of the reactant gas introduced into the aforementioned chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the desired effect can be sufficiently obtained. The amounts of purging gas and reactant gas introduced are each based on one cycle.

[0100] Preferably, the aforementioned activator and precursor compound can be delivered into the chamber via VFC, DLI, or LDS, and more preferably, via LDS.

[0101] As an example, the substrate loaded in the chamber can be heated to 50-400°C. Specifically, the activator or precursor compound can be injected onto the substrate in either an unheated or heated state, depending on the deposition efficiency. After injection in an unheated state, heating during the deposition process is also acceptable. As an example, the substrate can be injected at 50-400°C within 1-20 seconds.

[0102] The ratio of the aforementioned activator to the aforementioned precursor compound in the chamber (mg / cycle) is 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. Within this range, the improvement in step coverage and the reduction in process byproducts are significant.

[0103] In this invention, as an example, the aforementioned precursor compound can be mixed with a nonpolar solvent and introduced into the chamber, which has the advantage of making it easy to adjust the viscosity or vapor pressure of the precursor compound.

[0104] The aforementioned nonpolar solvent is preferably selected from one or more alkanes and cycloalkanes. In this case, it contains organic solvents with low reactivity and solubility and easy water management, and has the advantage of improving step coverage even when the deposition temperature is increased during film formation.

[0105] As a better example, the aforementioned nonpolar solvent may contain C1-C10 alkanes or C3-C10 cycloalkanes, preferably C3-C10 cycloalkanes, which have the advantages of low reactivity and solubility and easy moisture management.

[0106] In this invention, C1, C3, etc. represent the number of carbon atoms.

[0107] The aforementioned cycloalkanes are preferably C3 to C10 monocycloalkanes, and cyclopentane among the aforementioned monocycloalkanes is liquid at room temperature and has the highest vapor pressure, therefore it is preferred in the vapor deposition process, but is not limited thereto.

[0108] As an example, the solubility of the aforementioned nonpolar solvent in water (at 25°C) is below 200 mg / L, preferably 50~400 mg / L, and more preferably 135~175 mg / L. Within this range, it has the advantages of low reactivity to precursor compounds and easy water management.

[0109] In this invention, solubility can be measured using methods and standards conventionally used in the art. For example, saturated solutions can be measured by HPLC.

[0110] The aforementioned nonpolar solvent preferably comprises, relative to the total weight of the precursor compound and the nonpolar solvent, 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.

[0111] When the content of the aforementioned nonpolar solvent exceeds the upper limit, it will induce impurities, thereby increasing the resistance and impurity values ​​in the thin film. When the content of the aforementioned organic solvent is less than the lower limit, it has the disadvantage that the effect of adding solvent to improve the step coverage and reduce impurities such as chloride (Cl) ions is not significant.

[0112] As an example, in the aforementioned thin film formation method, when the aforementioned activator is used, the deposition rate increase rate expressed by Formula 1 can be 9% or more (deposition rate (DR) of 0.09 Å / cycle or more). Specifically, it can be 9% to 25% (DR of 0.09 to 0.25 Å / cycle), and preferably 9% to 15% (DR of 0.09 to 0.15 Å / cycle). At this time, based on the difference in adsorption distribution of the activator with the above-mentioned structure, a uniformly thick deposition layer is formed as a replacement region that will not remain in the thin film. Thus, while forming a relatively sparse thin film, the growth rate of the formed thin film is greatly reduced. Therefore, even when applied to substrates with complex structures, the uniformity of the thin film can be ensured, thereby greatly improving the step coverage. In particular, it is possible to deposit with a thinner thickness and improve the amount of residual O, Si, metals, metal oxides, and residual carbon that is difficult to reduce in the past as process byproducts.

[0113] [Mathematical Expression 1] The rate of increase in deposition rate (DR) = [{(DRi) - (DRf)} / (DRi)] × 100 In this formula, DR (Deposition rate, Å / cycle) is the deposition rate of the thin film. When depositing a thin film formed from precursors and reactants, DRi (initial deposition rate) is the deposition rate of the film without the addition of an activator. DRf (final deposition rate) is the deposition rate of the film with the addition of an activator during the above process. The deposition rate (DR) is the value of a 3-30 nm thick film measured using an ellipsometer under ambient temperature and pressure conditions, and the unit is Å / cycle.

[0114] The residual halogen intensity (c / s) in a 100 Å film, measured by SIMS using the aforementioned thin film formation method, is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and further preferably 10,000 or less. As a preferred embodiment, it can be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within this range, the effect of preventing corrosion and deterioration is excellent.

[0115] In this invention, the purging rate 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 in a single atomic layer or similar manner, which is therefore advantageous in terms of film quality.

[0116] The aforementioned ALD (Atomic Layer Deposition) process is highly advantageous for manufacturing integrated circuits (ICs) that require high aspect ratios. In particular, it offers advantages such as excellent conformality, uniformity, and precise thickness control based on a self-limiting thin film growth mechanism.

[0117] As an example, the aforementioned thin film formation method can be carried out at a deposition temperature in the range of 50°C to 800°C, preferably at a deposition temperature in the range of 100°C to 700°C, more preferably at a deposition temperature in the range of 200°C to 650°C, even more preferably at a deposition temperature in the range of 220°C to 400°C, and even more preferably at a deposition temperature in the range of 220°C to 300°C. Within this range, it has the effect of achieving ALD process characteristics and growing a thin film with excellent film quality.

[0118] As an example, the aforementioned thin film formation method can be carried out at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr, within which a thin film with uniform thickness is obtained.

[0119] In this invention, deposition temperature and deposition pressure can be measured by the temperature and pressure formed in the deposition chamber or by the temperature and pressure of the substrate applied to the deposition chamber.

[0120] Preferably, the aforementioned thin film formation method may include the following steps: raising the temperature inside the chamber to the deposition temperature before adding the aforementioned activator into the chamber; and / or injecting an inert gas into the chamber for purging before adding the aforementioned activator into the chamber.

[0121] Furthermore, in this invention, the thin film manufacturing apparatus capable of implementing the aforementioned thin film manufacturing method may include an ALD chamber, a first vaporizer for vaporizing the activator, a first delivery unit for delivering the vaporized activator into the ALD chamber, a second vaporizer for vaporizing the thin film precursor, and a second delivery unit for delivering the vaporized thin film precursor into the ALD chamber. The vaporizer and delivery unit may be any vaporizer and delivery unit conventionally used in the art.

[0122] As a specific example, the aforementioned thin film formation method is described. First, the substrate on which the thin film is to be formed is placed in a deposition chamber capable of atomic layer deposition.

[0123] The aforementioned substrate may include silicon substrates, silicon oxide and other semiconductor substrates.

[0124] The aforementioned substrate may further have a conductive layer or an insulating layer formed on its upper part.

[0125] Prepare the aforementioned activator and precursor compound or a mixture thereof with a nonpolar solvent to deposit a thin film on a substrate placed in the aforementioned deposition chamber.

[0126] Afterwards, the prepared activator is injected into the vaporizer and converted into a vapor phase to be transported to the deposition chamber and adsorbed onto the substrate. Then, purging is performed to remove any unadsorbed activator.

[0127] Next, after injecting the prepared precursor compound or a mixture thereof with a nonpolar solvent (a composition for thin film formation) into the vaporizer, it is converted into a vapor phase to be transported to the deposition chamber and adsorbed onto the substrate. The ligands in the precursor compound are replaced by a pre-injected activator, and the unadsorbed precursor compound is then purged.

[0128] In this invention, the order of the process of adsorbing the aforementioned activator onto the substrate and then purging to remove the unadsorbed activator, and the process of adsorbing the precursor compound onto the substrate and then purging to remove the unadsorbed precursor compound, can be changed as needed.

[0129] In this invention, as an example, the activator and precursor compound (thick film formation composition) are delivered to the deposition chamber by means of a vapor flow control (VFC) method or a liquid delivery system (LDS) method. Preferably, the LDS method is used.

[0130] At this time, as a carrier gas or dilution gas for delivering activators and precursor compounds to the substrate, one or more mixed gases selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but not limited thereto.

[0131] In this invention, as an example, the purging gas can be an inert gas, and preferably, the aforementioned carrier gas or dilution gas can be used.

[0132] Next, a reaction gas is supplied. The reaction gas can be any reaction gas conventionally used in the art, preferably containing a nitriding agent. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a nitrided film.

[0133] Preferably, the aforementioned nitriding agent can be nitrogen (N2), hydrazine gas (N2H4), or a mixture of nitrogen and hydrogen.

[0134] Next, an inert gas is used to purge the remaining unreacted reaction gases. This removes not only excess reaction gases but also the generated byproducts.

[0135] As described above, as an example, the aforementioned thin film formation method can take the steps of supplying an activator to a substrate, purging unadsorbed activator, adsorbing a precursor compound / thin film formation composition onto the substrate, purging unadsorbed precursor compound, supplying a reactive gas, and purging residual reactive gas as a unit cycle, and repeat the aforementioned unit cycle to form a thin film of the desired thickness.

[0136] As another example, the aforementioned thin film formation method can take the steps of adsorbing the precursor compound / thin film formation composition onto the substrate; purging the unadsorbed precursor compound; supplying an activator to the substrate; purging the unadsorbed activator; supplying a reactive gas; and purging the residual reactive gas as a unit cycle, and repeat the aforementioned unit cycle to form a thin film of the desired thickness.

[0137] As an example, the number of repetitions per unit period can be 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, it has the effect of well expressing the desired thin film characteristics.

[0138] The present invention also provides a semiconductor substrate, wherein the semiconductor substrate is manufactured by the thin film forming method of the present invention, wherein the thin film has excellent step coverage and thickness uniformity, and the thin film has excellent density and electrical properties.

[0139] Preferably, the thickness of the aforementioned thin film is less than 20 nm, with a resistivity of 0.1 to 400 μΩ·cm based on a film thickness of 10 nm, a halogen content of less than 10,000 ppm, and a step coverage of more than 90%. Within this range, it performs well as an anti-diffusion film and has the effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0140] As an example, the thickness of the aforementioned thin film can be 0.1~20nm, preferably 1~20nm, more preferably 3~20nm, and even more preferably 5~20nm. Within this range, it has excellent thin film properties.

[0141] As an example, based on a film thickness of 10 nm, the resistivity of the aforementioned film can be 0.1~400 μΩ·cm, preferably 15~300 μΩ·cm, more preferably 20~290 μΩ·cm, and even more preferably 25~280 μΩ·cm. Within this range, it exhibits excellent film properties.

[0142] The halogen content of the aforementioned thin film is preferably below 10,000 ppm or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm. Within this range, it exhibits excellent thin film properties and reduces the thin film growth rate. As an example, the halogen remaining in the aforementioned thin film can be Cl2, Cl, or Cl-. The lower the residual halogen content in the thin film, the better the film quality, and therefore, the better.

[0143] As an example, the aforementioned thin film can have a step coverage of 90% or more, preferably 92% or more, and even more preferably 95% or more. Within this range, even thin films with complex structures can be easily deposited on the substrate, thus having the advantage of being applicable to next-generation semiconductor devices.

[0144] Preferably, the thickness of the aforementioned thin film is less than 20 nm, and based on a film thickness of 10 nm, the content of carbon, nitrogen, and halogen is less than 10,000 ppm, and the step coverage is more than 90%. Within this range, it has excellent performance as a dielectric film or barrier film, but is not limited thereto.

[0145] As an example, the aforementioned thin film can be a multilayer structure with two or three layers, depending on the requirements. As a specific example, the aforementioned two-layer multilayer film can be a lower-middle-layer film structure, and as a specific example, the aforementioned three-layer multilayer film can be a lower-middle-upper-layer film structure.

[0146] As an example, the aforementioned lower layer film may contain one or more of the following: Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0147] As an example, the aforementioned intermediate membrane may contain TixNy, and preferably, it may contain TN.

[0148] As an example, the aforementioned upper membrane may contain one or more selected from W and Mo.

[0149] The following preferred embodiments and figures are presented to aid in understanding the present invention. Those skilled in the art will understand that the following embodiments and figures are merely illustrative of the present invention, and various changes and modifications can be made within the scope and technical concept of the present invention, and these variations and modifications fall within the scope of the appended patent applications.

[0150] [Example]

[0151] Examples 1 to 3 and Comparative Examples 1 to 3

[0152] Using the components shown in Table 1, the ALD deposition process was carried out according to Figure 1. Figure 1 is a diagram that schematically illustrates the deposition process sequence of the present invention in one cycle.

[0153] Specifically, prepare 5N hydrogen iodide as an activator.

[0154] In addition, bis(tert-butylamino)silane (BTBAS), di-isopropylaminosilane (DIPAS), and bis(diethylamino)silane (BDEAS) were prepared as precursors.

[0155] As shown in Figure 1, the prepared precursor compound was placed in a separate container and fed at a flow rate of 0.5 g / min into a separate vaporizer heated to 100°C using a Liquid Mass Flow Controller (LMFC) at room temperature. After the precursor, vaporized in the vaporizer, was introduced into the deposition chamber containing the substrate for 5 seconds, argon gas was supplied at 5000 sccm for 30 seconds for argon purging. During this time, the pressure within the reaction chamber was controlled at 2.5 Torr.

[0156] Next, at room temperature, the prepared activator was introduced into the deposition chamber containing the substrate at a flow rate of 500 sccm using a mass flow controller (MFC). After 10 seconds, argon gas was supplied at 5000 sccm for argon purging. At this time, the pressure in the reaction chamber was controlled at 3 Torr.

[0157] Next, ammonia gas was introduced into the aforementioned reaction chamber at 3000 sccm as a reactive gas for 10 seconds, followed by argon purging for 30 seconds. At this time, the substrate to which the metal thin film was to be formed was heated at the temperature conditions shown in Table 1.

[0158] This process was repeated 200 to 400 times to form a self-limiting atomic layer film with a thickness of 10 nm.

[0159] The deposition rate increase (DR increase) and SIMS C impurities of each film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following method and are shown in Table 1 and Figure 2.

[0160] Deposition rate increase (DR(dep.rate) increase): This represents the percentage increase in deposition rate after adding the activator compared to the DR before adding the activator. It is calculated as a percentage using the measured Å / cycle values.

[0161] Specifically, the thickness of the thin film measured using an ellipsometer is divided by the number of cycles to calculate the thickness of the thin film deposited in each cycle. The aforementioned ellipsometer is a device that can measure optical properties such as the thickness or refractive index of the manufactured thin film using the polarization characteristics of light.

[0162] [Table 1] category Membrane categories Activator Activator injection volume (sccm) Precursor types reactants type Deposition temperature (°C) DR (Å / cycle) Comparative Example 1 SiO2 - - BTBAS NH3 200 No growth Comparative Example 2 SiO2 - - BTBAS NH3 300 No growth Comparative Example 3 SiO2 - - BTBAS NH3 400 No growth Example 1 SiO2 HI 500 BTBAS NH3 200 0.14 Example 2 SiO2 HI 500 BTBAS NH3 300 0.09 Example 3 SiO2 HI 500 BTBAS NH3 400 0.11

[0163] In Table 1, BTBAS is an abbreviation for bis(tert-butylamino)silane.

[0164] As shown in Table 1 and Figure 2, it can be confirmed that Examples 1 to 3, which used the activator of the present invention, not only showed a significant improvement in the deposition rate increase rate compared with Comparative Examples 1 to 3, which did not use it, but also exhibited excellent impurity reduction characteristics.

[0165] In particular, it can be confirmed that Examples 1 to 3, which used the activator of the present invention, showed an excellent increase in film growth rate per cycle of 10% compared with Comparative Examples 1 to 3, which did not use the activator.

[0166] The above results indicate that when the activator of the present invention is vapor-coated after the precursor compound is adsorbed onto the surface and the lower part of the pore pattern, the activator with small molecular size can smoothly reach the surface of the substrate and the interior of the pore pattern, and replace the ligands in the precursor compound adsorbed on the reaction surface with appropriate substituents.

[0167] The ammonia gas injected subsequently, as a reactive gas, is able to reach the surface of the substrate and the interior of the hole pattern smoothly due to its small molecular size, thereby forming a good nitride film.

[0168] Therefore, it can be confirmed that when the activator of the present invention is used together with aminosilane as a precursor compound and ammonia as a reaction gas, a nitride film can be effectively formed even on a substrate with a complex pattern.

[0169] none.

Claims

1. A method for forming a thin film, comprising the following steps: An activator is injected into the chamber to replace the ligands in the precursor compound adsorbed on the surface of the loaded substrate; And the use of nitriding agents to manufacture nitrided films, wherein the aforementioned activator comprises a halogen compound, the aforementioned halogen compound being used to replace the ligand contained in the precursor compound represented by Chemical Formula 1, [Chemical Formula 1] In the aforementioned Chemical Formula 1, M is any one selected from Al, Si, Ti, V, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Hf, Ta, W, Re, Os, and Ir, L1, L2, L3, and L4 are -H, -X, -R, -OR, or -NR2 and are the same as or different from each other, wherein -X is F, Cl, Br, or I, and -R is a C1-C10 alkyl, C2-C10 alkenyl, or C2-C10 alkynyl and is linear or cyclic. The aforementioned activator is a pure hydrogen iodide of 3N to 15N, or a gaseous mixture of 1 to 99% by weight of hydrogen iodide of 3N to 15N and an inert gas with a balance of 100% by weight, or an aqueous mixture of 0.5 to 70% by weight of hydrogen iodide of 3N to 15N and water with a balance of 100% by weight, wherein the aforementioned inert gas is nitrogen, helium, or argon with a purity of 4N to 9N.

2. The thin film forming method as described in claim 1, wherein, In the aforementioned chemical formula 1, L1, L2, L3 and L4 are -H or -R and may be the same as or different from each other, wherein -R is a C1 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkynyl and has a linear or cyclic structure.

3. The thin film forming method as described in claim 1, wherein, In the aforementioned chemical formula 1, L1, L2, L3 and L4 are -H, -OR or -NR2 and may be the same as or different from each other, wherein -R is a C1 to C10 alkyl, C2 to C10 alkenyl or C2 to C10 alkynyl.

4. The thin film forming method as described in claim 1, wherein, In the aforementioned chemical formula 1, L1, L2, L3, and L4 are -H or -X and may be the same as or different from each other, wherein -X is F, Cl, Br, or I.

5. The thin film forming method as described in claim 1, wherein, The aforementioned activator activates the laminated film formed from the aforementioned precursor compound.

6. The thin film forming method as described in claim 1, wherein, The aforementioned activator is suitable for the formation of anti-diffusion films, etch stop films, electrode films, dielectric films, gate insulating films, bulk oxide films, or thin films for charge trapping.

7. The thin film forming method as described in claim 1, wherein, The aforementioned chambers are atomic layer deposition (ALD) chambers, chemical vapor deposition (CVD) chambers, plasma-enhanced atomic layer deposition (PEALD) chambers, or plasma-enhanced chemical vapor deposition (PECVD) chambers.

8. The thin film forming method as described in claim 1, wherein, The aforementioned activator is delivered into the chamber via gas flow control (VFC), direct liquid injection (DLI), or liquid transfer system (LDS), and the aforementioned film is a silicon nitride film, titanium nitride film, tungsten nitride film, or molybdenum nitride film.

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