Thin film precursor compound, thin film formation method using the same, and semiconductor substrate manufactured therefrom

Abstract

The present invention relates to a thin film forming method using a thin film precursor compound, a semiconductor substrate and a semiconductor device manufactured therefrom. According to the present invention, by using a thin film precursor compound represented by a predetermined chemical formula 2, the deposition rate is very fast, it is easy to handle when injected into a thin film deposition chamber, and in particular, since it has excellent thermal stability, it has a very high purity, excellent step coverage, and further suppresses side reactions and reduces the thin film growth rate. Even when forming a thin film on a substrate having a complex structure, the step coverage and the film thickness uniformity of the thin film can be significantly improved, and the density of the thin film can be improved to significantly improve the electrical characteristics of the thin film. There is an effect that a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom can be provided.

Description

Technical Field

[0001] The present invention relates to a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom. More specifically, since it is in a liquid state at room temperature, it has strong volatility and a very high vapor deposition rate, and is easy to handle when injected into a thin film vapor deposition chamber. In particular, due to its excellent thermal stability, it has a very high purity, and also has excellent step coverage. Furthermore, it suppresses side reactions and reduces the thin film growth rate. Even when forming a thin film on a substrate having a complex structure, it can significantly improve the step coverage and the film thickness uniformity of the thin film, improve the density of the thin film, and significantly improve the electrical properties of the thin film. The present invention relates to a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom.

Background Art

[0002] As the integration degree of existing two-dimensional planar semiconductor elements increases, the cell pitch becomes narrower, and accordingly, the generation of leakage current has become even more serious than before. To overcome this, 3D V(NAND) with a circuit stacked in a three-dimensional structure to increase the integration degree has been developed. In addition, when a thin film precursor material such as WF6 used as an electrode of a semiconductor element is adopted in CVD (H2 reduction), voids are generated by fluorine and a seam is generated in the cell, and the performance of the device deteriorates. In addition, an increase in resistance accompanying an increase in the number of NAND stages has been regarded as a problem. To overcome this, a Mo compound with a low specific resistance has been adopted. However, Mo compounds such as MoO2Cl2 currently in use have a problem that it is difficult to supply stably because the amount of sublimation is not constant since they are solids at room temperature.

[0003] [Prior Art Documents]

[0004] [Patent Documents]

[0005] (Patent Document 1) Korean Patent Publication No. 2006-0037241

Summary of the Invention

Problems to be Solved by the Invention

[0006] In order to solve the problems of the prior art as described above, since the present invention is in a liquid state at normal temperature, it has strong volatility and a very high vapor deposition rate, and is easy to handle when injected into a thin film vapor deposition chamber. In particular, because it has excellent thermal stability, it has very high purity, and also has excellent step coverage, suppresses side reactions and reduces the thin film growth rate, and removes process by-products in the thin film. Even when forming a thin film on a substrate having a complex structure, it is an object of the present invention to provide a thin film precursor compound capable of significantly improving step coverage and the film thickness uniformity of the thin film, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom.

[0007] The above object and other objects of the present invention can all be achieved by the present invention described below.

Means for Solving the Problems

[0008] In order to achieve the above object, the present invention provides a thin film precursor compound characterized by being represented by Chemical Formula 2.

[0009] [Chemical Formula 2]

[0010] ML1L2L3L4(L5) h (L6) i

[0011] (M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6; L1, L2, L3, L4, L5, and L6 are independently NRaRb; ORc; NRc; CO; RdCp; amidinate; guanidinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); Cp is cyclopentadienyl; Ra, Rb, Rc, and Rd are independently hydrogen or alkyl having 1 to 12 carbon atoms; h and i are independently 0 or 1; the overall oxidation number of the compound is an integer from -2 to 6; and one or more ligands selected from L1, L2, L3, L4, L5, and L6 are linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S).)

[0012] The thin film precursor compound may be a compound represented by the following Chemical Formula 3 or Chemical Formula 4.

[0013] [Chemical Formula 3]

[0014] [Chem.]

[0015] [Chemical Formula 4]

[0016] [Chem.]

[0017] (In the above Chemical Formulas 3 to 4, M is at least one selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, and R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, dimethylamine group, substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, and substituted or unsubstituted alkoxy group having 1 to 7 carbon atoms, and n is an integer from 0 to 2.)

[0018] The thin film precursor compound may be obtained using a compound represented by the following Chemical Formula 1 as an intermediate.

[0019] [Chemical Formula 1]

[0020] Mo(O)n(X)m(L)k

[0021] (Wherein Mo is molybdenum, O is oxygen, X is halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 1 to 3.)

[0022] The ligand may be a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S).

[0023] The intermediate may be (tBuN=)2MoCL2(DAE) (where DAE is a dialkoxyethane having 1 to 15 carbon atoms).

[0024] The thin film precursor compound may be liquid under the conditions of 20 °C and 1 bar and may have volatility.

[0025]

[0026] In addition, the present invention relates to Chemical Formula 2

[0027] [Chemical Formula 2]

[0028] ML1L2L3L4(L5) h (L6) i

[0029] (Wherein M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr) and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, and L1, L2, L3, L4, L5 and L6 are independently NRaRb; ORc; NRc; CO; RdCp; amidinate; guanidinate; ethylenediamine; propylenediamine; and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); Cp is cyclopentadienyl, Ra, Rb, Rc and Rd are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and i are independently 0 or 1, the overall oxidation number of the compound is an integer from -2 to 6, and one or more ligands selected from L1, L2, L3, L4, L5 and L6 are linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S).) Provided is a thin film forming method including a step of injecting a thin film precursor compound represented by the formula into a chamber and depositing it on the surface of a substrate carried in (loaded).

[0030]

[0031] The deposition step may include a step of vaporizing the thin film precursor compound and adsorbing it on the surface of a substrate carried into the chamber, a step of purging the inside of the chamber with a purge gas, a step of supplying a reaction gas into the chamber, and a step of purging the inside of the chamber with a purge gas.

[0032] In the vapor deposition step, the thin film precursor compound and the reaction gas can be simultaneously injected onto a substrate carried into the chamber.

[0033] The vapor deposition step can be carried out by an Atomic Layer Deposition (ALD process), a Chemical Vapor Deposition (CVD process), a Plasma Enhanced Atomic Layer Deposition (PEALD process), or a Plasma Enhanced Chemical Vapor Deposition (PECVD process).

[0034] In the thin film forming method, a nitriding agent, an oxidizing agent, or a reducing agent can be used as the reaction gas.

[0035] The thin film may include a metal nitride thin film, a metal oxide thin film, or a metal thin film.

[0036]

[0037] Furthermore, the present invention provides a semiconductor substrate manufactured by the thin film forming method described above.

[0038] Furthermore, the present invention provides a semiconductor device including the semiconductor substrate described above.

Advantages of the Invention

[0039] According to the present invention, since it is in a liquid state at room temperature, it has strong volatility and a very high vapor deposition rate, is easy to handle when injected into a thin film vapor deposition chamber, and in particular, because of its excellent thermal stability, it has a very high purity. Moreover, it has excellent step coverage, and further suppresses side reactions to lower the thin film growth rate and removes process by-products in the thin film. Even when forming a thin film on a substrate having a complex structure, it is possible to significantly improve the step coverage and the film thickness uniformity of the thin film. There is an effect that a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate manufactured therefrom can be provided.

Brief Description of the Drawings

[0040]

Figure 1

[0041]

Figure 2

[0042]

Figure 3

[0043]

Figure 4

[0044]

Figure 5

Embodiments for Carrying Out the Invention

[0045] Hereinafter, the thin film precursor compound described herein, the thin film formation method using the same, and the semiconductor substrate manufactured therefrom will be described in detail.

[0046] When the inventors adsorb a thin-film precursor compound having a predetermined structure on the surface of a substrate carried into the ALD chamber, since it is in a liquid state at room temperature, it has strong volatility, a very high vapor deposition rate, and is easy to handle when injected into the thin-film vapor deposition chamber. In particular, since it has excellent thermal stability, it has a very high purity, and it has been confirmed that step coverage and thin-film uniformity are improved. In addition, it has been confirmed that the amount of halides remaining as process by-products is significantly reduced, and as a result, the density, resistivity, etc. of the thin film are greatly improved. Based on such results, the inventors further conducted research on the thin-film precursor compound and completed the present invention.

[0047]

[0048] The thin-film precursor compound according to one aspect of the present invention has the following Chemical Formula 2

[0049] [Chemical Formula 2]

[0050] ML1L2L3L4(L5) h (L6) i

[0051] (M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr) and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, and L1, L2, L3, L4, L5 and L6 are independently NRaRb; ORc; NRc; CO; RdCp; amidinate; guanidinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); selected from the group consisting of Cp is cyclopentadienyl, Ra, Rb, Rc and Rd are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and i are independently 0 or 1, the overall oxidation number of the compound is an integer from -2 to 6, and one or more ligands selected from L1, L2, L3, L4, L5 and L6 are linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S).) It is characterized by being a compound represented by, and in this case, since it is in a liquid state at normal temperature, it has strong volatility and a very high deposition rate, is easy to handle when injected into a thin film deposition chamber, and especially has excellent thermal stability, so it has a very high purity and the effect of improving the step coverage.

[0052] The thin film precursor compound is represented by the following Chemical Formula 3 or Chemical Formula 4

[0053] [Chemical Formula 3] [Chemical Structure]

[0054]

[0055] [Chemical Formula 4]

[0056] [Chemical Structure]

[0057] (In the above Chemical Formulas 3 to 4, M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, and R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, a dimethylamine group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 7 carbon atoms, and n is an integer from 0 to 2.) It can be selected from among the compounds represented by this formula. In this case, since it is in a liquid state at normal temperature, it has strong volatility and a very high vapor deposition rate, is easy to handle when injected into a thin film vapor deposition chamber, and moreover, it induces selective bonding to suppress film contamination as much as possible, is easily removed by a reaction gas, has high purity, and has the advantage of excellent step coverage.

[0058] In the above Chemical Formulas 3 to 4, M can be one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), and has a charge of 0, +3, +4, +5, +6 and a coordination number of 6.

[0059] In the above Chemical Formulas 3 to 4, R1, R2, R3, R4, and R5 can be independently selected from the group consisting of H, a substituted or unsubstituted alkyl having 1 to 7 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 7 carbon atoms, and dimethylamine.

[0060] In the above Chemical Formulas 3 to 4, R1 and R5 can be independently selected from H and C1-C7 substituted or unsubstituted alkyls. As an example, they can be selected from methyl, ethyl, propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, sec-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, iso-hexyl, sec-hexyl, tert-hexyl, neo-butyl, iso-butyl, tert-butyl, tert-pentyl, neo-pentyl, hexane, iso-hexane, neo-hexane, heptane, iso-heptane, and neo-heptane.

[0061] In the above Chemical Formulas 3 to 4, R2 can be independently selected from the group consisting of H and C1-C7 substituted or unsubstituted alkyls. As an example, it can be selected from methyl, ethyl, propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, sec-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, iso-hexyl, sec-hexyl, tert-hexyl, neo-butyl, iso-butyl, tert-butyl, tert-pentyl, neo-pentyl, hexane, iso-hexane, neo-hexane, heptane, iso-heptane, and neo-heptane.

[0062] In the above Chemical Formulas 3 to 4, R3 and R4 can be independently selected from the group consisting of H and C1-C7 substituted or unsubstituted alkyls. As an example, they can be selected from methyl, ethyl, propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, sec-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, iso-hexyl, sec-hexyl, tert-hexyl, neo-butyl, iso-butyl, tert-butyl, tert-pentyl, neo-pentyl, hexane, iso-hexane, neo-hexane, heptane, iso-heptane, and neo-heptane.

[0063] In this description, C1-C7 alkyl may include, for example, one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a neo-pentyl group, a tert-butyl group and isomers thereof, but is not limited thereto.

[0064] In this description, C1-C7 alkoxy may include, for example, one selected from the group consisting of a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, a tert-butoxy group and isomers thereof, but is not limited thereto.

[0065] In the above Chemical Formula 3 and Chemical Formula 4, n may be an integer from 0 to 2.

[0066]

[0067] As a specific example, in the above Chemical Formula 3 to Chemical Formula 4, M is Mo (molybdenum), R1 and R5 are each independently selected from the group consisting of H and C1-C7 substituted and unsubstituted alkyl, R3 and R4 are each independently selected from the group consisting of H and C1-C5 substituted or unsubstituted alkyl, R2 may be each independently selected from the group consisting of H, C1-C5 substituted or unsubstituted alkyl, C1-C7 substituted or unsubstituted alkoxy and dimethylamine, and n may be an integer from 0 to 2.

[0068] Further, M is W (tungsten), R1 and R5 are each independently selected from the group consisting of H and substituted and unsubstituted alkyls having 1 to 7 carbon atoms, R3 and R4 are each independently selected from the group consisting of H and substituted or unsubstituted alkyls having 1 to 5 carbon atoms, R2 can be each independently selected from the group consisting of H, substituted or unsubstituted alkyls having 1 to 5 carbon atoms, substituted or unsubstituted alkoxys having 1 to 7 carbon atoms, and dimethylamine, and n can be an integer from 0 to 2.

[0069] Furthermore, M is Cr (chromium), R1 and R5 are each independently selected from the group consisting of H and substituted and unsubstituted alkyls having 1 to 7 carbon atoms, R3 and R4 are each independently selected from the group consisting of H and substituted or unsubstituted alkyls having 1 to 5 carbon atoms, R2 can be each independently selected from the group consisting of H, substituted or unsubstituted alkyls having 1 to 5 carbon atoms, substituted or unsubstituted alkoxys having 1 to 7 carbon atoms, and dimethylamine, and n can be an integer from 0 to 2.

[0070]

[0071] The thin film precursor compound according to one aspect of the present invention is, as an example, the following Chemical Formula 1

[0072] [Chemical Formula 1]

[0073] Mo(O)n(X)m(L)k

[0074] (wherein Mo is molybdenum, O is oxygen, X is a halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 1 to 3). It can be obtained using the compound represented as an intermediate. In this case, since it is in a liquid state at normal temperature, it has strong volatility and a very high vapor deposition rate, is easy to handle when injected into a thin film vapor deposition chamber, and in particular, induces selective bonding to suppress film contamination as much as possible, is easily removed by reaction gas, has high purity, and has the advantage of excellent step coverage.

[0075] When the ligand is a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S), it is in a liquid state at room temperature. Therefore, it has strong volatility, a very high vapor deposition rate, and is easy to handle when injected into a thin film vapor deposition chamber. In particular, it can induce selective binding to minimize film contamination, and is also easily removed by a reaction gas. In addition, it has the advantages of high purity and excellent step coverage.

[0076] The intermediate can preferably be produced by subjecting a molybdenum compound selected from the group consisting of MoX6, MoO2X2, MoOX4, MoO2X2, and MoO2X4 (where X represents a halogen) to a substitution reaction with the ligand.

[0077] As a specific example, the ligand can be t-butylamine, chlorotrimethylsilane, and 1,2-dimethoxyethane used in Synthesis Example 1 described later, but is not limited thereto.

[0078] The intermediate can preferably be (tBuN=)2MoCL2(DAE) (where DAE is a dialkoxyethane having 1 to 15 carbon atoms). Here, DAE can be, for example, DME (dimethoxyethane), DEE (diethoxyethane), or DEME (diethylmethoxy ethane), but is not limited thereto.

[0079] Since the thin film precursor compound obtained using the intermediate described above in the present invention is in a liquid state at room temperature, it has strong volatility, a very high vapor deposition rate, and is easy to handle when injected into a thin film vapor deposition chamber. In particular, it can induce selective binding to minimize film contamination, and is also easily removed by a reaction gas. In addition, it has the advantages of high purity and excellent step coverage.

[0080] The thin film precursor compound is preferably liquid under the conditions of 20°C and 1 bar and is characterized by being volatile. In this case, the vapor deposition rate is very fast, it is easy to handle when injected into the thin film deposition chamber, and moreover, because it has excellent thermal stability, it has a very high purity, excellent step coverage, and further suppresses side reactions and reduces the thin film growth rate. Even when forming a thin film on a substrate having a complex structure, it is possible to significantly improve the step coverage and the film thickness uniformity of the thin film, and there is an advantage of improving the density of the thin film and significantly improving the electrical properties of the thin film.

[0081] For reference, the reactants introduced into atomic layer deposition (ALD) are required to have high volatility, stability of the substance, and high reactivity. In the atomic layer deposition method (ALD), a thin film of less than a monolayer grows by surface reaction during one cycle of vapor deposition by supplying the reaction raw materials separately. The ligand of the reaction raw material adsorbed on the substrate is removed by a chemical reaction with other reaction raw materials supplied later. Therefore, when heating the precursor, which is a reactant for atomic layer vapor deposition, in the liquid phase is much more advantageous than in the solid phase in terms of reaction rate and process.

[0082] Here, the volatility means the volatility shown in a chamber at 300°C or higher unless otherwise specified in this specification. In this case, it is suitable for showing the effect of being uniformly distributed on the substrate.

[0083] The thin film precursor compound according to one aspect of the present invention can not only exist in a liquid state at room temperature by coordinating a hetero ligand to the central metal, but also exhibit improved vapor pressure and the like.

[0084] The above chemical formula 1, specifically, the thin film precursor compounds represented by the above chemical formula 3 or chemical formula 4, each have excellent thermal stability, so low-temperature deposition is also possible. For reference, when expanding the -NR5-C=C-NR3R4 fraction contained in the heteroligand, as the chain becomes longer, coordination bonds to other sides rather than the central metal side become possible, so there is a risk of being disadvantageous for deposition by chemical vapor deposition (CVD), metalorganic chemical vapor deposition (MOCVD), low-pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD).

[0085] In contrast, the above chemical formula 1 obtained using the aforementioned intermediate, specifically, the thin film precursor compounds represented by chemical formula 3 to chemical formula 4, can be purified under the conditions of 0.4 torr and 170 to 180 °C, which are relatively low temperatures. Therefore, not only do they have a relatively favorable vapor pressure for the evaluation of deposition, but they also have the advantage of providing the properties of a liquid phase.

[0086] Furthermore, the above chemical formula 1 obtained using the aforementioned intermediate, specifically, the thin film precursor compounds represented by chemical formula 3 to chemical formula 4, have low reactivity with moisture and no concern of spontaneous ignition, so they are easy to handle. Since they have a high vapor pressure, they are useful for forming thin films using deposition processes such as chemical vapor deposition and atomic layer deposition.

[0087] In particular, when forming a film, the physical properties of the thin film according to the process temperature show an ALD window region in the temperature range of 330 to 370 °C and can be used as an ALD precursor having a constant film-forming temperature in this range, thereby reducing the process cost.

[0088]

[0089] The thin film forming method of the present invention includes a step of injecting a thin film precursor compound represented by the aforementioned Chemical Formula 1, specifically, Chemical Formula 3 or Chemical Formula 4, into a chamber and depositing it on the surface of a substrate that has been loaded therein. In such a case, since it is in a liquid state at room temperature, it has strong volatility, a very high deposition rate, and is easy to handle when injecting into a thin film deposition chamber. Moreover, because it has excellent thermal stability, it has a very high purity, and also has excellent step coverage. By suppressing side reactions and reducing the thin film growth rate, and removing process by-products in the thin film, even when forming a thin film on a substrate having a complex structure, there is an advantage that the step coverage and the film thickness uniformity of the thin film can be significantly improved.

[0090] The thin film forming method of the present invention may include a step of vaporizing a thin film precursor compound represented by the aforementioned Chemical Formula 1, specifically, Chemical Formula 3 or Chemical Formula 4, and adsorbing it on the surface of a substrate loaded into a chamber, a step of purging the inside of the chamber with a purge gas, a step of supplying a reaction gas into the chamber, and a step of purging the inside of the chamber with a purge gas.

[0091] In the deposition step, the thin film precursor compound and the reaction gas may be sequentially or simultaneously injected into the substrate loaded into the chamber.

[0092]

[0093] The thin film forming method, except for using a thin film precursor compound represented by Chemical Formula 1, specifically, a thin film precursor compound of Chemical Formula 3 or Chemical Formula 4, is a normal method for manufacturing a metal thin film, for example, Atomic Layer Deposition (ALD process), Chemical Vapor Deposition (CVD process), Plasma Enhanced Atomic Layer Deposition (PEALD process), or Plasma Enhanced Chemical Vapor Deposition (PECVD process), and can preferably be carried out by chemical vapor deposition or atomic layer deposition, but is not limited thereto.

[0094] Specifically, the metal thin film is obtained by gasifying one or more of the thin film precursor compounds represented by the above Chemical Formula 1, specifically, the above Chemical Formulas 3 to 4, and supplying them onto a substrate, for example, a substrate such as TiN, SiO2, Si3N4, etc., and then decomposing the precursor.

[0095] The thin film precursor compound can be injected onto the substrate under temperature conditions suitable for the properties of the substance, and the deposition process conditions can be variously changed according to the deposition efficiency.

[0096] When considering the efficiency of the deposition process, the thin film precursor compound is preferably injected in a heated state. As an example, it can be injected onto the substrate for 1 to 20 seconds under temperature conditions of 50 to 400 °C, specifically, 50 to 350 °C.

[0097] At this time, as a method for gasifying the thin film precursor compound, a method including a step of purging the unadsorbed thin film precursor compound with an inert gas and then injecting a reaction gas can be mentioned.

[0098] Specifically, a method of directly vaporizing the thin film precursor compound or a method of injecting the thin film precursor compound into a thermostatic bath and then supplying an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to gasify it can be used.

[0099] The decomposition process of the thin film precursor compound can be carried out by methods such as heat treatment, plasma treatment, or light irradiation. At this time, it can be carried out in the presence of reactive gases such as water vapor, oxygen, ozone, hydrogen, ammonia, hydrazine, and silane. When the decomposition process of the thin film precursor compound is carried out in the presence of an oxidizing agent such as water vapor, oxygen, or ozone as a reaction gas, a metal oxide thin film can be formed. When the decomposition process of the thin film precursor compound is carried out using a reducing agent such as hydrogen, ammonia, hydrazine, or silane as a reaction gas, a metal thin film can be formed. When the decomposition process of the thin film precursor compound is carried out using a nitriding agent such as nitrogen, ammonia, or hydrazine as a reaction gas, a metal nitride thin film can be formed.

[0100] As a specific example, when decomposing the thin film precursor compound by heat treatment, the process can be carried out under temperature conditions of 100 to 1000 °C. The deposition temperature of the substrate can be, for example, 50 to 400 °C, preferably 200 to 400 °C.

[0101] As an example, the supply time (Feeding Time, sec) of the thin film precursor compound to the surface of the substrate per cycle can preferably be 1 to 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably 2 to 4 seconds. Within this range, there is an advantage of excellent step coverage and economy.

[0102] The supply time (Feeding Time) of the thin film precursor compound described above is based on, for example, a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s. More specifically, it is based on a chamber volume of 18 L and a flow rate of 1 to 2 mg / s.

[0103] The thin film precursor compound can preferably be conveyed into the chamber by a vapor flow control (VFC) method, a direct liquid introduction (DLI) method, or a liquid delivery system (LDS) method, and more preferably, can be conveyed into the chamber by a liquid delivery system (LDS) method.

[0104] In this description, the purge is preferably 1,000 to 10,000 sccm (standard cubic centimeters per minute), more preferably 2,000 to 7,000 sccm, and even more preferably 2,500 to 6,000 sccm. Within this range, the thin film growth rate per cycle decreases to a suitable range, and there is an effect of reducing process by-products.

[0105] The vapor deposition according to the present invention can be performed using vapor deposition equipment commonly used in the art. In the examples described later, a thin film can be manufactured by atomic layer deposition (ALD) using the vapor deposition apparatus shown in FIG. 4 below.

[0106] FIG. 4 below is a schematic diagram showing a vapor deposition apparatus for performing the atomic layer deposition method according to the present invention using NH3 gas as a nitriding agent. The source line and the reaction gas line were operated separately to maximize the properties of the substance by adjusting the temperature suitable for each property. However, manufacturing using an apparatus that operates the source line and the reaction gas line together does not deviate from the scope of the present invention.

[0107] Further, the present invention can include a thin film manufacturing apparatus capable of realizing the thin film manufacturing method, including an ALD chamber, a first vaporizer for vaporizing the thin film precursor compound, a first conveying means for conveying the vaporized thin film precursor compound into the ALD chamber, and a second conveying means for conveying the reaction gas into the ALD chamber. Here, the vaporizer and the conveying means are not particularly limited when they are vaporizers and conveying means commonly used in the technical field to which the present invention belongs.

[0108]

[0109] In the method for producing a metal-containing thin film according to the present invention as described above, by using a thin film precursor compound having excellent thermal stability, in the vapor deposition process, the vapor deposition process can be carried out at a lower temperature compared to the prior art. Without particle contamination and impurity contamination such as carbon caused by thermal decomposition of the precursor, the crystallinity can be improved, and a high-purity metal thin film, metal oxide or metal nitride thin film can be formed at a high vapor deposition rate without process by-products.

[0110] The thin film forming method according to the present invention can use known film quality improvers, thin film growth inhibitors, thin film growth activators, etc. in the art as needed.

[0111] Also, in this specification, the ALD chamber and the ALD process are described as examples, but it should be noted that the present invention is not limited thereto. For reference, ALD (Atomic Layer Deposition process) is very advantageous in the production of integrated circuits (ICs) that require a high aspect ratio. In particular, due to its self-limiting thin film growth mechanism, it has advantages such as excellent step coverage, uniform coating, and high-definition thickness control.

[0112] The thin film forming method can be carried out, for example, at a vapor deposition temperature in the range of 50 to 900°C, preferably at a vapor deposition temperature in the range of 300 to 700°C, more preferably at a vapor deposition temperature in the range of 350 to 600°C, still more preferably at a vapor deposition temperature in the range of 400 to 550°C, and even more preferably at a vapor deposition temperature in the range of 400 to 500°C. Within this range, while realizing the characteristics of the ALD process, there is an effect of growing a thin film with excellent film quality.

[0113] The thin film forming method can be carried out, for example, at a deposition pressure in the range of 0.1 to 10 Torr, preferably at a deposition pressure in the range of 0.5 to 5 Torr, and most preferably at a deposition pressure in the range of 1 to 3 Torr. Within this range, there is an effect that a thin film with a uniform film thickness can be obtained.

[0114] In this description, the deposition temperature and the deposition pressure can be measured as the temperature and pressure formed in the deposition chamber, or can be measured as the temperature and pressure applied to the substrate in the deposition chamber.

[0115] The thin film forming method preferably includes a step of raising the temperature in the chamber to the deposition temperature before introducing the thin film precursor compound into the chamber, and / or a step of injecting an inert gas into the chamber and purging it before introducing the thin film precursor compound into the chamber.

[0116]

[0117] As a specific example, to explain the thin film forming method, first, a substrate on which a thin film is to be formed is placed in a deposition chamber where atomic layer deposition is possible.

[0118] The substrate can cover semiconductor substrates such as silicon substrates and silicon oxides.

[0119] The substrate may further have a conductive layer or an insulating layer formed on its upper part.

[0120] To deposit a thin film on the substrate placed in the deposition chamber, the above-described thin film precursor compound is prepared.

[0121] Thereafter, the prepared thin film precursor compound is injected into a vaporizer, then changed into a vapor phase, transferred to the deposition chamber, adsorbed on the substrate, and the unadsorbed thin film precursor compound is purged.

[0122] In this description, as a method for delivering a thin film precursor compound or the like to a deposition chamber, as an example, a method of transporting a volatilized gas by utilizing a Mass Flow Controller (MFC) method (Vapor Flow Control; VFC) or a method of transporting a liquid by utilizing a Liquid Mass Flow Controller (LMFC) method (Liquid Delivery System; LDS) can be used, and preferably, the LDS method is used.

[0123] At this time, as the carrier gas or dilution gas for moving the thin film precursor compound and the precursor compound or the like onto the substrate, one or more mixed gases selected from argon (Ar), nitrogen (N2), and helium (He) can be used, but it is not limited thereto.

[0124] In this description, as the purge gas, as an example, an inert gas can be used, and preferably, the carrier gas or dilution gas can be used.

[0125]

[0126] Next, a reaction gas is supplied. The reaction gas can be used without any particular limitation when it is a reaction gas commonly used in the technical field to which the present invention belongs, and preferably, it may contain a reducing agent, a nitriding agent, or an oxidizing agent. The reducing agent reacts with the thin film precursor compound adsorbed on the substrate to form a metal thin film, a metal nitride thin film is formed by the nitriding agent, and a metal oxide thin film is formed by the oxidizing agent.

[0127] Next, the unreacted residual reaction gas is purged using an inert gas. Thereby, not only the excess reaction gas but also the generated by-products can be removed together.

[0128] As described above, a step of adsorbing a thin film precursor compound onto a substrate, a step of purging the unadsorbed composition for forming a thin film, a step of supplying a reaction gas, and a step of purging the residual reaction gas are defined as a unit cycle, and the unit cycle can be repeated in order to form a thin film having a desired film thickness.

[0129] The unit cycle can be, for example, 100 to 1,000 times, preferably 100 to 500 times, more preferably 150 to 300 times. Within this range, there is an effect that the desired thin film characteristics are well exhibited.

[0130] Conventionally, when a molybdenum-based thin film precursor (for example, MoO2Cl2) compound in a solid state is used under the conditions of 20°C and normal pressure in an ALD process, the solid is difficult to sublime and reacts with a reaction gas (for example, NH3), resulting in residues of process by-products such as NH4Cl and HCl in the thin film, thereby degrading the performance of the substrate due to corrosion and deterioration. However, when the thin film precursor compound according to the present invention is used, the thermal stability is improved, the deposition rate is increased, and process by-products such as NH4Cl and HCl generated by reacting with a reaction gas (for example, NH3) are removed together with the thin film precursor compound, thereby preventing corrosion and deterioration of the substrate, improving not only the step coverage and the uniformity of the thin film thickness, but also improving the density of the thin film and providing excellent electrical characteristics.

[0131]

[0132] According to another aspect of the present invention, a metal-containing film produced by the thin film forming method is provided.

[0133] The metal-containing film can be a metal nitride film, a metal oxide film, or a metal film depending on the reaction gas used. Such a metal-containing film can be a thin film having high conformity and thin film uniformity, together with the accuracy of thickness control, even when having a complex structure.

[0134] The semiconductor substrate of the present invention is characterized by being manufactured by the thin film forming method described herein. In such a case, by improving the deposition rate and removing process by-products in the thin film, corrosion and deterioration are prevented, and there is an effect that the step coverage and the film thickness uniformity of the thin film are extremely excellent.

[0135] The semiconductor substrate includes a base material such as a wafer and a thin film formed on the base material. The thin film may include those manufactured by the method described above.

[0136] The manufactured thin film preferably has a film thickness of 20 nm or less, a specific resistance value of 0.1 to 400 μΩ·cm, a halogen content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within this range, the performance as a diffusion prevention film is excellent, and there is an effect that the corrosion of the metal wiring material is reduced, but it is not limited to this.

[0137] The thin film may have a film thickness of, for example, 5 to 20 nm, preferably 10 to 20 nm, more preferably 15 to 18.5 nm, and even more preferably 17 to 18.5 nm. Within this range, there is an effect that the thin film characteristics are excellent.

[0138] The thin film may have a specific resistance value of, for example, 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm, and more preferably 100 to 300 μΩ·cm. Within this range, there is an effect that the thin film characteristics are excellent.

[0139] The halogen content of the thin film is more preferably 9,000 ppm or less or 1 to 9,000 ppm, even more preferably 8,500 ppm or less or 100 to 8,500 ppm, and even more preferably 8,200 ppm or less or 1,000 to 8,200 ppm. Within this range, while the thin film characteristics are excellent, there is an effect that the corrosion of the metal wiring material is reduced.

[0140] The thin film, as an example, has a step coverage rate of 80% or more, preferably 90% or more, more preferably 92% or more. Within this range, even for a thin film with a complex structure, it can be easily deposited on a substrate and has the advantage of being applicable to next-generation semiconductor devices.

[0141] The manufactured thin film can be, for example, a Mo thin film, a MoN thin film, a MoO thin film, a MoS2 thin film, or a MoSe2 thin film.

[0142]

[0143] According to still another aspect of the present invention, a semiconductor element including the semiconductor substrate is provided.

[0144] The semiconductor element can be, for example, low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal capacitor, a DRAM trench capacitor, 3D Gate-All-Around (GAA), or 3D NAND.

[0145]

[0146] Hereinafter, preferred examples are presented to deepen the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea. Such modifications and changes naturally belong to the scope of the appended claims.

[0147] [Example]

[0148] Synthesis Example 1: Synthesis of (tBuN=)2MoCL2(DME)

[0149] (tBuN=)2MoCL2DME was synthesized from Na2MoO4 according to the following reaction formula 1.

[0150] [Reaction formula 1]

[0151] TIFF2025518867000006.tif29168

[0152] Specifically, 67 g (486 mmol) of Na2MoO4, 1 L of 1,2-dimethoxyethane, 180 mL of trimethylamine, 374 mL of chlorotrimethylsilane, and 80 mL of t-butylamine were sequentially added to a 3 L reaction flask under an atmosphere of dry argon gas, and the reaction was carried out over 24 hours while refluxing under temperature conditions of 65 °C. After that, the completion of the reaction was confirmed using NMR.

[0153] Unless otherwise specified, all substances used in the above reaction formula were synthesized and purified and used as products with a purity of 99% or higher. After filtering the obtained yellow solution, it was washed with hexane, and the filtrate was dried under vacuum. The obtained solid was repeatedly washed with hexane to obtain 27 g of (tBuN=)2MoCL2(DME) (yield rate: 21 wt%). By performing NMR analysis on this, it was confirmed that an intermediate of the (tBuN=)2MoCL2DME structure was obtained.

[0154] 1 H NMR (in C6D6) (3.48 ppm, s, 6H), (3.22 ppm, s, 4H) (1.42 ppm, s, 18H)

[0155]

[0156] Synthesis example 2: Synthesis of (tBuN=)2Mo(TBDMAE)(DMA)

[0157] (tBuN=)2Mo(TBDMAE)(DMA) was synthesized from (tBuN=)2MoCL2(DME) obtained in the above synthesis example 1 according to the following reaction formula 2.

[0158] [Reaction Formula 2]

[0159] TIFF2025518867000007.tif31160

[0160] Specifically, after adding 95.5 g (239.2 mmol) of (tBuN=)2MoCL2DME to a 1 L Schlenk flask, 160 ml of anhydrous toluene was added, and it was cooled to -5 °C using ethanol and dry ice.

[0161] 12.2 g (239.2 mmol) of lithium dimethylamine [LiDMA] dissolved in 30 ml of toluene was added dropwise to the 1 L Schlenk flask using a cannula, stirred at room temperature for 2 hours, and the synthesis was confirmed using NMR.

[0162] Next, 38 g of Li-TBDMAE synthesized separately was dissolved in hexane and added dropwise at -5 °C to the 1 L Schlenk flask. Here, the abbreviation TBDMAE means 1-(tert-butylamino)-2-(dimethylamino)ethane. After terminating the reaction using NMR, it was filtered to remove the solvent.

[0163] The obtained compound was purified through a purification tube, and 20 g (yield rate: 30 wt%) of pure (tBuN=)2Mo(TBDMAE)(DMA) was obtained. 1 The results of 1H NMR analysis are shown in Figure 1 below.

[0164] As is clear from Figure 1 below, 1 It was confirmed that the substance synthesized using 1H NMR analysis was (tBuN=)2Mo(TBDMAE)(DMA), the substance to be manufactured.

[0165]

[0166] Synthesis Example 3: Synthesis of (tBuN=)2Mo(TBDMAE)(tBuO)

[0167] Using (tBuN=)2MoCL2(DME) obtained in Synthesis Example 1 above, (tBuN=)2Mo(TBDMAE)(tBuO) was synthesized according to the following Reaction Formula 3.

[0168] [Reaction Formula 3]

[0169] TIFF2025518867000008.tif33154

[0170] Specifically, 4.43 mL (25 mmol) of TBDMAE and 30 mL of anhydrous hexane were stirred in a 100 mL Schlenk flask, and 10 mL (25 mmol) of n-BuLi was added at 0 °C. After stirring for 30 minutes, 2.41 g (25 mmol) of sodium tert-butoxide was mixed. Here, the abbreviation TBDMAE means 1-(tert-butylamino)-2-(dimethylamino)ethane.

[0171] The above mixture was cooled to 0 °C or below and added to a 250 mL Schlenk flask together with 10 g (25 mmol) of (tBuN=)2MoCL2(DME) and 50 mL of anhydrous toluene, and then stirred at room temperature for 12 hours.

[0172] Separately synthesized Li-TBDMAE (38 g) was dissolved in hexane and added dropwise to the 250 mL Schlenk flask at -5 °C.

[0173] The stirred solution was filtered, and the filtrate was concentrated under reduced pressure to obtain (tBuN=)2Mo(TBDMAE)(tBuO).

[0174] The obtained crude (tBuN=)2Mo(TBDMAE)(tBuO) was purified to obtain 5 g of a brown liquid (yield rate: 50 wt%). 1 As a result of performing 1H NMR analysis, it was confirmed that the compound represented by (tBuN=)2Mo(TBDMAE)(tBuO) to be produced was synthesized.

[0175]

[0176] [Test Example 1] Confirmation of the Properties of the Thin Film Precursor Compound

[0177] As a result of confirming the properties of the thin film precursor compounds produced in Synthesis Examples 1 to 2 at 20°C and 1 atm, it was confirmed that all were in a liquid state and had high volatility.

[0178]

[0179] [Test Example 2] Thermogravimetric Analysis (TG analysis) of the Thin Film Precursor Compound

[0180] Thermogravimetric analysis (TG analysis) of the thin film precursor compounds produced in Synthesis Examples 1 to 2 was carried out.

[0181] The instrument used for the thermogravimetric analysis (TGA) was a TGA / DSC 1 STARe System manufactured by Mettler Toledo, and an alumina crucible with a capacity of 50 μL was used. The content of all samples was 8 - 11 mg, and the measurement was carried out from 30°C to 500°C.

[0182] The measured results of the thermogravimetric analysis are shown in Figures 2 - 3 below respectively. Figure 2 below is a diagram showing the differential scanning calorimetry - thermogravimetric analysis (DSC - TG analysis) results of the thin film precursor compound synthesized in Synthesis Example 2, and Figure 3 below is a diagram showing the differential scanning calorimetry analysis (DSC analysis) results of the thin film precursor compound synthesized in Synthesis Example 2.

[0183] As is clear from FIGS. 2 to 3 below, it was confirmed that the T1 / 2 of the thin film precursor compound (tBuN=)2Mo(TBDMAE)(DMA) obtained in Synthesis Example 2 was 118° C. and the Tend was 237° C., and it was confirmed that it showed excellent thermogravimetric analysis values. Further, in the case of the thin film precursor compound (tBuN=)2Mo(TBDMAE)(tBuO) obtained in Synthesis Example 3, it can be confirmed that the thermogravimetric analysis value is even larger than that of the thin film precursor compound (tBuN=)2Mo(TBDMAE)(DMA) obtained in Synthesis Example 2.

[0184] Furthermore, as a result of performing heat flow analysis, it was found that the thin film precursor compound of the present invention decomposes into one pattern (see the graph of the blue ink in FIG. 2 below).

[0185]

[0186] [Examples]

[0187] Examples 1 to 4

[0188] The thin film precursor compound described in Table 1 was put into a canister and supplied to a vaporizer using a liquid mass flow controller (LMFC) at room temperature.

[0189] After the thin film precursor compound vaporized into the vapor phase in the vaporizer was introduced into a deposition chamber into which a substrate was carried, atomic layer deposition (ALD) was performed using the deposition equipment shown in FIG. 4 below under the deposition temperature conditions described in Table 1 to form a film.

[0190] Specific deposition conditions are further shown in Table 2 below.

[0191]

Table 1

[0192]

[0193]

Table 2

[0194]

[0195] The thin film precursor compound was placed in a stainless steel canister, and at room temperature, it was supplied to a vaporizer heated to 150 °C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller). The injection time of the precursor from the vaporizer into the chamber was fixed at 2 seconds, the purge time of the precursor was 4 seconds, the injection time of NH3 was 3 seconds, and the purge time of NH3 was fixed at 6 seconds to perform atomic layer deposition (see Table 2). First, a silicon wafer was immersed in an HF aqueous solution diluted by mixing 50 wt% hydrofluoric acid (HF) and D.I (H2O) at a ratio of 3:2 for 1 minute and then taken out, and then immersed in a D.I solution for 4 minutes to remove the native oxide film, and a substrate with a pure silicon surface was prepared. After that, it was carried into the chamber and heated to 300 - 350 °C.

[0196] Next, the compound vaporized into the vapor phase by heating was injected into a deposition chamber where the substrate was carried in for 2 seconds using argon (Ar) gas with a flow rate of 500 sccm as a carrier gas. Then, argon (Ar) gas was supplied at 500 sccm for 4 seconds to perform an argon purge. The pressure in the reaction chamber was controlled to 2.5 Torr.

[0197] Then, 1000 sccm of NH3 gas was injected for 3 seconds to form a nitride film, and then argon (Ar) gas was supplied at 500 sccm for 6 seconds to perform an argon purge. At this time, the substrate on which the metal thin film was to be formed was heated to 300 - 450 °C.

[0198] Such a process was repeated 200 times to form a MoN thin film with self-limiting atomic layers.

[0199]

[0200] [Test Example 3] Evaluation of Film Formation Using ALD Deposition of Thin Film Precursor Compounds

[0201] As a result of performing film formation evaluation on the nitride films of Examples 1 to 4, the physical properties of the thin films according to the process temperature showed an ALD window region in the temperature range of 330 to 370 °C, and it was confirmed that it is an ALD precursor having a constant thin film growth temperature in this range.

[0202] Specifically, the deposition rate and the resistivity value (sheet resistance) were measured for the thin films obtained according to Example 1 and Example 2.

[0203] * Deposition rate (thin film growth rate per cycle, Dep. Rate; GPC) (°C / cycle (cycle)): GPC is an abbreviation for Growth Per Cycle. The thin film is formed by advancing several cycles based on one cycle of supplying the precursor, reactant, and purge gas. After measuring the optical thickness of the formed thin film with an ellipsometer equipment, the growth rate of the thin film formed per cycle was calculated from the total thickness of the formed thin film and is shown in Table 3 below.

[0204] * Sheet resistance (Resistance; Re) (uΩ.cm): The sheet resistance was measured by the four-point probe method of the substance and calculated by substituting the correction coefficient.

[0205] Specifically, as a four-point probe equipment, four probes were arranged on the surface of the specimen using the CMT-SERIES model number manufactured by Micro-Nix Co., Ltd. A current was applied to the outer probes, the voltage was specified at the middle probe to obtain the resistance value, and then the resistance value was read in the CMT-SR1000NH system.

[0206] Also, the correction coefficient was calculated using three types of coefficients up to the sample size, the thickness of the thin film, and the temperature at the time of specification. The sample size coefficient applies 4.532, which is a value normally applied to samples with a diameter of 40 mm or more. The thin film thickness coefficient applies 1, which is a value normally applied when the thin film thickness is about 400 μm or less. For the temperature, when the temperature of the sample is about 23 °C according to the temperature coefficient of the sample, a value close to 1 was utilized and calculated from Equation 1 below.

[0207] [Formula 1]

[0208] Correction factor (C.F) = cf1 × cf2 × cf3

[0209] Substitute the resistance value read in the CMT-SR1000NH system and the correction factor (C.F) calculated from the above Formula 1 into the following Formula 2, calculate it in ohm / sq which is the unit of sheet resistance, and summarize and show it in Table 3 below.

[0210] [Formula 2]

[0211] Resistance value (ohm) × Correction factor (C.F) = Sheet resistance (ohm / sq)

[0212]

Table 3

[0213] As is clear from Table 3 above, in the case of the thin film precursor compound according to the present invention, it has excellent thermal stability at deposition temperatures of 350°C and 400°C respectively, and it was confirmed that a high deposition rate is provided when depositing at a low temperature. Also, it was confirmed that the sheet resistance values as the film formation characteristics at deposition temperatures of 350°C and 400°C show significant levels when correcting the resistance value considering the thickness of the specimen.

[0214] Furthermore, referring to Table 3 above and comparing the cases of deposition temperatures of 350°C and 400°C, it was confirmed that when depositing at 350°C, the deposition rate is 0.74 Å / cycle, and when increasing the deposition temperature to 400°C, it increases by nearly 144% to 1.81 Å / cycle.

[0215] Example 2 has a higher deposition rate compared to Example 1. Different from the conventional technology, an unexpected phenomenon occurs where, as the deposition rate increases, the impurities are not increased but rather reduced. It was confirmed that there are other significant advantages when linked to the aspect of production capacity (throughput).

[0216]

[0217] [Test Example 4] Analysis of the thickness of the thin film cross-section using ALD deposition of the thin film precursor compound

[0218] The thickness and thin film density of the thin film cross-section obtained in Test Example 3 were analyzed as follows.

[0219] * Thin film density (g / cm 3 ): Measured by the X-ray reflectometry (XRR) analysis method. This analysis method was applied to a thin film specimen formed by a technique of observing the pattern that appears when X-rays are incident and reflected between the surface and the interface, and physical properties such as the film thickness, density, surface, and interface roughness were measured.

[0220] As a result of the measurement, it was confirmed that in Example 1 deposited at 350°C, it showed an average cross-section thickness of 43.4 Å, and in Example 2 deposited at 400°C, it showed an average cross-section thickness of 156.9 Å.

[0221]

[0222] [Test Example 5] Confirmation of the thin film thickness and step coverage of the thin film precursor compound

[0223] The thin film thickness and step coverage of the thin film cross-section obtained in Test Example 3 were confirmed by taking TEM photographs. The following Figure 5 is a TEM photograph of the thickness of the thin film cross-section formed using the thin film precursor compound synthesized in Synthesis Example 2 with the vapor deposition equipment in Figure 4. The left figure corresponds to the deposition condition of 350°C, and the right figure corresponds to the deposition condition of 400°C.

[0224] As is clear from FIG. 5 below, it was confirmed that the thin film thickness was uniform, and when forming a film at a specific deposition temperature, it has excellent step coverage and uniform coating property due to a self-limiting thin film growth mechanism, and moreover, it can be seen that accurate thickness control is possible.

[0225] In addition, as a result of confirming the step coverage of the Mo thin films deposited in Example 1 and Example 2 using TEM, it was confirmed that both had a high step coverage rate.

[0226]

[0227] [Test Example 6] Analysis of Carbon Concentration of Thin Films Using ALD Deposition of Thin Film Precursor Compounds

[0228] The carbon concentration of the thin film obtained in Test Example 3 was analyzed as follows, and the results are shown in Table 4 below.

[0229] *Carbon Concentration: By performing depth profile analysis with an X-ray photoelectron spectrometer (XPS: X-ray Photoelectron Spectrometer), the constituent elements, composition ratio, and chemical bonding state in the thin film were confirmed.

[0230]

Table 4

[0231] As is clear from Table 4 above, from the depth profile results of the X-ray photoelectron spectrometer (XPS: X-ray Photoelectron Spectrometer) of the thin films obtained in Example 1 and Example 2, it was confirmed that they were MoN thin films, and it was also confirmed that they provided a significant carbon concentration.

Claims

1. A thin film precursor compound, characterized by being represented by Chemical Formula 2: [Chemical Formula 2] ML １ L ２ L ３ L ４ (L ５ ) ｈ (L ６ ) ｉ (Wherein M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6; the L １ , L ２ , L ３ , L ４ , L ５ and L ６ are independently selected from the group consisting of NR a R b ; OR c ; NR c ; CO; R d Cp; amidinate; guanidinate; ethylenediamine; propylenediamine; and linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); Cp is cyclopentadienyl; R a, R b, R c, and R d are independently hydrogen or alkyl having 1 to 12 carbon atoms; h and i are independently 0 or 1; the overall oxidation number of the compound is an integer from -2 to 6; and one or more ligands selected from among the L １ , L ２ , L ３ , L ４ , L ５ and L ６ are linear or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S).)

2. The thin film precursor compound according to claim 1, characterized in that the thin film precursor compound is a compound represented by the following Chemical Formula 3 or Chemical Formula 4: [Chemical Formula 3] 【Chemical Formula 1】 [Chemical Formula 4] [Chemical Formula 2] (In the above Chemical Formulas 3 to 4, M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, R １ , R ２ , R ３ , R ４ and R ５ are independently selected from the group consisting of hydrogen, dimethylamine group, substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, and substituted or unsubstituted alkoxy group having 1 to 7 carbon atoms, and n is an integer from 0 to 2.)

3. The thin film precursor compound is characterized in that it is obtained using the compound represented by the following Chemical Formula 1 as an intermediate, the thin film precursor compound according to Claim 1. [Chemical Formula 1] Mo(O)n(X)m(L)k (Wherein Mo is molybdenum, O is oxygen, X is halogen, L is a ligand, n is an integer from 0 to 2, m is an integer from 2 to 6, and k is an integer from 1 to 3.)

4. The ligand is a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S), the thin film precursor compound according to Claim 3.

5. The intermediate is (tBuN=) ２ MoCl ２ (DAE) (where DAE is a dialkoxyethane having 1 to 15 carbon atoms), the thin film precursor compound according to Claim 3.

6. The thin film precursor compound is liquid under the conditions of 20 °C and 1 bar and has volatility, the thin film precursor compound according to Claim 1.

7. A thin film forming method, comprising the step of injecting a thin film precursor compound represented by Chemical Formula 2 into a chamber and depositing it on the surface of a substrate that has been loaded (loaded): [Chemical Formula 2] ML １ L ２ L ３ L ４ (L ５ ) ｈ (L ６ ) ｉ (Wherein M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, and the L １ , L ２ , L ３ , L ４ , L ５ and L ６ are independently NR a R b; OR c; NR c; CO; R d Cp; amidinate; guanidinate; ethylenediamine; propylenediamine; and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S); selected from the group consisting of, wherein Cp is cyclopentadienyl, R a, R b, R c and R d are independently hydrogen or alkyl having 1 to 12 carbon atoms, h and i are independently 0 or 1, the overall oxidation number of the compound is an integer from -2 to 6, and one or more ligands selected from among the L １ , L ２ , L ３ , L ４ , L ５ , L ６ is a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S). )

8. The vapor deposition step includes a step of vaporizing the thin film precursor compound and adsorbing it on the surface of a substrate carried into the chamber, a step of purging the inside of the chamber with a purge gas, a step of supplying a reaction gas into the chamber, and a step of purging the inside of the chamber with a purge gas. The thin film forming method according to claim 7 is characterized by this.

9. The vapor deposition step of the thin film forming method according to claim 7 is characterized in that the thin film precursor compound and the reaction gas are simultaneously injected onto a substrate carried into the chamber.

10. The vapor deposition step of the thin film forming method according to claim 7 is carried out by an atomic layer deposition method (Atomic Layer Deposition; ALD process), a chemical vapor deposition method (Chemical Vapor Deposition; CVD process), a plasma atomic layer deposition method (PEALD process), or a plasma chemical vapor deposition method (PECVD process).

11. The thin film forming method according to claim 9 is characterized in that a nitriding agent, an oxidizing agent, or a reducing agent is used as the reaction gas.

12. The thin film of the thin film forming method according to claim 7 is characterized by including a metal nitride thin film, a metal oxide thin film, or a metal thin film.

13. A semiconductor substrate manufactured by the thin film forming method according to claim 7.

14. A semiconductor device including the semiconductor substrate according to claim 13.

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