Activator, thin film formation method using same, semiconductor substrate and semiconductor device manufactured by the same

Abstract

The present invention relates to an activator, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. The present invention provides an activator having a specific structure, which effectively replaces the ligand of an adsorbed precursor, thereby improving the reaction rate and appropriately reducing the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and reducing impurities.

Description

[Technical field]

[0001] The present invention relates to an activator, a method for forming a thin film using the same, and a semiconductor substrate and a semiconductor device manufactured thereby. More particularly, the present invention relates to an activator that provides a compound having a specific structure as an activator to effectively replace ligands of a precursor adsorbed on a substrate, thereby improving a reaction rate and appropriately reducing a thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, and significantly reducing impurities, a method for forming a thin film using the same, and a semiconductor substrate manufactured thereby. [Background technology]

[0002] Conventionally, thin films formed through the atomic layer deposition (ALD) process have a risk of the ligands of the precursor compounds injected during the deposition process not being sufficiently removed, resulting in the ligands remaining in the growing thin film, which can lead to contamination by impurities flowing into the thin film.

[0003] In other words, as semiconductor devices become finer, impurities (C, Cl) in the thin film originating from the ligands are generated when the thin film is formed in the horizontal direction. - , F - etc.) may disrupt the crystal arrangement and reduce the density of the formed thin film.

[0004] There is concern that the low density may cause problems in terms of electrical conductivity, and as semiconductor devices become smaller and more stacked, the use of substrates including deep via holes or trenches is increasing.

[0005] When filling a cylindrical hole pattern or trench or forming a thin film along the vertical inner wall, it is difficult to achieve nearly 100% step coverage, which is the uniform thickness of the thin film formed on the top of the pattern and the bottom of the trench.

[0006] As a specific example, referring to the prior art document J. Vac. Sci. Technol. A37, 060904 (2019), it is disclosed that since aminosilane precursors cannot be nitrided using NH3, a nitriding technique is used to nitridize the precursors using NH3 plasma and N2 plasma.

[0007] However, even if plasma is applied to a substrate with a narrow and deep hole pattern, the plasma reaches only the upper part of the substrate, where a nitride film is formed, and the plasma-converted N radicals have a short lifetime and therefore cannot reach the inside of the hole, resulting in a problem that a nitride film cannot be formed.

[0008] Therefore, there is a demand for a thin film formation method that can sufficiently remove the ligands of the precursor compound injected during the deposition process, thereby enabling the formation of a thin film with a complex structure, while reducing the amount of residual impurities, and significantly improving step coverage and thin film thickness uniformity, as well as a semiconductor substrate manufactured thereby. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made to solve the above-mentioned problems of the prior art, and aims to provide an activator that provides a compound of a specific structure as an activator to effectively replace ligands of an adsorbed precursor, thereby improving the reaction rate and appropriately reducing the thin film growth rate, thereby significantly improving step coverage and thin film thickness uniformity even when a thin film is formed on a substrate having a complex structure, a thin film formation method using the same, and a semiconductor substrate manufactured thereby.

[0010] The present invention aims to improve the crystallinity and oxidation fraction of a thin film, thereby improving the density, electrical properties, and dielectric properties of the thin film.

[0011] The above and other objects of the present invention can be achieved by the present invention described below. [Means for solving the problem]

[0012] In order to achieve the above object, the present invention provides an activator comprising a halogenated compound for substituting a ligand contained in a precursor compound represented by the following Chemical Formula 1:

[0013] [Chemical formula 1]

[0014] [ka]

[0015] (In the above formula 1, M is at least one 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; L 1 , L 2 , L 3 and L 4are -H, -X, -R, -OR, or -NR2, which may be the same or different, where -X is F, Cl, Br, or I, and -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 Depending on the oxidation value of the central metal, the n number of L may be 2 to 6.

[0016] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different from each other.

[0017] In the above Chemical Formula 1, L 1 , L 2 , L 3 and L 4 are -H or -R, which may be the same or different, and where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may be linear or cyclic.

[0018] In the above Chemical Formula 1, L 1 , L 2 , L 3 and L 4 are -H, -OR, or -NR2, which may be the same or different, where -R is H, C1 to C 10 Alkyl, C1-C 10Alkenes, C1-C 10 alkanes, iPr, or tBu.

[0019] In the above Chemical Formula 1, L 1 , L 2 , L 3 and L 4 are -H, or -X, which may be the same or different, where -X is F, Cl, Br, or I.

[0020] The halogen compound may be at least one selected from hydrogen iodide, hydrogen iodide water, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, isopropyl iodide, and t-butyl iodide.

[0021] The activator is a single substance of 3N-15N hydrogen iodide, a gas mixture of 1-99% by weight of 3N-15N hydrogen iodide and the balance of an inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5-70% by weight of 3N-15N hydrogen iodide and the balance of water to make the total amount 100% by weight, where the inert gas can be nitrogen, helium or argon having a purity of 4N-9N.

[0022] The activator may have an increase in deposition rate, represented by the following Equation 1, of 10% or more.

[0023] [Formula 1]

[0024] Rate of increase in deposition rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0025] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (Initial Deposition Rate) is the deposition rate of the thin film formed without adding any reaction surface control agent. DR f(Final deposition rate) is the deposition rate of a thin film formed by adding an activator when the above-mentioned process is carried out. Here, the deposition rate (DR) is a value measured by an ellipsometer device under conditions of room temperature and normal pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.)

[0026] In Equation 1, the thin film growth rate per cycle when an activator is used and when an activator is not used means the deposition thickness (Å / cycle) of the thin film per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by measuring the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure, and then dividing the measured thickness by the total number of cycles to obtain an average deposition rate.

[0027]

[0028] The activator may have a refractive index of 1.40 or more, 1.42 to 1.50, 1.43 to 1.48, or 1.44 to 1.48.

[0029] The activator may provide a replacement region for an oxide film, a nitride film, a metal film, or selective thin films thereof.

[0030] The replacement region may be formed on the entire substrate or a portion of the substrate on which the oxide film, nitride film, metal film, or selective thin film thereof is formed.

[0031] When the total area of ​​the entire substrate or part of the substrate (total area of ​​the substrate) is taken as 100%, the ligand adsorption region may occupy 10 to 95% of the area, and the ligand non-adsorbed region may occupy the remaining area.

[0032] When the total area of ​​the entire substrate or part of the substrate (total area of ​​the substrate) is taken as 100%, the first ligand adsorption region may occupy 10 to 95% of the area, the second ligand adsorption region may occupy 10 to 95% of the remaining area, and the remaining area may be occupied by ligand-unadsorbed regions.

[0033] The thin film may be one that activates one or more laminated films selected from the group consisting 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.

[0034] The thin film can be applied to the formation of a thin film for use as a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap.

[0035]

[0036] The present invention also provides a method for forming a thin film, comprising the step of injecting the activator into a chamber to replace ligands of a precursor compound adsorbed on a surface of a loaded substrate.

[0037]

[0038] Furthermore, the present invention provides a method for producing a

[0039] 1-i) vaporizing the activator to replace the ligands of the precursor compound adsorbed on the surface of the substrate loaded in the chamber;

[0040] 1-ii) a step of first purging the inside of the chamber with a purge gas;

[0041] 1-iii) vaporizing a precursor compound and adsorbing it in a region outside the replacement region;

[0042] 1-iv) a step of second purging the inside of the chamber with a purge gas;

[0043] 1-v) supplying a reaction gas into the chamber;

[0044] 1-vi) a third step of purging the inside of the chamber with a purge gas.

[0045]

[0046] Furthermore, the present invention relates to a method for producing a pharmaceutical composition comprising the steps of:

[0047] 2-i) vaporizing a precursor compound and adsorbing it on a surface of a substrate loaded in a chamber;

[0048] 2-ii) performing a first purge of the inside of the chamber with a purge gas;

[0049] 2-iii) vaporizing the activator to replace ligands of the precursor compound adsorbed on the surface of the substrate loaded in the chamber;

[0050] 2-iv) a second purging step of the inside of the chamber with a purge gas;

[0051] 2-v) supplying a reaction gas into the chamber;

[0052] 2-vi) a third step of purging the inside of the chamber with a purge gas.

[0053] The precursor compound may be a molecule composed of one or more elements selected from the group consisting 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, and may be a precursor having a vapor pressure at 25°C of more than 0.01 mTorr and not more than 100 Torr.

[0054] The chamber may be an atomic layer deposition (ALD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, or a plasma enhanced chemical vapor deposition (PECVD) chamber.

[0055] After the activator or precursor compound has been vaporized and injected, a step of plasma post-treatment may be included.

[0056] The amount of purge gas introduced into the chamber in each of steps 1-ii) and 1-iv), and steps 2-ii) and 2-iv) may be 10 to 100,000 times the volume of the introduced activator.

[0057] The reactant gas may be an oxidant, a nitridant or a reductant, and the reactant gas, activator and precursor compound may be delivered into the chamber by a Vapor Flow Control (VFC) method, a Direct Liquid Introduction (DLI) method or a Liquid Delivery System (LDS) method.

[0058] The thin film may be a molybdenum film, a tungsten film, a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0059] The substrate loaded into the chamber may be heated to 100 to 800° C., and the ratio of the amount (mg / cycle) of the activator to the precursor compound input into the chamber may be 1:1 to 1:20.

[0060]

[0061] The present invention also provides a semiconductor substrate produced by the above-mentioned thin film formation method.

[0062] The thin film may be a multi-layer structure of two or three layers.

[0063]

[0064] The present invention further provides a semiconductor device including the semiconductor substrate described above.

[0065] The semiconductor substrate can be low resistive metal gate interconnects, high aspect ratio 3D metal-insulator-metal (MIM) capacitors, DRAM trench capacitors, 3D Gate-All-Around (GAA), or 3D NAND flash memory. Effect of the Invention

[0066] According to the present invention, it is possible to provide an activator that effectively replaces the ligands of a precursor adsorbed on a substrate to improve the reaction rate, appropriately increases the thin film growth rate, and improves the productivity of the thin film.

[0067] In addition, the process by-products during the formation of the thin film are more effectively reduced, corrosion and deterioration are prevented, and the crystallinity of the thin film is improved, thereby improving the roughness, dielectric constant, and electrical properties of the thin film.

[0068] Furthermore, the step coverage and density of the thin film can be improved, and further, a thin film forming method using the same and a semiconductor substrate manufactured thereby can be provided. [Brief description of the drawings]

[0069] [Figure 1] FIG. 2 is a diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0070] [Diagram 2] FIG. 2 is a graph showing a comparison between the increase rate of deposition rate in Examples 1 to 3 in which an activator according to the present invention was used and the increase rate of deposition rate in Comparative Examples 1 to 3 in which an activator was not used according to the conventional technology. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0071] The activator described above, the thin film formation method using the same, and the semiconductor substrate produced thereby will be described in detail below.

[0072] The present inventors have found that in order to form a thin film on the surface of a substrate loaded inside a chamber, a compound capable of replacing the ligand of an adsorbed precursor compound is provided as an activator, thereby improving the reaction rate due to the activation energy reduction mechanism of the activator, and even if applied to a substrate with a complex structure, the uniformity of the thin film is ensured, the step coverage is greatly improved, and in particular, it is possible to deposit a thin film, and the amount of O, Si, metal, metal oxide, and even carbon remaining as process by-products, which was difficult to reduce in the past, can be improved. Based on this finding, the present inventors have incorporated the findings into research on activators and completed the present invention.

[0073]

[0074] The thin film may be provided as one or more precursors selected from the group consisting of, for example, 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, and may provide an oxide film, a nitride film, or a metal film. In this case, the effects to be achieved in the present invention may be sufficiently obtained.

[0075] As specific examples, the thin film may have a film composition of a molybdenum film, a tungsten film, a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film, or an aluminum oxide film.

[0076] The thin film may contain the above-mentioned film compositions alone or as selective areas, but is not limited thereto, and is meant to include SiH and SiOH.

[0077] The thin film can be used in semiconductor devices not only as a commonly used diffusion barrier film, but also as an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a charge trap.

[0078]

[0079] In the present invention, the precursor compound used to form a thin film is a molecule having a central metal atom (M) 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, or Nd, and one or more ligands consisting of C, N, O, H, or X (halogens), and in the case of a precursor having a vapor pressure of 1 mTorr to 100 Torr at 25° C., the effect of being substituted with an activator, which will be described later, can be maximized.

[0080] As the precursor compound, for example, a compound represented by the following Chemical Formula 1 can be used.

[0081] [Chemical formula 1]

[0082] [ka]

[0083] (In the above formula 1, M is at least one 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; L 1 , L 2 , L 3 and L 4 are -H, -X, -R, -OR, or -NR2, which may be the same or different, where -X is F, Cl, Br, or I, and -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 which may be linear or cyclic, 1 , L 2 , L 3 and L 4 Depending on the oxidation value of the central metal (M), the n number of L can be 2 to 6.

[0084] As an example, when the central metal is divalent, L 1 and L 2 can be attached to the central metal as a ligand, and if the central metal is hexavalent, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 can be attached to the central metal, and L 1 ~L 6 The ligands corresponding to may be the same or different.

[0085] In the formula 1, M is hafnium (Hf), silicon (Si), zirconium (Zr) or aluminum (Al), preferably hafnium (Hf) or silicon (Si). In this case, there are advantages in that the effect of reducing process by-products is large, the step coverage is excellent, the effect of improving the thin film density, and the electrical properties, insulating properties and dielectric properties of the thin film are further excellent.

[0086] Said L 1, L 2 , L 3 and L 4 are -H or -R, which may be the same or different, and where -R is C1 to C 10 Alkyl, C1-C 10 Alkenes, or C1-C 10 and may have a linear or cyclic structure, in which case it has a suitable degree of reaction energy to be displaced by an activating agent, as described below.

[0087] In addition, the above-mentioned L 1 , L 2 , L 3 and L 4 are -H, -OR, or -NR2, which may be the same or different, where -R is H, C1 to C 10 Alkyl, C1-C 10 Alkenes, C1-C 10 alkane, iPr, or tBu, in which case it has a suitable degree of reaction energy to be displaced by an activating agent, as described below.

[0088] Furthermore, in the above Chemical Formula 1, L 1 , L 2 , L 3 and L 4 is -H, or -X, which may be the same or different, where -X may be F, Cl, Br, or I, and has a suitable degree of reaction energy to be replaced by an activating agent as described below.

[0089] Specifically, examples of silicon precursor compounds include SiH4, SiHCl3, SiH2Cl2, SiCl4, Si2Cl6, Si3Cl8, and Si4Cl. 10, SiH2[NH(C4H9)]2, Si2(NHC2H5)4, Si3NH4(CH3)3 and SiH3[N(CH3)2], SiH2[N(CH3)2]2, SiH[N(CH3)2]3, Si[N(CH3)2]4, TEOS (tetraethyl orthosilicate, Si(OC2H5)4), DIPAS ([di-isopropylaminosilane, H3Si[N{(CH)(CH3)2}]), BTBAS (bis(t-butylamino)silane), (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)Si(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(NHtBu)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(NHEt)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、(NH 2)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、(NEt2)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(NHiPr)2、(NnPr2)2Si(NHnBu)2、(NnPr2)2Si(NHiBu)2、(NnPr2)2Si(NHtBu)2、(NiPr2)2Si(NHMe)2、(NiPr2)2Si(NHEt)2、(NiPr2)2Si(NHnPr)2、(NiPr2)2Si(NHi Pr)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(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(MeNC H2CH2NMe)2、Si(EtNCH2CH2NEt)2、Si(nPrNCH2CH2NnPr)2、Si(iPrNCH2CH2NiPr)2、Si(nBuNCH2CH2NnBu)2、Si(iBuNCH2CH2NiBu)2、Si(tBu NCH2CH2NtBu)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(nBuNCH2CH2NnBu)、(iBuNCHCHNiBu)S i(iBuNCH2CH2NiBu)、(tBuNCHCHNtBu)Si(tBuNCH2CH2NtBu)、(NHtBu)2Si(HNCH2CH2NH)、(NHtBu)2Si(MeNCH2CH2NMe)、(NHtBu)2Si(EtNCH 2CH2NEt)、(NHtBu)2Si(nPrNCH2CH2NnPr)、(NHtBu)2Si(iPrNCH2CH2NiPr)(NHtBu)2Si(nBuNCH2CH2NnBu)、(NHtBu)2Si(iBuNCH2CH2NiBu)、 , (NHtBu)2Si(tBuNCH2CH2NtBu), (NHtBu)2Si(HNCHCHNH), (NHtBu)2Si(MeNCHCHNMe), (NHtBu)2 Si(EtNCHCHNEt), (NHtBu)2Si(nPrNCHCHNnPr), (NHtBu)2Si(iPrNCHCHNiPr), (NHtBu)2Si(nBuNC HCHNnBu), (NHtBu)2Si(iBuNCHCHNiBu), (NHtBu)2Si(tBuNCHCHNtBu), (iPrNCH2CH2NiPr)Si(NH Me)2, (iPrNCH2CH2NiPr)Si(NHEt)2, (iPrNCH2CH2NiPr)Si(NHnPr)2, (iPrNCH2CH2NiPr)Si(NHiP r)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 can be used, and in this case, it has a suitable degree of reaction energy to be substituted by an activator described later.

[0090] Examples of hafnium precursor compounds that can be used include tris(dimethylamido)cyclopentadienylhafnium, CpHf(NMe2)3, and (methyl-3-cyclopentadienylpropylamino)bis(dimethylamino)hafnium, Cp(CH2)3NM3Hf(NMe2)2, which have a suitable reaction energy for replacement with an activator, which will be described later.

[0091]

[0092] The activator of the present invention can effectively replace the ligand in the precursor compound by lowering the activation energy of the precursor compound adsorbed on the substrate. In other words, it is preferable to use a compound that can provide a replacement region for the ligand of the precursor compound adsorbed on the substrate.

[0093] For example, the replacement region may be formed on the entire substrate or a portion of the substrate on which the thin film is formed.

[0094] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate (the entire area of ​​the substrate) is taken as 100%, the substituted region may, for example, occupy an area of ​​10 to 95%, specifically, an area of ​​15 to 90%, preferably an area of ​​20 to 85%, more preferably an area of ​​30 to 80%, even more preferably an area of ​​40 to 75%, and even more preferably an area of ​​40 to 70%, and the unsubstituted region may occupy the remaining area.

[0095] Furthermore, when the total area of ​​the entire substrate or a portion of the substrate (the entire area of ​​the substrate) is taken as 100%, the first substituted region may occupy an area of ​​10 to 95%, specifically 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70% of the remaining area, the second substituted region may occupy an area of ​​10 to 95%, specifically 15 to 90%, preferably 20 to 85%, more preferably 30 to 80%, even more preferably 40 to 75%, and even more preferably 40 to 70% of the remaining area, and the remaining area may be occupied by an unsubstituted region.

[0096]

[0097] The activator is at least one selected from hydrogen iodide, hydrogen iodide water, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, isopropyl iodide, and t-butyl iodide. In this case, a ligand-substituted region that does not remain in the thin film is formed during the formation of the thin film, forming a relatively sparse thin film, suppressing side reactions, controlling the thin film growth rate, reducing process by-products in the thin film, reducing corrosion and deterioration, improving the crystallinity of the thin film, and allowing a stoichiometric oxidation state to be reached during the formation of a metal oxide film. Even when a thin film is formed on a substrate having a complex structure, there are effects of significantly improving step coverage and thickness uniformity of the thin film.

[0098] As a specific example, the activator is a single substance of 3N-15N hydrogen iodide, a gas mixture of 1-99% by weight of 3N-15N hydrogen iodide and the balance of an inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5-70% by weight of 3N-15N hydrogen iodide and the balance of water to make the total amount 100% by weight, whereby when the inert gas is nitrogen, helium or argon having a purity of 4N-9N, it has a large effect of reducing process by-products and excellent step coverage, as well as an effect of improving the thin film density and electrical properties of the thin film.

[0099] Preferably, the activator is a single substance of 5N-6N hydrogen iodide, a gas mixture of 1-99% by weight of 5N-6N hydrogen iodide and the remaining amount of inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5-70% by weight of 5N-6N hydrogen iodide and the remaining amount of water to make the total amount 100% by weight, where the inert gas can be nitrogen, helium or argon having a purity of 4N-9N. In this case, a substitution region that does not remain in the thin film is formed during the formation of the thin film to form a relatively sparse thin film, side reactions are suppressed, the thin film growth rate is controlled, process by-products in the thin film are reduced, corrosion and deterioration are reduced, the crystallinity of the thin film is improved, and even when the thin film is formed on a substrate having a complex structure, step coverage and thickness uniformity of the thin film can be significantly improved.

[0100]

[0101] The activator is preferably a single substance of 5N to 6N hydrogen iodide, a gas mixture of 1 to 99% by weight of 5N to 6N hydrogen iodide and a remaining amount of inert gas to make the total amount 100% by weight, or an aqueous solution mixture of 0.5 to 70% by weight of 5N to 6N hydrogen iodide and a remaining amount of water to make the total amount 100% by weight, where the inert gas is nitrogen, helium or argon having a purity of 4N to 9N. The compound has an increase rate of the deposition rate represented by the following mathematical formula 1 of 9% or more (deposition rate (D / R) 0.09 Å / cycle or more), specifically 9 to 25% (D / R 0.09 to 0.25 Å / cycle), or 9 to 15% (D / R In this case, a deposition rate of a uniform layer thickness by the activator having the above-mentioned structure is formed as a substitution region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the thin film formed is significantly reduced. Even if the thin film is applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, it is possible to provide an effect that the deposition rate of a thin thin film can be improved, and O, Si, metal, metal oxide, and even carbon residues that were difficult to reduce as process by-products can be reduced.

[0102] [Formula 1]

[0103] Rate of increase in deposition rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0104] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any reaction surface control agent. DR f(Final Deposition Rate) is the deposition rate of a thin film formed by adding an activator when the above-mentioned process is carried out. Here, the deposition rate (DR) is a value measured by an ellipsometer device under conditions of room temperature and normal pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0105] In Equation 1, the thin film growth rate per cycle when an activator is used and when an activator is not used means the deposition thickness (Å / cycle) of the thin film per cycle, i.e., the deposition rate. For example, the deposition rate can be calculated by measuring the final thickness of a thin film having a thickness of 3 to 30 nm by ellipsometry under conditions of room temperature and pressure, and then dividing the measured thickness by the total number of cycles to obtain an average deposition rate.

[0106]

[0107] In the above formula 1, "when no activator was used" refers to a case where only a precursor compound is adsorbed onto a substrate during a thin film deposition process to produce a thin film. A specific example of the thin film formation method is a case where a thin film is formed by omitting the steps of adsorbing an activator and purging unadsorbed activator.

[0108]

[0109] When the activator is, for example, a hydrogen iodide compound, the activator may be a compound having a refractive index within the range of 1.4 to 1.42, or 1.43 to 1.5, specifically, 1.41 to 1.417, or 1.43 to 1.47, preferably 1.413 to 1.417, or 1.450 to 1.452.

[0110] In such a case, the activation energy required for the ligand substitution reaction of the activator having the above-mentioned structure on the substrate is reduced, and the activator appropriately substitutes with the ligand in the precursor compound adsorbed on the substrate, thereby improving the reaction rate, and even when a thin film is formed on a substrate having a complex structure, the step coverage and the thickness uniformity of the thin film are significantly improved, and the adsorption of not only the thin film precursor but also process by-products is prevented, thereby effectively protecting the surface of the substrate, and the process by-products are effectively removed.

[0111] In particular, a relatively sparse thin film is formed, and the growth rate of the formed thin film is significantly reduced. Therefore, even if the thin film is applied to a substrate having a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, the method can provide an effect of improving the amount of O, Si, metal, metal oxide, and even carbon residues that are left as process by-products and that were previously difficult to reduce.

[0112]

[0113] The replacement region for the thin film is characterized in that it does not remain in the thin film.

[0114] In this case, unless otherwise specified, "not remaining" refers to the presence of C element at 0.1 atomic % (atom %), Si element at less than 0.1 atomic % (atom %), N element at less than 0.1 atomic % (atom %), and halogen element at less than 0.1 atomic % (atom %) when the components are analyzed by X-ray photoelectron spectroscopy (XPS). More preferably, in a measurement method using secondary ion mass spectrometry (SIMS) in which measurements are made while digging into the substrate in the depth direction, or a measurement method using X-ray photoelectron spectroscopy (XPS), when considering the increase / decrease rate of C, N, Si, and halogen impurities before and after using an activator under the same deposition conditions, it is preferable that the increase / decrease rate of the signal sensitivity (intensity) of each element type does not exceed 5%.

[0115] As an example, the thin film may contain halogen compounds at 100 ppm or less.

[0116] The 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 to these.

[0117] The activator 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 a compound having a purity of less than 99% is used, there is a risk that impurities may remain in the thin film or cause side reactions with the precursor or reactant, so it is preferable to use a substance having a purity of 99% or more whenever possible.

[0118]

[0119] The activator is preferably used in an atomic layer deposition (ALD) process, and in this case, it has the advantages of effectively protecting the substrate surface and effectively removing process by-products by being used as an activator while not interfering with the adsorption of the precursor compound.

[0120] The activator preferably has a density of 0.8 to 2.5 g / cm 3 or 0.8~1.5g / cm 3 The vapor pressure (20° C.) may be 0.1 to 300 mmHg or 1 to 300 mmHg. Within this range, the substitution region is effectively formed, and there is an effect that the step coverage, the film thickness uniformity of the thin film, and the improvement of the film quality are excellent.

[0121] More preferably, the activator has a density of 0.75 to 2.0 g / cm 3 or 0.8~1.3g / cm 3 The vapor pressure (20° C.) can be 1 to 260 mmHg. Within this range, the substitution region is effectively formed, and there is an effect that the step coverage, the film thickness uniformity of the thin film, and the improvement of the film quality are excellent.

[0122]

[0123] The method for forming a thin film of the present invention is characterized by including a step of injecting the above-mentioned activator into a chamber to replace ligands of a precursor compound adsorbed on the surface of a loaded substrate. In this case, the ligands of the precursor adsorbed on the substrate are effectively replaced to improve the reaction rate and appropriately reduce the thin film growth rate, thereby significantly improving step coverage and thickness uniformity of the thin film even when a thin film is formed on a substrate having a complex structure.

[0124]

[0125] In the step of shielding the activator on the surface of the substrate, the feeding time (seconds (sec)) of the activator to the surface of the substrate is preferably 0.01 to 5 seconds per cycle, 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, there are advantages such as a low thin film growth rate, excellent step coverage, and excellent cost performance.

[0126] In this description, the feeding time of the activator is based on a flow rate of 0.1 to 500 mg / cycle in a chamber volume of 15 to 20 L, and more specifically, based on a flow rate of 0.8 to 200 mg / cycle in a chamber volume of 18 L.

[0127]

[0128] As a preferred embodiment, the method for forming a thin film may include the steps of: 1-i) vaporizing the activator to replace the ligand of the precursor compound adsorbed on the surface of the substrate loaded in the chamber; 1-ii) first purging the inside of the chamber with a purge gas; 1-iii) vaporizing the precursor compound to adsorb it on the surface of the substrate loaded in the chamber; 1-iv) second purging the inside of the chamber with a purge gas; 1-v) supplying a reaction gas into the chamber; and 1-vi) third purging the inside of the chamber with a purge gas. At this time, the steps 1-i) to 1-vi) are regarded as a unit cycle, and the cycle can be repeated until a thin film having a desired thickness is obtained. In this way, when the activator of the present invention is introduced before the precursor compound in one cycle and adsorbed on the substrate, even if the deposition is performed at a high temperature, the thin film growth rate can be appropriately reduced, and the resistivity of the thin film can be reduced by effectively removing the process by-products generated, and the step coverage is significantly improved.

[0129]

[0130] As another preferred embodiment, the thin film forming method may include the steps of 2-i) vaporizing a precursor compound and adsorbing it on the surface of a substrate loaded in a chamber, 2-ii) first purging the inside of the chamber with a purge gas, 2-iii) vaporizing the activator to replace the ligand of the precursor compound adsorbed on the surface of the substrate loaded in the chamber, 2-iv) second purging the inside of the chamber with a purge gas, 2-v) supplying a reaction gas into the inside of the chamber, and 2-vi) third purging the inside of the chamber with a purge gas. At this time, the steps 2-i) to 2-vi) are set as a unit cycle, and the cycle can be repeated until a thin film of a desired thickness is obtained. In this way, when the activator of the present invention is added after the precursor compound in one cycle and adsorbed on the substrate, the activator can act as a growth activator for thin film formation, and in this case, there are advantages in that the thin film growth rate is increased, the density and crystallinity of the thin film are increased, the resistivity of the thin film is reduced, and the electrical properties are significantly improved.

[0131]

[0132] As a preferred example of the thin film formation method of the present invention, the activator of the present invention can be added prior to the precursor compound within one cycle to be adsorbed onto the substrate. In this case, even if the thin film is deposited at a high temperature, the thin film growth rate can be appropriately reduced, so that process by-products can be significantly reduced, step coverage can be significantly improved, and the crystallinity of the thin film can be increased to reduce the resistivity of the thin film. Even when applied to a semiconductor device with a large aspect ratio, the uniformity of the thin film thickness can be significantly improved, ensuring the reliability of the semiconductor device.

[0133]

[0134] In the thin film formation method, for example, when the activator is deposited before or after deposition of the precursor compound, a unit cycle can be repeated 1 to 99,999 times as necessary, and preferably a unit cycle can be repeated 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the effect to be achieved in the present invention can be sufficiently obtained while obtaining the desired thin film thickness.

[0135]

[0136] In the present invention, the chamber may be, for example, an ALD chamber, a CVD chamber, a PEALD chamber or a PECVD chamber.

[0137] In the present invention, the activator or precursor compound may be vaporized and injected, followed by a step of plasma post-treatment, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0138]

[0139] In the case where the activator is first adsorbed on the substrate and then the precursor compound is adsorbed, or the precursor compound is first adsorbed and then the activator is adsorbed, the amount of purge gas introduced into the chamber in the step of purging the unadsorbed activator is not particularly limited as long as it is an amount sufficient to remove the unadsorbed activator, but as an example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, and within this range, the unadsorbed activator is sufficiently removed to form a thin film uniformly and prevent deterioration of film quality. Here, the amounts of the purge gas and the activator introduced are based on one cycle, and the volume of the activator means the volume of the vaporized activator vapor.

[0140] As a specific example, when the activator is injected (per cycle) at a flow rate of 1.66 mL / s and an injection time of 0.5 sec, and in the step of purging unadsorbed activator, a purge gas is injected (per cycle) at a flow rate of 166.6 mL / s and an injection time of 3 sec, the amount of purge gas injected is 602 times the amount of activator injected.

[0141]

[0142] In addition, in the step of purging the unadsorbed precursor compound, the amount of purge gas introduced into the chamber is not particularly limited as long as it is an amount sufficient to remove the unadsorbed precursor compound, but as an example, it may be 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times based on the volume of the precursor compound introduced into the chamber, and within this range, the unadsorbed precursor compound can be sufficiently removed to form a thin film uniformly and prevent deterioration of the film quality. Here, the amounts of the purge gas and the precursor compound introduced are each based on one cycle, and the volume of the precursor compound means the volume of the vaporized precursor compound vapor.

[0143]

[0144] Furthermore, in the purge step performed immediately after the reaction gas supply step, the amount of purge gas introduced into the chamber may be, for example, 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times the volume of the reaction gas introduced into the chamber, and within this range, the desired effect can be sufficiently obtained. Here, the amounts of the purge gas and reaction gas introduced are each based on one cycle.

[0145]

[0146] The activator and precursor compound can be preferably delivered into the chamber by the VFC method, the DLI method or the LDS method, and more preferably are delivered into the chamber by the LDS method.

[0147] The substrate loaded in the chamber may be heated to, for example, 50 to 400° C., and the activator or precursor compound may be injected onto the substrate in an unheated or heated state, and the heating conditions may be adjusted during the deposition process after being injected unheated depending on deposition efficiency. For example, the activator or precursor compound may be injected onto the substrate at a temperature of 50 to 400° C. for 1 to 20 seconds.

[0148] The ratio of the amount (mg / cycle) of the activator to the precursor compound put 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. Within this range, the effect of improving step coverage and the effect of reducing process by-products are large.

[0149] In the present invention, the precursor compound may be mixed with a non-polar solvent and then introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the precursor compound can be easily adjusted.

[0150] The non-polar solvent may be at least one selected from the group consisting of alkanes and cycloalkanes. In this case, the non-polar solvent has the advantage of improving step coverage even when the deposition temperature is increased during the formation of a thin film, while containing an organic solvent having low reactivity and solubility and easy moisture management.

[0151] In a more preferred example, the non-polar solvent is a C1 to C 10 Alkanes of C3 to C 10 and preferably C3 to C 10 In this case, the reactivity and solubility are low, and water management is easy.

[0152] In this description, C1, C3, etc. refer to the carbon numbers.

[0153] The cycloalkane is preferably a C3 to C 10 Among the monocycloalkanes, cyclopentane is liquid at room temperature and has the highest vapor pressure, and therefore is suitable for the vapor deposition process, but is not limited thereto.

[0154] The non-polar solvent has, for example, a solubility in water (25° C.) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, the non-polar solvent has the advantages of low reactivity with the precursor compound and easy moisture control.

[0155] In this description, the solubility is not particularly limited to the measurement methods and standards commonly used in the technical field to which the present invention pertains, and as an example, a saturated solution can be measured by high performance liquid chromatography (HPLC).

[0156] The non-polar solvent may preferably comprise 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, based on the total weight of the precursor compound and the non-polar solvent.

[0157] If the content of the non-polar solvent exceeds the upper limit, impurities are induced, and the value of impurities in the thin film and the resistance is increased. If the content of the organic solvent is less than the lower limit, the effect of improving step coverage and the effect of reducing impurities such as chlorine (Cl) ions by adding the solvent are not sufficiently obtained.

[0158]

[0159] In the thin film forming method, when the activator is used, for example, the increase rate of the deposition rate represented by the following formula 1 may be 9% or more (deposition rate (D / R) 0.09 Å / cycle or more), specifically, 9 to 25% (D / R 0.09 to 0.25 Å / cycle) or 9 to 15% (D / R 0.09 to 0.15 Å / cycle). In this case, a deposition layer having a uniform layer thickness due to the difference in the adsorption distribution degree of the activator having the above-mentioned structure is formed as a replacement region that does not remain in the thin film, forming a relatively sparse thin film, and the growth rate of the formed thin film is significantly reduced, so that even if it is applied to a substrate with a complex structure, the uniformity of the thin film is ensured and the step coverage is significantly improved. In particular, it is possible to provide an effect that the deposition can be performed on a thin thin film, and O, Si, metal, metal oxide, which remain as process by-products, and even carbon residues, which were difficult to reduce in the past, are improved.

[0160] [Formula 1]

[0161] Rate of increase in deposition rate = [{(DR i )-(DR f )} / (DR i )] x 100

[0162] (In the above formula, DR (Deposition rate, Å / cycle) is the rate at which a thin film is deposited. When a thin film is deposited by a precursor and a reactant, DR i (initial deposition rate) is the deposition rate of the thin film formed without adding any reaction surface control agent. DR f (Final Deposition Rate) is the deposition rate of a thin film formed by adding an activator when the above-mentioned process is carried out. Here, the deposition rate (DR) is a value measured by an ellipsometer device under conditions of room temperature and normal pressure for a thin film having a thickness of 3 to 30 nm, and is expressed in Å / cycle units.

[0163]

[0164] In the thin film formation method, the strength (c / s) of residual halogen in the thin film, based on a thin film thickness of 100 Å, measured based on SIMS, can be preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less, and in a preferred embodiment, can be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within such a range, the effect of preventing corrosion and deterioration is outstanding.

[0165] In this description, the purge rate is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeters per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, and deposition is performed as or approximately as an atomic mono-layer, which is advantageous in terms of film quality.

[0166]

[0167] The ALD (atomic layer deposition) process is very advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and has advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin film growth mechanism.

[0168] The 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 100 to 700°C, more preferably at a deposition temperature in the range of 200 to 650°C, even more preferably at a deposition temperature in the range of 220 to 400°C, and even more preferably at a deposition temperature in the range of 220 to 300°C. Within this range, there is an effect of growing a thin film with excellent film quality while realizing the ALD process characteristics.

[0169] The thin film formation method can be carried out, for example, at a deposition pressure in the range of 0.01 to 20 Torr, preferably at a deposition pressure in the range of 0.1 to 20 Torr, more preferably at a deposition pressure in the range of 0.1 to 10 Torr, and most preferably at a deposition pressure in the range of 0.3 to 7 Torr. Within this range, there is an effect that a thin film with a uniform thickness can be obtained.

[0170] In this description, deposition temperature and deposition pressure may be measured as the temperature and pressure established within a deposition chamber, or may be measured as the temperature and pressure applied to a substrate within the deposition chamber.

[0171] The thin film formation method may preferably include a step of raising the temperature in the chamber to a deposition temperature before introducing the activator into the chamber, and / or a step of injecting an inert gas into the chamber to purge the chamber before introducing the activator into the chamber.

[0172] The present invention may also include a thin film manufacturing apparatus capable of implementing the thin film manufacturing method, the thin film manufacturing apparatus including an ALD chamber, a first vaporizer for vaporizing an activator, a first transport means for transporting the vaporized activator into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second transport means for transporting the vaporized thin film 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.

[0173]

[0174] As a specific example, the method for forming the thin film will be described below. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of depositing atomic layers.

[0175] The substrate may be a semiconductor substrate such as a silicon substrate or a silicon oxide substrate.

[0176] The substrate may further have a conductive or insulating layer formed thereon.

[0177] In order to deposit a thin film on a substrate placed in the deposition chamber, the above-mentioned activator and a precursor compound or a mixture thereof with a non-polar solvent are prepared.

[0178] Then, the prepared activator is injected into a vaporizer, converted into a vapor phase, and delivered to a deposition chamber to be adsorbed on a substrate, and then purged to remove unadsorbed activator.

[0179] Next, the prepared precursor compound or a mixture of the precursor compound and a non-polar solvent (a composition for forming a thin film) is injected into a vaporizer, converted into a vapor phase, and transferred to a deposition chamber to be adsorbed onto a substrate. The ligand of the precursor compound is replaced by an activator that was injected beforehand, while unadsorbed precursor compound is purged.

[0180] In this description, the steps of adsorbing the activator onto the substrate and then purging to remove any unadsorbed activator, and of adsorbing a precursor compound onto the substrate and then purging to remove any unadsorbed precursor compound, may be performed in different orders, if necessary.

[0181] In this description, examples of a method for delivering an activator and a precursor compound (a composition for forming a thin film) to a deposition chamber include a method for delivering a volatilized gas using a mass flow controller (MFC) (Vapor Flow Control: VFC), or a method for delivering a liquid using a liquid mass flow controller (LMFC) (Liquid Delivery System: LDS), and preferably an LDS method is used.

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

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

[0184]

[0185] Then, 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. The nitriding agent reacts with the precursor compound adsorbed on the substrate to form a nitride film.

[0186] Preferably, the nitriding agent can be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas.

[0187] The remaining unreacted reactant gas is then purged with an inert gas, which removes not only the excess reactant gas but also any by-products that are produced.

[0188] As described above, the thin film formation method, for example, has a unit cycle including the steps of supplying an activator onto a substrate, purging unadsorbed activator, adsorbing a precursor compound / thin film formation composition onto the substrate, purging unadsorbed precursor compound, supplying a reactant gas, and purging residual reactant gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0189] As another example, the thin film formation method has a unit cycle consisting of the steps of adsorbing a precursor compound / thin film formation composition onto a substrate, purging unadsorbed precursor compound, supplying an activator onto the substrate, purging unadsorbed activator, supplying a reactant gas, and purging residual reactant gas, and the unit cycle can be repeated to form a thin film of a desired thickness.

[0190] The unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film properties can be effectively exhibited.

[0191]

[0192] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the thin film formation method described above. In such a case, the thin film has excellent step coverage and thickness uniformity, and has excellent density and electrical properties.

[0193]

[0194] The thin film thus produced preferably has a thickness of 20 nm or less, a resistivity of 50 to 400 μΩ·cm based on a thin film thickness of 10 nm, a halogen content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within these ranges, the thin film has excellent performance as a diffusion barrier film and has the effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0195] The thin film may have a thickness of, for example, 0.1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 25 nm, and even more preferably 5 to 20 nm. Within this range, the thin film has excellent thin film properties.

[0196] The thin film may have a resistivity of, for example, 0.1 to 400 μΩ·cm, preferably 15 to 300 μΩ·cm, more preferably 20 to 290 μΩ·cm, and even more preferably 25 to 280 μΩ·cm, based on a thin film thickness of 10 nm. Within this range, the thin film has the effect of having excellent thin film characteristics.

[0197] The 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. 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 may be, for example, Cl2, Cl, or Cl. - The lower the amount of residual halogen in the thin film, the better the film quality will be, which is preferable.

[0198] As an example, the thin film has a step coverage of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even if the thin film has a complex structure, it can be easily deposited on a substrate, and has the advantage of being applicable to next-generation semiconductor devices.

[0199] The thin film thus produced preferably has a thickness of 20 nm or less, a carbon, nitrogen, and halogen content of 10,000 ppm or less based on a thickness of 10 nm, and a step coverage rate of 90% or more. Within these ranges, the thin film has the effect of exhibiting excellent performance as a dielectric film or blocking film, but is not limited thereto.

[0200]

[0201] The thin film may have a multilayer structure of two or three layers as required, for example. The multilayer film having a two-layer structure may have a structure of a lower layer film-middle layer film as a specific example, and the multilayer film having a three-layer structure may have a structure of a lower layer film-middle layer film-upper layer film as a specific example.

[0202] The underlayer film may, for example, comprise one or more selected from the group consisting of Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, and TiO2.

[0203] The intermediate layer is, for example, Ti x N y , preferably TN.

[0204] The upper layer film may contain, for example, one or more selected from the group consisting of W and Mo.

[0205]

[0206] Below, preferred embodiments and drawings are presented to deepen understanding of the present invention. However, the following embodiments and drawings are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the technical spirit thereof. It goes without saying that such changes and modifications are also included within the scope of the appended claims.

[0207]

[0208] [Example]

[0209] Examples 1 to 3, Comparative Examples 1 to 3

[0210] An ALD deposition process was carried out according to FIG. 1 below using the components shown in Table 1 below.

[0211] FIG. 1 is a schematic diagram illustrating a deposition process sequence according to the present invention, focusing on one cycle.

[0212] Specifically, 5N hydrogen iodide was prepared as the activating agent.

[0213] As precursors, bis(t-butylamino)silane (BTBAS), diisopropylaminosilane (DIPAS), and bisdiethylaminosilane (BDEAS) were prepared.

[0214] As shown in Figure 1 below, the prepared precursor compound was placed in a separate canister and supplied to a separate vaporizer heated to 100°C at a flow rate of 0.5g / min using a liquid mass flow controller (LMFC) at room temperature. The precursor vaporized in the vaporizer was introduced into the deposition chamber for 5 seconds, and then argon gas was supplied at 5000sccm for 30 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled to 2.5Torr.

[0215] The prepared activator was then introduced into the deposition chamber containing the substrate at room temperature at a flow rate of 500 sccm for 10 seconds using a mass flow controller (MFC), and argon gas was then supplied at 5000 sccm for 30 seconds to perform argon purging. At this time, the pressure inside the reaction chamber was controlled at 3 Torr.

[0216] Next, 3000 sccm of ammonia as a reactive gas was introduced into the reaction chamber for 10 seconds, and then argon purging was performed for 30 seconds. At this time, the substrate on which the metal thin film was to be formed was heated under the temperature conditions shown in Table 1 below.

[0217] This process was repeated 200 to 400 times to form a self-limiting atomic layer thin film with a thickness of 10 nm.

[0218] The deposition rate increase rate (D / R increase rate) and secondary ion mass spectrometry (SIMS) C impurities were measured for each of the obtained thin films of Examples 1 to 3 and Comparative Examples 1 to 3 by the following method, and the results are shown in Table 1 and FIG.

[0219] * Deposition rate increase rate (D / R (dep. rate) increase rate): This refers to the ratio of the deposition rate reduction after the introduction of the shielding agent compared to the D / R before the introduction of the activator, and was calculated as a percentage using the measured Å / cycle value.

[0220] Specifically, the film thickness of the thin film was measured using an ellipsometer, a device that can measure optical properties such as the film thickness and refractive index of a thin film using the polarization characteristics of light, and divided by the number of cycles to calculate the film thickness deposited per cycle.

[0221] [Table 1]

[0222] (BTBAS in Table 1 above is an abbreviation for bis(t-butylamino)silane.)

[0223] As shown in Table 1 above and FIG. 2 below, it was confirmed that Examples 1 to 3 using the activator according to the present invention not only showed a significant improvement in the increase rate of deposition rate, but also had excellent impurity reduction properties compared to Comparative Examples 1 to 3 not using the activator.

[0224] In particular, it was confirmed that Examples 1 to 3, in which the activator according to the present invention was used, showed an increase in the thin film growth rate per cycle of 9 to 14%, which was superior to Comparative Examples 1 to 3, in which the activator was not used.

[0225] The above results show that when the precursor compound is adsorbed to the surface and the bottom of the hole pattern, and then the activator according to the present invention is applied in a gas phase, the activator, which has a small molecular size, can easily reach the surface of the substrate and the inside of the hole pattern, and replace the ligands of the precursor compound adsorbed on the reaction surface with appropriate substituents.

[0226] The reactive gas, ammonia, which is injected afterwards also has a small molecular size and can easily reach the surface of the substrate and the inside of the hole pattern, thereby successfully forming a nitride film.

[0227] Therefore, it was confirmed that when the activator of the present invention is used in combination with aminosilane as a precursor compound and ammonia as a reactive gas, a nitride film can be effectively formed even on a substrate having a complex pattern.

Claims

1. An activator comprising a halogenated compound for replacing a ligand contained in a precursor compound represented by the following formula 1: [Chemical formula 1] 【Chemistry 1】 (In the above formula 1, M is at least one 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; L １ , L ２ , L ３ and L ４ is -H, -X, -R, -OR, or -NR ２ and may be the same or different, where -X is F, Cl, Br, or I, and -R is C １ ~C １０ Alkyl, C １ ~C １０ or C １ ~C １０ and may be linear or cyclic.

2. In the above formula 1, L １ , L ２ , L ３ and L ４ are -H or -R, which may be the same or different, where -R is C １ ~C １０ Alkyl, C １ ~C １０ or C １ ~C １０ 2. The activator according to claim 1, characterized in that it is an alkane of the formula (I) and substitutes a ligand having a linear or cyclic structure.

3. In the above formula 1, L １ , L ２ , L ３ and L ４ is -H, -OR, or -NR ２ may be the same or different, where -R is H, C １ ~C １０ Alkyl, C １ ~C １０ Alkenes of C １ ~C １０ 2. The activator according to claim 1, characterized in that it substitutes a ligand which is an alkane of iPr, iPr, or tBu.

4. In the above formula 1, L １ , L ２ , L ３ and L ４ is -H or -X, which may be the same or different, and where -X substitutes a ligand that is F, Cl, Br, or I.

5. The activator according to claim 1, wherein the halogen compound is at least one selected from the group consisting of hydrogen iodide, hydrogen iodide water, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, isopropyl iodide, and t-butyl iodide.

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

7. The activator according to claim 1, wherein the thin film activates a laminated film formed from one or more precursor compounds selected from the group consisting 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.

8. The activator according to claim 1 , wherein the thin film is used for forming a diffusion barrier film, an etching stop film, an electrode film, a dielectric film, a gate insulating film, a block oxide film, or a thin film for a charge trap.

9. A method for forming a thin film, comprising the step of injecting the activator according to any one of claims 1 to 8 into a chamber to replace ligands of a precursor compound adsorbed on a surface of a loaded substrate.

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

11. 10. The method of claim 9, wherein the activator is delivered into the chamber by a vapor flow control (VFC), direct liquid introduction (DLI) or liquid delivery system (LDS), and the thin film is a molybdenum film, a tungsten film, a silicon nitride film, a silicon oxide film, a titanium nitride film, a titanium oxide film, a tungsten nitride film, a molybdenum nitride film, a hafnium oxide film, a zirconium oxide film, a tungsten oxide film or an aluminum oxide film.

12. A semiconductor substrate manufactured by the thin film forming method according to claim 9.

13. The semiconductor substrate according to claim 12, wherein the thin film has a multi-layer structure of two or three layers.

14. A semiconductor device comprising the semiconductor substrate of claim 12.

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