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 formation method using the same, and a semiconductor substrate manufactured therefrom. More specifically, the present invention relates to a thin film precursor compound that is in a liquid state at room temperature, is highly volatile, has a very fast deposition rate, is easy to handle when injected into a thin film deposition chamber, and in particular has excellent thermal stability, resulting in very high purity, excellent step coverage, and further suppresses side reactions to lower the thin film growth rate. Even when forming a thin film on a substrate with a complex structure, it can significantly improve step coverage and the uniformity of the thin film thickness, thereby improving the density of the thin film and significantly improving the electrical properties of the thin film. [Background technology]

[0002] As the integration density of existing two-dimensional planar semiconductor devices increases, the cell spacing narrows, leading to a significant increase in leakage current. To overcome this, 3D V (NAND) was developed, which increases integration density by stacking circuits in a three-dimensional structure. Furthermore, when thin-film precursor materials such as WF6, used as electrodes in semiconductor devices, are subjected to CVD (H2 reduction), fluorine-induced cracks (voids) occur, creating seams in the cells and degrading device performance. In addition, the increase in resistance due to the increase in the number of NAND stages is a concern. To overcome this, Mo compounds with low resistivity have been adopted. However, Mo compounds such as MoO2Cl2 currently in use are solids at room temperature, and therefore the amount that sublimes is not constant, making stable supply difficult.

[0003] [Prior art document]

[0004] [Patent]

[0005] (Patent Document 1) Korean Published Patent No. 2006-0037241 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] To solve the problems of the conventional technology described above, the present invention aims to provide a thin film precursor compound that is liquid at room temperature, is highly volatile and has a very fast deposition rate, is easy to handle when injected into a thin film deposition chamber, and in particular has excellent thermal stability, resulting in very high purity, excellent step coverage, suppresses side reactions to lower the thin film growth rate, and removes process by-products within the thin film, thereby significantly improving step coverage and thickness uniformity of the thin film even when forming a thin film on a substrate with a complex structure, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom.

[0007] The above-mentioned and other objectives of the present invention can all be achieved by the present invention as described below. [Means for solving the problem]

[0008] To achieve the above objective, 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] (The M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), having charges of 0, +3, +4, +5, +6 and a coordination number of 6, and the L1, L2, L3, L4, L5, and L6 are independently NRaRb;ORc;NRc;CO;RdCp;amidinate;guanidinate;ethylenediamine;propylenediamine;and linear or cyclic saturated or having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) or L1 is selected from the group consisting of unsaturated hydrocarbons; where Cp is cyclopentadienyl; Ra, Rb, Rc, and Rd are independently hydrogen or C1-C12 alkyl groups; 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-C15 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] [ka]

[0015] [Chemical formula 4]

[0016] [ka]

[0017] (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, 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 the compound represented by the following Chemical Formula 1 as an intermediate.

[0019] [Chemical Formula 1]

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

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

[0022] [[ID=第十九]] 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 and volatile under the conditions of 20 °C and 1 bar.

[0025]

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

[0027] [Chemical Formula 2]

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

[0029] (The M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), having charges of 0, +3, +4, +5, +6 and a coordination number of 6, and the L1, L2, L3, L4, L5, and L6 are independently NRaRb;ORc;NRc;CO;RdCp;amidinate;guanidinate;ethylenediamine;propylenediamine;and linear or cyclic saturated or having 3 to 15 carbon atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S) or L1 is selected from the group consisting of unsaturated hydrocarbons; where Cp is cyclopentadienyl; Ra, Rb, Rc, and Rd are independently hydrogen or C1-C12 alkyl groups; 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-C15 atoms and substituted with one or more nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S). The present invention provides a thin film formation method characterized by including the step of injecting a thin film precursor compound represented by into a chamber and depositing it onto the surface of a substrate that has been loaded.

[0030]

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

[0032] The deposition step may involve simultaneously injecting the thin film precursor compound and the reaction gas into a substrate that has been brought into the chamber.

[0033] The deposition step may be carried out by atomic layer deposition (ALD), chemical vapor deposition (CVD), plasma atomic layer deposition (PEALD), or plasma chemical vapor deposition (PECVD).

[0034] The aforementioned thin film formation method may use a nitride agent, an oxidizing agent, or a reducing agent 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 formation method described above.

[0038] Furthermore, the present invention provides a semiconductor device including the aforementioned semiconductor substrate. [Effects of the Invention]

[0039] According to the present invention, because it is in a liquid state at room temperature, it is highly volatile and has a very fast deposition rate, making it easy to handle when injected into a thin film deposition chamber. In particular, it has excellent thermal stability, resulting in very high purity and excellent step coverage. Furthermore, by suppressing side reactions and lowering the thin film growth rate, and by removing process by-products within the thin film, it is possible to provide a thin film precursor compound, a thin film formation method using the same, and a semiconductor substrate manufactured therefrom, which can significantly improve step coverage and thin film thickness uniformity even when forming a thin film on a substrate with a complex structure. [Brief explanation of the drawing]

[0040] [Figure 1] This is the NMR (nuclear magnetic resonance) spectrum of the thin-film precursor compound synthesized in Synthesis Example 2.

[0041] [Figure 2] This figure shows the differential scanning calorimetry-thermogravimetric analysis (DSC-TG analysis) results of the thin film precursor compound synthesized in Synthesis Example 2.

[0042] [Figure 3] This figure shows the results of parallax scanning calorimetry (DSC analysis) of the thin film precursor compound synthesized in Synthesis Example 2.

[0043] [Figure 4] This figure schematically shows the deposition equipment used for atomic layer deposition using a thin film precursor compound in Example 1 or 2.

[0044] [Figure 5] The images show transmission electron microscope (TEM) photographs of the thickness of the thin film cross-section formed using the deposition equipment shown in Figure 4, where the left image corresponds to a deposition condition of 350°C, and the right image corresponds to a deposition condition of 400°C. [Modes for carrying out the invention]

[0045] The following provides a detailed explanation of the thin-film precursor compound described herein, the thin-film formation method using it, and the semiconductor substrate produced therefrom.

[0046] The inventors confirmed that when a thin-film precursor compound having a predetermined structure is adsorbed onto the surface of a substrate introduced into an ALD chamber, it is highly volatile and has a very fast deposition rate because it is in a liquid state at room temperature, making it easy to handle when injected into the thin-film deposition chamber. In particular, it has excellent thermal stability, resulting in very high purity, improved step coverage and thin-film uniformity. They also confirmed that the amount of halide residue remaining as a process by-product is significantly reduced, resulting in a substantial improvement in the density and resistivity of the thin film. Based on these results, the inventors continued their research on thin-film precursor compounds and completed the present invention.

[0047]

[0048] A thin film precursor compound according to one aspect of the present invention is given by the following chemical formula 2

[0049] [Chemical formula 2]

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

[0051] (The above M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), having charges of 0, +3, +4, +5, +6 and a coordination number of 6; the above L1, L2, L3, L4, L5, and L6 are independently selected from the group consisting of NRaRb; ORc; NRC; CO; RdCp; amidinates; guanidinates; ethylenediamines; propylenediamines; 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); the above Cp is cyclopentadienyl; and the above Ra, Rb, Rc, and Rd are independently hydrogen... The compound is characterized by being an alkyl group having 1 to 12 carbon atoms, where 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). In this case, because it is in a liquid state at room temperature, it is highly volatile, has a very fast deposition rate, is easy to handle when injected into a thin film deposition chamber, and, in particular, has excellent thermal stability, resulting in very high purity and improved step coverage.

[0052] The thin film precursor compound is defined by the following chemical formula 3 or chemical formula 4

[0053] [Chemical formula 3] [ka]

[0054]

[0055] [Chemical formula 4]

[0056] [ka]

[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), and has a charge of 0, +3, +4, +5, +6 and a coordination number of 6; R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, a dimethylamine group, a substituted or unsubstituted C1-C7 alkyl group, and a substituted or unsubstituted C1-C7 alkoxy group; and n is an integer from 0 to 2.) The compound may be selected from among those represented by these formulas, and in this case, since it is in a liquid state at room temperature, it is highly volatile and has a very fast deposition rate, making it easy to handle when injected into a thin film deposition chamber. In particular, it has the advantages of inducing selective bonding to minimize contamination of the thin film and being easy to remove with reaction gases, as well as high purity and excellent step coverage.

[0058] In the above chemical formulas 3 to 4, M is one or more elements selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), and may have charges of 0, +3, +4, +5, or +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, substituted or unsubstituted alkyl groups of C1 to C7, substituted or unsubstituted alkoxy groups of C1 to C7, and dimethylamines.

[0060] In the above chemical formulas 3 to 4, R1 and R5 can be independently selected from H and C1 to C7 substituted or unsubstituted alkyl groups, for example, 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 alkyl groups, and 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 alkyl groups, for example, 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 groups may include, but are not limited to, one selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-butyl, and their isomers.

[0064] In this description, the C1-C7 alkoxys may include, but are not limited to, 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 their isomers.

[0065] In chemical formulas 3 and 4 above, n can be an integer between 0 and 2.

[0066]

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

[0068] Furthermore, M is W (tungsten), R1 and R5 are independently selected from the group consisting of H and substituted and unsubstituted alkyl groups from C1 to C7, R3 and R4 are independently selected from the group consisting of H and substituted or unsubstituted alkyl groups from C1 to C5, R2 may be independently selected from the group consisting of H, substituted or unsubstituted alkyl groups from C1 to C5, substituted or unsubstituted alkoxy groups from C1 to C7, and dimethylamine, and n may be an integer from 0 to 2.

[0069] Furthermore, M is Cr (chromium), R1 and R5 are independently selected from the group consisting of H and substituted and unsubstituted alkyl groups from C1 to C7, R3 and R4 are independently selected from the group consisting of H and substituted or unsubstituted alkyl groups from C1 to C5, R2 may be independently selected from the group consisting of H, substituted or unsubstituted alkyl groups from C1 to C5, substituted or unsubstituted alkoxy groups from C1 to C7, and dimethylamine, and n may be an integer from 0 to 2.

[0070]

[0071] A thin film precursor compound according to one aspect of the present invention is, for example, one of the following chemical formulas 1

[0072] [Chemical formula 1]

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

[0074] The compound obtained as an intermediate is represented by (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). In this case, since it is in a liquid state at room temperature, it is highly volatile and has a very fast deposition rate, making it easy to handle when injected into a thin film deposition chamber. In particular, it has the advantages of inducing selective bonding to minimize contamination of the thin film and being easily removed by reaction gases, as well as having high purity and 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, which gives it high volatility, a very fast deposition rate, and makes it easy to handle when injected into a thin film deposition chamber. In particular, it has the advantages of inducing selective bonding to minimize contamination of the thin film, being easily removed by reaction gases, having high purity, and exhibiting excellent step coverage.

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

[0077] As specific examples, the ligand may be t-butylamine and chlorotrimethylsilane, as well as 1,2-dimethoxyethane, as used in Synthesis Example 1 described later, but is not limited to these.

[0078] The intermediate is preferably (tBuN=)2MoCl2(DAE) (where DAE is a dialkoxyethane having 1 to 15 carbon atoms), where DAE may, but is not limited to, DME (dimethoxyethane), DEE (diethoxyethane), or DEME (diethylmethoxyethane).

[0079] The thin-film precursor compound obtained using the aforementioned intermediate in the present invention is in a liquid state at room temperature, making it highly volatile, resulting in a very fast deposition rate. It is easy to handle when injected into a thin-film deposition chamber, and in particular, it has the advantages of inducing selective bonding to minimize contamination of the thin film, being easily removed by reaction gases, having high purity, and exhibiting excellent step coverage.

[0080] The thin-film precursor compound is preferably liquid and volatile under conditions of 20°C and 1 bar. In this case, the deposition rate is very fast, it is easy to handle when injected into the thin-film deposition chamber, and in particular, it has excellent thermal stability, resulting in very high purity, excellent step coverage, and furthermore, it has the advantage of suppressing side reactions and lowering the thin-film growth rate, significantly improving step coverage and thickness uniformity of the thin film even when forming a thin film on a substrate with a complex structure, and improving the density of the thin film, thereby significantly improving the electrical properties of the thin film.

[0081] For reference, reactants used in atomic layer deposition (ALD) are required to be highly volatile, stable, and highly reactive. In ALD, a thin film of monolayer thickness or less grows during one cycle of deposition by surface reactions, with each reactant supplied separately. Ligands of the reactants adsorbed onto the substrate are removed by chemical reactions with other reactants supplied later. Therefore, when heating the precursor reactants for atomic layer deposition, being in the liquid phase is far more advantageous than being in the solid phase in terms of reaction rate and process efficiency.

[0082] Here, unless otherwise specified herein, volatility refers to volatility exhibited in a chamber at 300°C or higher, and in this case, it is suitable for exhibiting the effect of uniform distribution on a substrate.

[0083] A thin-film precursor compound according to one aspect of the present invention, by coordinating a heteroligand to a central metal, not only exists in a liquid state at room temperature but can also exhibit improved vapor pressure and other properties.

[0084] The thin-film precursor compounds represented by chemical formula 1 above, and specifically by chemical formulas 3 or 4 above, exhibit excellent thermal stability, making low-temperature deposition possible. For reference, when extending the -NR5-C=C-NR3R4 fraction contained in the heteroligand, as the chain lengthens, coordination bonds can be formed on the other side rather than the central metal side, which may be disadvantageous for deposition by chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), low-pressure vapor deposition (LPCVD), plasma-enhanced vapor deposition (PECVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD).

[0085] In contrast, the thin-film precursor compounds represented by chemical formula 1, specifically chemical formulas 3 to 4, obtained using the aforementioned intermediates, can be purified under relatively low temperatures of 0.4 torr and 170-180°C. This offers the advantage of not only having a relatively favorable vapor pressure for evaluating deposition, but also providing the properties of a liquid phase.

[0086] Furthermore, the thin-film precursor compounds obtained using the aforementioned intermediates, represented by chemical formula 1, and specifically by chemical formulas 3 to 4, are easy to handle due to their low reactivity with water and lack of risk of spontaneous combustion. They also possess high vapor pressures, making them useful for forming thin films using deposition processes such as chemical vapor deposition and atomic layer deposition.

[0087] In particular, during film formation, the physical properties of the thin film, depending on the process temperature, exhibit an ALD window region in the temperature range of 330-370°C. This allows the thin film to be used as an ALD precursor with a constant film formation temperature within this range, thereby reducing process costs.

[0088]

[0089] The present invention provides a thin film formation method that includes the step of injecting a thin film precursor compound represented by chemical formula 1, specifically chemical formula 3 or chemical formula 4, into a chamber and depositing it onto the surface of a loaded substrate. In this case, because it is in a liquid state at room temperature, it is highly volatile, has a very fast deposition rate, is easy to handle when injecting it into a thin film deposition chamber, and, in particular, has excellent thermal stability, resulting in very high purity and excellent step coverage. Furthermore, by suppressing side reactions and lowering the thin film growth rate, and by removing process by-products within the thin film, it has the advantage of significantly improving step coverage and thin film thickness uniformity, even when forming a thin film on a substrate with a complex structure.

[0090] The thin film formation method of the present invention may include the steps of: vaporizing a thin film precursor compound represented by the aforementioned chemical formula 1, or more specifically, chemical formula 3 or chemical formula 4, and adsorbing it onto the surface of a substrate loaded into a chamber; purging the inside of the chamber with a purge gas; supplying a reaction gas to the inside of the chamber; and purging the inside of the chamber with a purge gas.

[0091] The deposition step can be performed by sequentially or simultaneously injecting the thin film precursor compound and the reaction gas into the substrate that has been brought into the chamber.

[0092]

[0093] The thin film formation method described above can be carried out by conventional methods for manufacturing metal thin films, such as atomic layer deposition (ALD), chemical vapor deposition (CVD), plasma atomic layer deposition (PEALD), or plasma chemical vapor deposition (PECVD), except that a thin film precursor compound of chemical formula 1, or more specifically, chemical formula 3 or chemical formula 4, is used as the thin film precursor compound. Preferably, it can be carried out by chemical vapor deposition or atomic layer deposition, but is not limited thereto.

[0094] Specifically, the metal thin film can be formed by supplying one or more of the thin film precursor compounds represented by chemical formula 1, or more specifically, chemical formulas 3 to 4, onto a substrate such as TiN, SiO2, or Si3N4, and then decomposing the precursor.

[0095] The thin-film precursor compound can be injected onto the substrate under temperature conditions suitable for the material's properties, and the deposition process conditions can be varied depending on the deposition efficiency.

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

[0097] In this case, a method for gasifying the thin film precursor compound includes the step of purging the unadsorbed thin film precursor compound with an inert gas, and then injecting a reaction gas.

[0098] Specifically, methods can be used in which the thin-film precursor compound is vaporized directly, or in which the thin-film precursor compound is injected into a constant-temperature bath and then vaporized by supplying an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen.

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

[0100] As a specific example, in the decomposition of the thin film precursor compound by heat treatment, the above step may be carried out under temperature conditions of 100 to 1000°C, and the deposition temperature of the substrate may, for example, be 50 to 400°C, preferably 200 to 400°C.

[0101] For example, the feeding time (sec) of the thin film precursor compound to the surface of the substrate may be preferably 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 per cycle. Within this range, there is an advantage in that it offers excellent step coverage and cost-effectiveness.

[0102] The feeding time for the thin-film precursor compound mentioned above is based, for example, on a chamber volume of 15-20 L and a flow rate of 0.5-5 mg / s, and more specifically, on a chamber volume of 18 L and a flow rate of 1-2 mg / s.

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

[0104] In this description, the purging 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 is reduced to a suitable range, and process by-products are reduced.

[0105] The deposition according to the present invention can be carried out using deposition equipment commonly used in the industry, and in the embodiments described later, a thin film can be manufactured by atomic layer deposition (ALD) using the deposition apparatus shown in Figure 4 below.

[0106] Figure 4 below schematically shows a deposition apparatus that performs atomic layer deposition according to the present invention using NH3 gas as a nitride agent. In this diagram, the source line and reaction gas line are operated separately to maximize the properties of the material by adjusting the temperature to suit each characteristic. However, even when manufacturing using an apparatus that operates the source line and reaction gas line together, it does not deviate from the scope of the present invention.

[0107] Furthermore, the present invention may include a thin film manufacturing apparatus capable of realizing the thin film manufacturing method, comprising an ALD chamber, a first vaporizer for vaporizing a thin film precursor compound, a first transport means for transporting the vaporized thin film precursor compound into the ALD chamber, and a second transport means for transporting a reaction gas into the ALD chamber. Here, the vaporizer and transport means are not particularly limited, as long as they are vaporizers and transport means commonly used in the art to which the present invention belongs.

[0108]

[0109] The metal-containing thin film manufacturing method according to the present invention, as described above, uses a thin film precursor compound with excellent thermal stability, allowing the deposition process to be carried out at a lower temperature than conventional methods. This enables good crystallinity without particle contamination or impurity contamination such as carbon caused by thermal decomposition of the precursor, and allows for the formation of high-purity metal thin films, metal oxides, or metal nitride thin films at a high deposition rate without process byproducts.

[0110] The thin film formation method according to the present invention may, as necessary, utilize known film quality improving agents, thin film growth inhibitors, or thin film growth activators in the industry.

[0111] Furthermore, although this specification uses ALD chambers and ALD processes as examples, it should be noted that the present invention is not limited in any way to these. For reference, ALD (atomic layer deposition) is very advantageous when manufacturing integrated circuits (ICs) that require high aspect ratios, and in particular, its self-limiting thin-film growth mechanism offers advantages such as excellent conformality, uniformity, and high-precision thickness control.

[0112] The thin film formation method described above can be carried out, for example, at an evaporation temperature in the range of 50 to 900°C, preferably in the range of 300 to 700°C, more preferably in the range of 350 to 600°C, even more preferably in the range of 400 to 550°C, and even more preferably in the range of 400 to 500°C. Within this range, it is possible to grow a thin film with excellent film quality while achieving the ALD process characteristics.

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

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

[0115] The thin film formation method may preferably include the steps of raising the temperature inside the chamber to the deposition temperature before introducing the thin film precursor compound into the chamber, and / or purging the chamber by injecting an inert gas into the chamber before introducing the thin film precursor compound into the chamber.

[0116]

[0117] To give a specific example of the thin film formation method, first, a substrate on which a thin film is to be formed is placed inside a deposition chamber capable of depositing atomic layers.

[0118] The aforementioned substrate can encompass semiconductor substrates such as silicon substrates and silicon oxide.

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

[0120] To deposit a thin film onto a substrate located in the aforementioned deposition chamber, the thin film precursor compound described above is prepared.

[0121] Subsequently, the prepared thin-film precursor compound is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber where it is adsorbed onto the substrate. Any unadsorbed thin-film precursor compound is then purged.

[0122] In this description, as a method for transferring thin film precursor compounds and the like to the deposition chamber, one example is to use a Mass Flow Controller (MFC) method to transport volatile gases (VFC) or a Liquid Mass Flow Controller (LMFC) method to transport liquids (Liquid Delivery System (LDS)). Preferably, the LDS method is used.

[0123] In this process, one or more gases selected from argon (Ar), nitrogen (N2), and helium (He) can be used as the carrier gas or diluent gas for moving the thin film precursor compound and other precursor compounds onto the substrate, but there are no limitations to this.

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

[0125]

[0126] Next, a reaction gas is supplied. The reaction gas can be any reaction gas commonly used in the art to which the present invention belongs, without any particular limitations, and preferably may include a reducing agent, a nitride 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 depending on the nitride agent, and a metal oxide thin film is formed depending on the oxidizing agent.

[0127] Next, an inert gas is used to purge any unreacted residual reaction gas. This removes not only the excess reaction gas but also any by-products that have been generated.

[0128] As described above, the process consists of a unit cycle comprising the steps of adsorbing a thin film precursor compound onto a substrate, purging any unadsorbed thin film formation composition, supplying a reaction gas, and purging any residual reaction gas. This unit cycle can be repeated to form a thin film of a desired thickness.

[0129] The aforementioned unit cycle may, for example, be 100 to 1,000 times, preferably 100 to 500 times, and more preferably 150 to 300 times, and within this range, the desired thin film characteristics are successfully achieved.

[0130] Conventionally, when using a molybdenum-based thin-film precursor compound (e.g., MoO2Cl2) in a solid state under 20°C and atmospheric pressure conditions in the ALD process, the solid is difficult to sublimate and reacts with reaction gases (e.g., NH3), resulting in the retention of process by-products such as NH4Cl and HCl in the thin film, which degrades the performance of the substrate due to corrosion and degradation. However, when using the thin-film precursor compound according to the present invention, thermal stability is improved and the deposition rate is increased. Process by-products such as NH4Cl and HCl, which are generated by the reaction with reaction gases (e.g., NH3), are removed along with the thin-film precursor compound, preventing corrosion and degradation of the substrate. This not only improves step coverage and uniformity of thin-film thickness but also improves the density of the thin film, providing excellent electrical properties.

[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 may 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 with high consistency and thin-film uniformity, even if it has a complex structure, along with precise thickness control.

[0134] The semiconductor substrate of the present invention is characterized by being manufactured by the thin film formation method described herein. In this case, the deposition rate is improved, and process by-products within the thin film are removed, thereby preventing corrosion and degradation, and resulting in significantly superior step coverage and uniformity of the thin film thickness.

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

[0136] Preferably, the manufactured thin film has a film thickness of 20 nm or less, a resistivity of 0.1 to 400 μΩ·cm, a halogen content of 10,000 ppm or less, and a step coverage ratio of 90% or more. Within this range, it exhibits outstanding performance as a diffusion-blocking film and has the effect of reducing corrosion of metal wiring materials, but is not limited thereto.

[0137] The thin film may have a 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, and within this range, it has the effect of exhibiting excellent thin film properties.

[0138] The aforementioned thin film may have a resistivity of, for example, 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm, and more preferably 100 to 300 μΩ·cm, and within this range, it has the effect of exhibiting excellent thin film properties.

[0139] The thin film may have a halogen content of 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, the thin film exhibits excellent thin-film properties while reducing corrosion of the metal wiring material.

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

[0141] The manufactured thin film may, for example, be 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 yet another aspect of the present invention, a semiconductor device including the semiconductor substrate is provided.

[0144] The semiconductor device may, for example, be a low-resistive metal gate interconnect, a high-aspect-ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D gate-all-around (GAA) circuit, or 3D NAND.

[0145]

[0146] The following are preferred embodiments to further the understanding of the present invention. However, these embodiments are merely illustrative of the present invention, and it will be obvious to those skilled in the art that a wide variety of changes and modifications can be made within the scope of the present invention and the technical concept. It goes without saying that such modifications and changes also fall within the scope of the appended claims.

[0147] [Examples]

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

[0149] (tBuN=)2MoCl2DME was synthesized from Na2MoO4 according to the following reaction equation 1.

[0150] [Reaction Equation 1]

[0151] TIFF0007892079000005.tif29168

[0152] Specifically, under a dry argon gas atmosphere, 467 g (486 mmol) of Na2MoO, 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. The reaction was carried out over 24 hours under reflux at a temperature of 65°C, and the completion of the reaction was confirmed by NMR.

[0153] Unless otherwise specified, all substances used in the above reaction equations were synthesized and purified to produce high-purity products of 99% or higher. The resulting yellow solution was filtered, washed with hexane, and the filtrate was vacuum-dried. The resulting solid was repeatedly washed with hexane to obtain 27 g of (tBuN=)2MoCl2(DME) (yield: 21 wt%), and NMR analysis of this was performed to confirm that an intermediate with the (tBuN=)2MoCl2DME structure was obtained.

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

[0155]

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

[0157] Using the (tBuN=)2MoCl2(DME) obtained in the above synthesis example 1, (tBuN=)2Mo(TBDMAE)(DMA) was synthesized according to the following reaction equation 2.

[0158] [Reaction Formula 2]

[0159] TIFF0007892079000006.tif31160

[0160] Specifically, after charging 95.5 g (239.2 mmol) of (tBuN=)2MoCL2DME into a 1 L Schlenk flask, 160 ml of anhydrous toluene was charged, 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 synthetic product was purified through a purification column, 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 the (tBuN=)2MoCl2(DME) obtained in the above synthesis example 1, (tBuN=)2Mo(TBDMAE)(tBuO) was synthesized according to the following reaction equation 3.

[0168] [Reaction Equation 3]

[0169] TIFF0007892079000007.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 in. Here, the abbreviation TBDMAE refers to 1-(tert-butylamino)-2-(dimethylamino)ethane.

[0171] The mixture was then placed in a 250 mL Schlenk flask along with 10 g (25 mmol) of (tBuN=)2MoCl2(DME) and 50 ml of anhydrous toluene, after being cooled to below 0°C, and then stirred at room temperature for 12 hours.

[0172] 38 g of Li-TBDMAE, which had been synthesized separately, was dissolved in hexane in the aforementioned 250 mL Schlenk flask, and then added dropwise at -5°C.

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

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

[0175]

[0176] [Test Example 1] Confirmation of properties of thin film precursor compounds

[0177] The properties of the thin-film precursor compounds produced in Synthesis Examples 1 and 2 were confirmed at 20°C and 1 atm, and both were found to be in a liquid state, indicating high volatility.

[0178]

[0179] [Test Example 2] Thermogravimetric analysis (TG analysis) of thin film precursor compounds

[0180] Thermogravimetric analysis (TG analysis) was performed on the thin film precursor compounds produced in the above synthesis examples 1 and 2.

[0181] The thermogravimetric analysis (TGA) was performed using a Mettler-Toledo TGA / DSC 1 STARe System in a 50 μL aluminium vessel. All samples had a content of 8–11 mg, and measurements were performed at temperatures ranging from 30°C to 500°C.

[0182] The measured values ​​obtained from thermogravimetric analysis are shown in Figures 2 and 3 below, respectively. Figure 2 below shows 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 shows the parallax scanning calorimetry analysis (DSC analysis) results of the thin film precursor compound synthesized in Synthesis Example 2.

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

[0184] Furthermore, thermal flow analysis revealed that the thin-film precursor compound of the present invention decomposes into a single pattern (see the blue ink graph in Figure 2 below).

[0185]

[0186] [Examples]

[0187] Examples 1-4

[0188] The thin-film precursor compounds listed in Table 1 were placed in canisters and supplied to a vaporizer using a liquid mass flow controller (LMFC) at room temperature.

[0189] After vaporizing the thin-film precursor compound into the vapor phase in the vaporizer, the substrate was introduced into the deposition chamber. Then, under the deposition temperature conditions listed in Table 1, atomic layer deposition (ALD) was performed using the deposition equipment shown in Figure 4 below to form the film.

[0190] The 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 supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller) at room temperature. Atomic layer deposition was performed with the precursor injection time from the vaporizer to the chamber fixed at 2 seconds, the precursor purging time at 4 seconds, the NH3 injection time at 3 seconds, and the NH3 purging time at 6 seconds (see Table 2). First, a silicon wafer was immersed for 1 minute in an aqueous HF solution prepared by mixing 50 wt% hydrofluoric acid (HF) and DI)(H2O) in a 3:2 ratio, then removed, and immersed in a DI solution for 4 minutes to remove the native oxide film, thereby preparing a substrate with a pure silicon surface. This substrate was then transferred to the chamber and heated to 300-350°C.

[0196] Next, the compound vaporized into the vapor phase by heating was injected into the deposition chamber into which the substrate was placed, using argon (Ar) gas with a flow rate of 500 sccm as a carrier gas for 2 seconds. Then, argon purging was performed by supplying argon (Ar) gas at 500 sccm for 4 seconds. The pressure inside the reaction chamber was controlled to 2.5 Torr.

[0197] Then, a nitride film was formed by injecting 1000 sccm of NH3 gas for 3 seconds, followed by argon purging by supplying 500 sccm of argon (Ar) gas for 6 seconds. At this time, the substrate on which the metal thin film was to be formed was heated to 300-450°C.

[0198] This process was repeated 200 times to form a MoN thin film, which is a self-limiting atomic layer.

[0199]

[0200] [Test Example 3] Evaluation of thin film deposition using ALD deposition of thin film precursor compounds

[0201] As a result of evaluating the film formation of the nitride films in Examples 1 to 4, the physical properties of the thin films, depending on the process temperature, showed an ALD window region in the temperature range of 330 to 370°C, confirming that they are ALD precursors with a constant thin film growth temperature in this range.

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

[0203] *Deposition rate (Dep. Rate; GPC) (°C / cycle): GPC is an abbreviation for Growth Per Cycle, where the supply of precursors, reactants, and purge gas is carried out in several cycles, with one cycle being the baseline, to deposit a thin film. After measuring the optical thickness of the deposited thin film using an ellipsometer, the growth rate of the thin film deposited per cycle is calculated from the total thickness of the deposited thin film and is shown in Table 3 below.

[0204] *Surface resistance (Re) (uΩ.cm): Surface resistance was calculated by measuring the surface resistance of the material using a four-point probe method and substituting a correction factor.

[0205] Specifically, using a four-point probe system, the CMT-SERIES model from Micronics Co., Ltd. was used, with four probes positioned on the surface of the specimen. Current was applied to the outer probes, and the voltage was determined on the middle probe to obtain the resistance value. This resistance value was then read using the CMT-SR1000NH system.

[0206] Furthermore, the correction factor was calculated using three types of coefficients: sample size, thin film thickness, and temperature at a specific time. For the sample size coefficient, a value of 4.532, which is normally applied to samples with a diameter of 40 mm or more, was applied. For the thin film thickness coefficient, a value of 1, which is normally applied when the thin film thickness is approximately 400 μm or less, was applied. For the temperature, a value close to 1 when the temperature is approximately 23°C was used, depending on the temperature coefficient of the sample, and the calculation was performed using the following formula 1.

[0207] [Formula 1]

[0208] Correction factor (CF) = cf1 × cf2 × cf3

[0209] The resistance values ​​read in the CMT-SR1000NH system and the correction coefficient (CF) calculated from Equation 1 are substituted into Equation 2 below to calculate the surface resistance in ohm / sq, which is summarized in Table 3 below.

[0210] [Formula 2]

[0211] Resistance (ohm) × Correction factor (CF) = Surface resistance (ohm / sq)

[0212] [Table 3]

[0213] As is clear from Table 3 above, the thin-film precursor compound according to the present invention exhibits excellent thermal stability at deposition temperatures of 350°C and 400°C, respectively, and it was confirmed that it provides a high deposition rate when deposition is performed at low temperatures. Furthermore, it was confirmed that the surface resistance values, as film formation characteristics at deposition temperatures of 350°C and 400°C, show a significant level when the resistance values ​​are corrected considering the thickness of the specimen.

[0214] Furthermore, referring to Table 3 above, a comparison of the cases at deposition temperatures of 350°C and 400°C revealed that the deposition rate was 0.74 Å / cycle when deposited at 350°C, and increased to 1.81 Å / cycle when the deposition temperature was raised to 400°C, showing an increase of nearly 144%.

[0215] In Example 2, the deposition rate is higher compared to Example 1. Unlike conventional techniques, this unexpected phenomenon occurs where, instead of an increase in impurities, the amount of impurities decreases as the deposition rate increases. This, when combined with increased production capacity (throughput), provides further significant advantages.

[0216]

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

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

[0219] *Thin film density (g / cm 3 ): Measured using X-ray reflectivity (XRR) analysis. This method observes the appearance that appears when X-rays are incident on the surface and reflect between the surface and the interface. By applying this analysis method to thin film specimens, the physical properties of the film, such as thickness, density, and surface and interface roughness, were measured.

[0220] The measurement results confirmed that Example 1, which was deposited at 350°C, showed an average cross-sectional thickness of 43.4 Å, while Example 2, which was deposited at 400°C, showed an average cross-sectional thickness of 156.9 Å.

[0221]

[0222] [Test Example 5] Confirmation of thin film thickness and step coverage properties of thin film precursor compounds

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

[0224] As is clear from Figure 5 below, the thin film thickness is confirmed to be uniform, and it can be seen that when the film is deposited at a specific deposition temperature, it exhibits excellent step-level coating properties and uniform coverage due to a self-limiting thin film growth mechanism, and moreover, it is possible to control the thickness with high precision.

[0225] Furthermore, when the step coverage of the Mo thin films deposited in Example 1 and Example 2 was confirmed using TEM, it was confirmed that both had high step coverage.

[0226]

[0227] [Test Example 6] Analysis of carbon concentration in thin films using ALD deposition of thin film precursor compounds

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

[0229] *Carbon concentration: The constituent elements, composition ratio, and chemical bonding state within the thin film were confirmed by performing depth profile analysis using an X-ray photoelectron spectrometer (XPS).

[0230] [Table 4]

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

Claims

1. A thin-film precursor compound represented by chemical formula 2, characterized in that the thin-film precursor compound is a compound represented by chemical formula 3 or chemical formula 4: [Chemical formula 2] ML １ L ２ L ３ L ４ (L ５ ) ｈ (L ６ ) ｉ (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 selected from the group consisting of: 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); where 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 among 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).) [Chemical formula 3] 【Chemistry 1】 [Chemical formula 4] 【Chemistry 2】 (In chemical formulas 3 to 4 above, M is 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, or +6 and a coordination number of 6; R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, a dimethylamine group, a substituted or unsubstituted C1-C7 alkyl group, and a substituted or unsubstituted C1-C7 alkoxy group; and n is an integer from 0 to 2.)

2. The thin film precursor compound according to claim 1, characterized in that the thin film precursor compound was obtained using a compound represented by the following chemical formula 1 as an intermediate. [Chemical formula 1] Mo(O)n(X)m(L)k (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.)

3. The thin-film precursor compound according to claim 2, characterized in that 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).

4. The aforementioned intermediate is (tBuN = ) ２ MoCl ２ The thin film precursor compound according to claim 2, characterized in that it is (DAE) (where DAE is a dialkoxyethane having 1 to 15 carbon atoms).

5. The thin film precursor compound according to claim 1, characterized in that the thin film precursor compound is liquid under conditions of 20°C and 1 bar, and is volatile.

6. A thin film formation method characterized by comprising the step of injecting a thin film precursor compound represented by chemical formula 2, wherein the thin film precursor compound is a compound represented by chemical formula 3 or chemical formula 4, into a chamber and depositing it onto the surface of a loaded substrate: [Chemical formula 2] ML １ L ２ L ３ L ４ (L ５ ) ｈ (L ６ ) ｉ (The aforementioned M is one or more selected from the group consisting of molybdenum (Mo), tungsten (W), chromium (Cr), and seaborgium (Sg), and has charges of 0, +3, +4, +5, +6 and a coordination number of 6, and the aforementioned L １ , L ２ , L ３ , L ４ , L ５ and L ６ Rd is independently selected from the group consisting of NRaRb;ORc;NRc;CO;RdCp;amidinates;guanidinates;ethylenediamines;propylenediamines;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); wherein Cp is cyclopentadienyl, Ra, Rb, Rc, and Rd are independently hydrogen or alkyl groups 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 L １ , L ２ , L ３ , L ４ , L ５ and L ６ One or more ligands selected from among 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). [Chemical formula 3] 【Transformation 3】 [Chemical formula 4] 【Chemistry 4】 (In chemical formulas 3 to 4 above, M is 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, or +6 and a coordination number of 6; R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, a dimethylamine group, a substituted or unsubstituted C1-C7 alkyl group, and a substituted or unsubstituted C1-C7 alkoxy group; and n is an integer from 0 to 2.)

7. The thin film forming method according to claim 6, characterized in that the deposition step includes a step of vaporizing the thin film precursor compound and adsorbing it onto the surface of a substrate introduced into the chamber, a step of purging the inside of the chamber with a purge gas, a step of supplying a reaction gas to the inside of the chamber, and a step of purging the inside of the chamber with a purge gas.

8. The thin film formation method according to claim 6, characterized in that the deposition step involves simultaneously injecting the thin film precursor compound and the reaction gas into a substrate that has been brought into the chamber.

9. The thin film formation method according to claim 6, characterized in that the deposition step is carried out by atomic layer deposition (ALD process), chemical vapor deposition (CVD process), plasma atomic layer deposition (PEALD process), or plasma chemical vapor deposition (PECVD process).

10. The thin film formation method according to claim 8, characterized in that a nitride agent, an oxidizing agent, or a reducing agent is used as the reaction gas.

11. The thin film formation method according to claim 6, characterized in that the thin film includes a metal nitride thin film, a metal oxide thin film, or a metal thin film.

12. A semiconductor substrate manufactured by the thin-film formation method described in claim 6.

13. A semiconductor device comprising the semiconductor substrate described in claim 12.

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