Thin film precursor compound, thin film forming method using same, and semiconductor substrate prepared thereby

Abstract

The present invention relates to a thin film forming method using a thin film precursor compound, a semiconductor substrate prepared thereby, and a semiconductor device, and according to the present invention, there is provided a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate prepared thereby, using a thin film precursor compound represented by a prescribed chemical formula 2, the present invention has the effects of very fast deposition speed, easy handling when injected into a thin film deposition chamber, particularly, very high purity and excellent step coverage due to significant thermal stability, and further, by suppressing a side reaction, a thin film growth rate is reduced, and even when a thin film is formed on a substrate having a complex structure, the thin film can be easily deposited on a substrate having a complex structure. According to the present invention, the step coverage and the thickness uniformity of the thin film can be substantially improved, and the density of the thin film can be improved, thereby substantially improving the electrical characteristics of the thin film.

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 prepared thereby. More specifically, the present invention relates to a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate prepared thereby. The thin film precursor compound is liquid at room temperature and highly volatile, so the deposition speed is very fast and it is easy to handle when injected into a thin film deposition chamber. In particular, due to its significant thermal stability, it has very high purity and excellent step coverage, thereby inhibiting side reactions and reducing the film growth rate. Even when a thin film is formed on a substrate with a complex structure, the step coverage and thickness uniformity of the thin film can be greatly improved, and the density of the thin film can be increased, thereby greatly improving the electrical properties of the thin film. Background Art

[0002] As the integration level of the conventional two-dimensional planar semiconductor device increases, the leakage current is aggravated while the cell pitch is narrowed. To overcome this situation, a 3D V NAND is developed that uses a three-dimensional structure to stack circuits to increase the integration level. In addition, when the thin film precursor material such as WF used as the electrode of the semiconductor device is used 6 Etc. for CVD (H 2 When the NAND is reduced, voids are generated due to fluorine, which creates cracks in the cell and reduces device performance. As the number of NAND layers increases, resistance increases. To overcome this problem, Mo compounds with low specific resistance are used. However, the Mo compounds currently used (such as MoO 2 Cl 2 etc.) are solid at room temperature, and the amount of sublimation is not constant, so there is a problem of difficulty in stable supply.

[0003] Prior art literature

[0004] Patent Literature

[0005] Korean Patent Publication No. 2006-0037241 Summary of the invention

[0006] Problem that the invention aims to solve

[0007] In order to solve the problems in the prior art as described above, the purpose of the present invention is to provide a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate prepared thereby. The thin film precursor compound is liquid at room temperature and has strong volatility, so the deposition speed is very fast and it is easy to handle when injected into a thin film deposition chamber. In particular, due to its significant thermal stability, it has very high purity and excellent step coverage, thereby inhibiting side reactions and reducing the thin film growth rate. Even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0008] The above-mentioned object and other objects of the present invention can all be achieved by the present invention described below.

[0009] Means used to solve problems

[0010] In order to achieve the above object, the present invention is characterized in that a thin film precursor compound represented by Chemical Formula 2 is provided.

[0011] [Chemical formula 2]

[0012] ML 1 L 2 L 3 L 4 (L 5 ) h (L 6 ) i

[0013] (Wherein, the M is selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, wherein L 1 , L 2 , L 3 , L 4 , L 5 and L 6 independently selected from the group consisting of NRaRb, ORc, NRc, CO, RdCp, amidino, guanidino, ethylenediamine, propylenediamine, and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), wherein Cp is a cyclopentadienyl group, wherein Ra, Rb, Rc and Rd are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein h and i are independently 0 or 1, and the total oxidation number of the compound is an integer from -2 to 6, and wherein L is selected from 1 , L 2 , L 3 , L 4 , L 5 and L6 One or more ligands are straight-chain or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S).

[0014] The thin film precursor compound may be a compound represented by the following Chemical Formula 3 or Chemical Formula 4.

[0015] [Chemical formula 3]

[0016]

[0017] [Chemical formula 4]

[0018]

[0019] (In the chemical formula 3 and the chemical formula 4, M is selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and 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, dimethylamino, substituted or unsubstituted alkyl having 1 to 7 carbon atoms, and substituted or unsubstituted alkoxy having 1 to 7 carbon atoms, and n is an integer from 0 to 2. )

[0020] The thin film precursor compound may be obtained by using a compound represented by the following Chemical Formula 1 as an intermediate.

[0021] [Chemical formula 1]

[0022] Mo(O)n(X)m(L)k

[0023] (The Mo is molybdenum, the O is oxygen, the X is a halogen, the L is a ligand, the n is an integer from 0 to 2, the m is an integer from 2 to 6, and the k is an integer from 1 to 3.)

[0024] 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).

[0025] The intermediate may be (tBuN=) 2 MoCl 2 (DAE) (wherein DAE may be a dialkoxyethane having 1 to 15 carbon atoms).

[0026] The thin film precursor compound may be liquid and volatile at 20° C. and 1 bar.

[0027] In addition, the present invention provides a thin film forming method, characterized in that the method comprises the steps of injecting a thin film precursor compound represented by Chemical Formula 2 into a chamber and depositing it on the surface of a loaded substrate.

[0028] [Chemical formula 2]

[0029] ML 1 L 2 L 3 L 4 (L 5 ) h (L 6 ) i

[0030] (M is selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, wherein L 1 , L 2 , L 3 , L 4 , L 5 and L 6 independently selected from the group consisting of NRaRb, ORc, NRc, CO, RdCp, amidino, guanidino, ethylenediamine, propylenediamine, and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), wherein Cp is a cyclopentadienyl group, wherein Ra, Rb, Rc and Rd are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein h and i are independently 0 or 1, and the total oxidation number of the compound is an integer from -2 to 6, and wherein L is selected from 1 , L 2 , L 3 , L 4 , L 5 and L 6 One or more ligands are straight-chain or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S).

[0031] The deposition step may include the following steps: vaporizing the thin film precursor compound and adsorbing it on the surface of a substrate loaded in a chamber; purging the interior of the chamber with a purge gas; supplying a reaction gas to the interior of the chamber; and purging the interior of the chamber with a purge gas.

[0032] During the deposition step, the thin film precursor compound and the reaction gas may be simultaneously injected onto the substrate loaded in the chamber.

[0033] The deposition step may be performed by 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).

[0034] The thin film forming method may use a nitriding agent, an oxidizing agent, or a reducing agent as a reaction gas.

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

[0036] Furthermore, the present invention provides a semiconductor substrate produced by the aforementioned thin film forming method.

[0037] Furthermore, the present invention provides a semiconductor device including the aforementioned semiconductor substrate.

[0038] Effects of the Invention

[0039] According to the present invention, a thin film precursor compound, a thin film forming method using the same, and a semiconductor substrate prepared thereby are provided, which have the following effects: the thin film precursor compound is liquid at room temperature and highly volatile, so the deposition speed is very fast, and it is easy to handle when injected into a thin film deposition chamber. In particular, due to its significant thermal stability, it has very high purity and excellent step coverage, thereby inhibiting side reactions and reducing the thin film growth rate. Even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0041] Figure 2 This is a graph showing the results of thermogravimetric analysis (DSC-TG analysis) of the thin film precursor compound synthesized in Synthesis Example 2.

[0042] Figure 3 This is a graph showing the results of differential scanning calorimetry (DSC) analysis of the thin film precursor compound synthesized in Synthesis Example 2.

[0043] Figure 4 This is a diagram schematically showing a deposition apparatus for performing atomic layer deposition using a thin film precursor compound in Example 1 or Example 2.

[0044] Figure 5The film precursor compound synthesized in Synthesis Example 2 was determined by using Figure 4 TEM of the thickness of the thin film cross section formed by the deposition equipment. The left picture corresponds to the deposition condition of 350℃, and the right picture corresponds to the deposition condition of 400℃. DETAILED DESCRIPTION

[0045] Hereinafter, the thin film precursor compound of the present invention, the thin film forming method using the same, and the semiconductor substrate produced thereby will be described in detail.

[0046] The inventors of the present invention have confirmed that when a thin film precursor compound having a prescribed structure is adsorbed on the surface of a substrate loaded inside an ALD chamber, it is in a liquid state at room temperature and highly volatile, so the deposition rate is very fast, and it is easy to handle when injected into a thin film deposition chamber. In particular, due to its remarkable thermal stability, the purity is very high, and the step coverage and film uniformity are improved. In addition, the inventors have confirmed that the residual halide as a process by-product is greatly reduced, thereby greatly improving the density and resistivity of the film. Based on these results, further research was conducted to complete the present invention.

[0047] The thin film precursor compound of one embodiment of the present invention is characterized in that the compound is represented by the following chemical formula 2. At this time, it is liquid at room temperature and has strong volatility, so the deposition speed is very fast and it is easy to handle when injected into the thin film deposition chamber. In particular, due to its significant thermal stability, it has a very high purity and improves step coverage.

[0048] [Chemical formula 2]

[0049] ML 1 L 2 L 3 L 4 (L 5 ) h (L 6 ) i

[0050] (M is selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and has a charge of 0, +3, +4, +5, +6 and a coordination number of 6, wherein L 1 , L 2 , L 3 , L 4 , L 5 and L 6independently selected from the group consisting of NRaRb, ORc, NRc, CO, RdCp, amidino, guanidino, ethylenediamine, propylenediamine, and a linear or cyclic saturated or unsaturated hydrocarbon having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), wherein Cp is a cyclopentadienyl group, wherein Ra, Rb, Rc and Rd are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein h and i are independently 0 or 1, and the total oxidation number of the compound is an integer from -2 to 6, and wherein L is selected from 1 , L 2 , L 3 , L 4 , L 5 and L 6 One or more ligands are straight-chain or cyclic saturated or unsaturated hydrocarbons having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S).

[0051] The thin film precursor compound can be selected from the compounds represented by the following chemical formula 3 or chemical formula 4. In this case, it is liquid at room temperature and highly volatile, so the deposition speed is very fast. It is easy to handle when injected into the thin film deposition chamber, especially, it induces selective bonding, thereby minimizing the contamination of the thin film. In addition, it is easy to remove with a reaction gas, thus having the advantages of high purity and excellent step coverage.

[0052] [Chemical formula 3]

[0053]

[0054] [Chemical formula 4]

[0055]

[0056] (In the chemical formula 3 and the chemical formula 4, M is selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and 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, dimethylamino, substituted or unsubstituted alkyl having 1 to 7 carbon atoms, and substituted or unsubstituted alkoxy having 1 to 7 carbon atoms, and n is an integer from 0 to 2. )

[0057] In the chemical formula 3 and the chemical formula 4, M may be selected from molybdenum (Mo), tungsten (W), chromium (Cr) and (Sg) and has charges of 0, +3, +4, +5, and +6 and a coordination number of 6.

[0058] In the chemical formula 3 and the chemical formula 4, R 1 , R 2 , R 3 , R 4 and R 5 The groups may be independently selected from the group consisting of H, substituted or unsubstituted C1 to C7 alkyl, substituted or unsubstituted C1 to C7 alkoxy and dimethylamine.

[0059] In the chemical formula 3 and the chemical formula 4, the R 1 and R 5 The radicals may be independently selected from H and substituted or unsubstituted C1 to C7 alkyl groups. For example, the radicals may be selected from methyl, ethyl, propyl, isopropyl, sec-butyl, isobutyl, tert-butyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, isohexyl, sec-hexyl, tert-hexyl, neobutyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, hexane, isohexane, neohexane, heptane, isoheptane and neoheptane.

[0060] In the chemical formula 3 and the chemical formula 4, R 2 The alkyl radicals may be independently selected from the group consisting of H and substituted or unsubstituted C1 to C7 alkyl radicals. For example, the alkyl radicals may be selected from methyl, ethyl, propyl, isopropyl, sec-butyl, isobutyl, tert-butyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, isohexyl, sec-hexyl, tert-hexyl, neobutyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, hexane, isohexane, neohexane, heptane, isoheptane and neoheptane.

[0061] In the chemical formula 3 and the chemical formula 4, the R 3 and R 4 The alkyl radicals may be independently selected from the group consisting of H and substituted or unsubstituted C1 to C7 alkyl radicals. For example, the alkyl radicals may be selected from methyl, ethyl, propyl, isopropyl, sec-butyl, isobutyl, tert-butyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, isohexyl, sec-hexyl, tert-hexyl, neobutyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, hexane, isohexane, neohexane, heptane, isoheptane and neoheptane.

[0062] In the present invention, as an example, C 1 To C 7 The alkyl group may include one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-butyl, and isomers thereof, but is not limited thereto.

[0063] In the present invention, as an example, C 1 To C7 The alkoxy group may include one selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentyl, neopentyl, tert-butoxy and isomers thereof, but is not limited thereto.

[0064] In the chemical formula 3 and the chemical formula 4, n may be an integer from 0 to 2.

[0065] As a specific example, in the chemical formula 3 and the chemical formula 4, M is molybdenum (Mo), R 1 and R 5 may be independently selected from H and substituted or unsubstituted C 1 To C 7 In the group consisting of alkyl groups, R 3 and R 4 may be independently selected from H and substituted or unsubstituted C 1 To C 5 In the group consisting of alkyl groups, R 2 The radicals may be independently selected from the group consisting of H, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C1 to C7 alkoxy, and dimethylamine, and n may be an integer of 0 to 2.

[0066] In addition, M is tungsten (W), R 1 and R 5 may be independently selected from H and substituted or unsubstituted C 1 To C 7 In the group consisting of alkyl groups, R 3 and R 4 may be independently selected from H and substituted or unsubstituted C 1 To C 5 In the group consisting of alkyl groups, R 2 can be independently selected from H, substituted or unsubstituted C 1 To C 5 Alkyl, substituted or unsubstituted C 1 To C 7 The present invention is selected from the group consisting of an alkoxy group and dimethylamine, and n may be an integer from 0 to 2.

[0067] In addition, M is chromium (Cr), R 1 and R 5 may be independently selected from H and substituted or unsubstituted C 1 To C 7 In the group consisting of alkyl groups, R 3 and R 4 may be independently selected from H and substituted or unsubstituted C 1 To C 5In the group consisting of alkyl groups, R 2 can be independently selected from H, substituted or unsubstituted C 1 To C 5 Alkyl, substituted or unsubstituted C 1 To C 7 The present invention is selected from the group consisting of an alkoxy group and dimethylamine, and n may be an integer from 0 to 2.

[0068] As an example, a thin film precursor compound of an implementation example of the present invention can be obtained by using the compound represented by the following chemical formula 1 as an intermediate. In this case, it is liquid at room temperature and highly volatile, so the deposition speed is very fast. It is easy to handle when injected into the thin film deposition chamber, and in particular, it induces selective bonding, thereby minimizing the contamination of the thin film. In addition, it is easy to remove with a reaction gas, thus having the advantages of high purity and excellent step coverage.

[0069] [Chemical formula 1]

[0070] Mo(O)n(X)m(L)k

[0071] (The Mo is molybdenum, the O is oxygen, the X is a halogen, the L is a ligand, the n is an integer from 0 to 2, the m is an integer from 2 to 6, and the k is an integer from 1 to 3.)

[0072] When the ligand is a straight-chain or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted by one or more nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), it is liquid at room temperature and highly volatile, so the deposition speed is very fast and it is easy to handle when injected into the thin film deposition chamber. In particular, it induces selective bonding, thereby minimizing contamination of the thin film. In addition, it is easy to remove with a reaction gas, thus having the advantages of high purity and excellent step coverage.

[0073] Preferably, the intermediate can be prepared by reacting a selected from the group consisting of MoX 6 、MoO 2 X 2 、MoOX 4 、MoO 2 X 2 and MoO 2 X 4 The molybdenum compound in the group consisting of (wherein X represents a halogen) is prepared by a substitution reaction with the ligand.

[0074] As a specific example, the ligand may be tert-butylamine, trimethylsilyl chloride, and 1,2-dimethoxyethane used in Synthesis Example 1 described later, but is not limited thereto.

[0075] Preferably, the intermediate may be (tBuN=) 2 MoCl2 (DAE) (wherein DAE can be a dialkoxyethane having a carbon number of 1 to 15), wherein, as an example, DAE can be ethylene glycol dimethyl ether (dimethoxyethane, DME), ethylene glycol diethyl ether (diethoxyethane, DEE) or diethylene glycol methyl ethyl ether (diethylmethoxy ethane, DEME), but is not limited thereto.

[0076] In the present invention, the thin film precursor compound obtained using the aforementioned intermediate is liquid at room temperature and highly volatile, so the deposition speed is very fast and it is easy to handle when injected into the thin film deposition chamber. In particular, it induces selective bonding, thereby minimizing the contamination of the thin film. In addition, it is easy to remove with a reaction gas, thus having the advantages of high purity and excellent step coverage.

[0077] Preferably, the thin film precursor compound is liquid and volatile under the conditions of 20°C and 1 bar. In this case, the deposition speed is very fast and it is easy to handle when injected into the thin film deposition chamber. In particular, it has significant thermal stability, so that the purity is very high and the step coverage is excellent. Furthermore, side reactions are inhibited, thereby reducing the film growth rate. Even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved, and the density of the thin film can be increased, thereby greatly improving the electrical properties of the thin film.

[0078] For reference, the reactants used in atomic layer deposition (ALD) need to have high volatility, material stability, and high reactivity. When ALD is performed in one cycle by separating the reaction raw materials and supplying them separately, a thin film below a monolayer is generated by surface reaction, and the ligands of the reaction raw materials adsorbed on the substrate are removed by chemical reaction with other reaction raw materials supplied later. Therefore, when heating the precursor as a reactant for atomic layer deposition, the liquid phase is obviously more advantageous than the solid phase in terms of reaction speed and process.

[0079] Unless otherwise specified, volatility refers to volatility exhibited in a chamber at 300° C. or higher, and in this case, it is suitable to exhibit an effect of being uniformly distributed on the substrate.

[0080] The thin film precursor compound of one embodiment of the present invention has a heteroligand coordinatedly bonded to the central metal, so that it not only exists in a liquid state at room temperature but also exhibits improved vapor pressure, etc.

[0081] The thin film precursor compound represented by the chemical formula 1, as a specific example, the thin film precursor compound represented by the chemical formula 3 or the chemical formula 4 each has excellent thermal stability, and thus can also be deposited at a low temperature. For reference, when the -NR 5 -C=C-NR 3 R 4 During grading, the chains become longer and can form coordination bonds with other parts besides the central metal. Therefore, it may be unfavorable for deposition based on chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), low pressure vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD).

[0082] On the contrary, the thin film precursor compound represented by the chemical formula 1 obtained using the aforementioned intermediate, as a specific example, the thin film precursor compound represented by the chemical formula 3 and the chemical formula 4 is purified at a relatively low temperature, i.e., 0.4 torr and 170°C to 180°C, and therefore not only has a good vapor pressure that is relatively favorable for deposition evaluation, but also has the advantage of providing liquid properties.

[0083] Furthermore, the thin film precursor compound represented by the chemical formula 1 obtained using the aforementioned intermediate, as a specific example, the thin film precursor compound represented by the chemical formula 3 and the chemical formula 4 has low reactivity with water, and thus has no risk of spontaneous combustion, and is easy to handle. Due to its high vapor pressure, it is helpful to form a thin film through deposition processes such as chemical deposition and atomic layer deposition.

[0084] In particular, during film formation, the physical properties of the thin film according to the process temperature show an ALD window area in the temperature range of 330°C to 370°C. In this range, an ALD precursor with a constant film formation temperature can be used, thereby reducing process costs.

[0085] The thin film forming method of the present invention is characterized in that it includes the following steps: injecting a thin film precursor compound represented by the aforementioned chemical formula 1, as a specific example, injecting a thin film precursor compound represented by chemical formula 3 or chemical formula 4 into the interior of a chamber and depositing it on the surface of a loaded substrate. At this time, it is liquid at room temperature and has strong volatility, so the deposition speed is very fast, and it is easy to handle when injected into a thin film deposition chamber. In particular, due to its significant thermal stability, it has very high purity and excellent step coverage, and it inhibits side reactions, thereby reducing the film growth rate. In addition, it removes process by-products in the thin film, so that even when a thin film is formed on a substrate with a complex structure, the step coverage and the thickness uniformity of the thin film can be greatly improved.

[0086] The thin film forming method of the present invention may include the following steps: vaporizing the thin film precursor compound represented by the aforementioned chemical formula 1, as a specific example, vaporizing the thin film precursor compound represented by chemical formula 3 or chemical formula 4 and adsorbing it on the surface of a substrate loaded in a chamber; purging the interior of the chamber with a purge gas; supplying a reaction gas to the interior of the chamber; and purging the interior of the chamber with a purge gas.

[0087] In the deposition step, the thin film precursor compound and the reaction gas may be injected sequentially or simultaneously onto the substrate loaded in the chamber.

[0088] In addition to using the thin film gold precursor compound of Chemical Formula 1, as a specific example, in addition to using the thin film gold precursor compound of Chemical Formula 3 or Chemical Formula 4 as a thin film precursor compound, the thin film forming method can be implemented by a conventional metal thin film preparation method, for example, atomic layer deposition (Atomic Layer Deposition, ALD process), chemical vapor deposition (Chemical Vapor Deposition, CVD process), plasma enhanced atomic layer deposition (PEALD process) or plasma chemical vapor deposition (PECVD process), preferably, it can be implemented by chemical vapor deposition or atomic layer deposition, but is not limited thereto.

[0089] Specifically, the metal thin film can be a thin film precursor compound represented by the chemical formula 1, which is vaporized. As a specific example, one or more of the thin film precursor compounds represented by the chemical formulas 3 to 4 are vaporized and supplied to a substrate on which a metal thin film layer is desired, for example, TiN, SiO 2 、Si 3 N 4 After being placed on a substrate such as the above, the precursor is decomposed to form a .

[0090] The thin film precursor compound may be injected onto the substrate at a temperature condition that matches the material properties, and the deposition process conditions may be varied according to the deposition efficiency.

[0091] Considering the efficiency of the deposition process, the film precursor compound is preferably injected in a heated state, for example, at 50°C to 400°C, and as a specific example, at 50°C to 350°C, for 1 second to 20 seconds on the substrate.

[0092] At this time, the method for gasifying the thin film precursor compound may include the following steps: using an inert gas to purge the non-adsorbed thin film precursor compound, and then injecting a reactive gas.

[0093] Specifically, a method of directly vaporizing the thin film precursor compound or injecting the thin film precursor compound into a constant temperature bath and then supplying an inert gas such as helium, neon, argon, krypton, xenon or nitrogen may be used.

[0094] The decomposition process of the film precursor compound can be carried out by heat treatment, plasma treatment or light irradiation, and 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 an oxidizing agent such as water vapor, oxygen and ozone is used as a reactive gas and the decomposition process of the film precursor compound is carried out, a metal oxide film can be formed, when a reducing agent such as hydrogen, ammonia, hydrazine and silane is used as a reactive gas and the decomposition process of the film precursor compound is carried out, a metal film can be formed, and when a nitriding agent such as nitrogen, ammonia, hydrazine and silane is used as a reactive gas and the decomposition process of the film precursor compound is carried out, a metal nitride film can be formed.

[0095] As a specific example, when the thin film precursor compound is decomposed by heat treatment, the process can be performed at 100°C to 1000°C. As an example, the deposition temperature of the substrate can be 50°C to 400°C, preferably 200°C to 400°C.

[0096] As an example, the feeding time (Feeding Time) of each cycle of supplying the thin film precursor compound to the substrate surface is preferably 1 second to 10 seconds, more preferably 1 second to 5 seconds, further preferably 2 seconds to 5 seconds, and most preferably 2 seconds to 4 seconds. Within this range, it has the advantages of excellent step coverage and economy.

[0097] As an example, the feeding time (Feeding Time) of the aforementioned thin film precursor compound is based on the chamber volume of 15L to 20L and the flow rate of 0.5mg / s to 5mg / s. More specifically, it can be based on the chamber volume of 18L and the flow rate of 1mg / s to 2mg / s. When the volume and flow rate of the chamber change, the optimal deposition efficiency can also be achieved by adjusting the feeding time.

[0098] Preferably, the thin film precursor compound can be transferred into the chamber by VFC, direct liquid injection (DLI) or liquid delivery system (LDS), and more preferably, can be transferred into the chamber by LDS.

[0099] In the present invention, the purge is preferably 1000 sccm to 10000 sccm, more preferably 2000 sccm to 7000 sccm, and further preferably 2500 sccm to 6000 sccm. Within this range, the film growth rate of each cycle is reduced within a preferred range and has the effect of reducing process by-products.

[0100] The deposition of the present invention can be carried out using deposition equipment commonly used in the art. In the embodiments described below, Figure 4 The deposition equipment shown in FIG. 1 is used to prepare a thin film by atomic layer deposition (ALD).

[0101] the following, Figure 4 This is a schematic diagram showing the use of NH 3 The diagram of the deposition equipment that uses gas as a nitriding agent and performs the atomic layer deposition method of the present invention, operates the raw material circuit and the reaction gas circuit separately so that the properties of the material can be maximized by adjusting the temperature to meet each property. However, when prepared by using equipment that integrates the operation of the raw material circuit and the reaction gas circuit, it does not depart from the scope of the rights of the present invention.

[0102] In addition, in the present invention, a thin film preparation device that can implement the thin film preparation method may include: an ALD chamber; a first vaporizer that vaporizes a thin film precursor compound; a first transfer device that transfers the vaporized thin film precursor compound into the ALD chamber; and a second transfer device that transfers the reaction gas into the ALD chamber. When the vaporizer and the transfer device are commonly used in the technical field to which the present invention belongs, no particular limitation is imposed.

[0103] In the preparation method of the metal-containing film of the present invention as described above, by using a thin film precursor compound with excellent thermal stability, when performing the deposition process, compared with the prior art, the deposition process can be carried out at a low temperature without particle contamination or impurity (carbon, etc.) contamination caused by thermal decomposition of the precursor, so that the crystallinity is excellent, thereby forming a high-purity metal film, metal oxide or metal nitride film at a fast deposition rate without process by-products.

[0104] In the thin film forming method of the present invention, a film quality improver, a thin film growth inhibitor, a thin film growth activator, or the like known in the art may be used as necessary.

[0105] In addition, the ALD chamber or ALD process is exemplarily described in this specification, but is not limited thereto. For reference, the atomic layer deposition process (ALD) is very advantageous in the preparation of integrated circuits (ICs) requiring high aspect ratios, and in particular, has advantages such as excellent step coating (conformality), uniform coverage (uniformity) and precise thickness control through a self-limiting film growth mechanism.

[0106] As an example, the thin film forming method can be implemented at a deposition temperature in the range of 50°C to 900°C, preferably in the range of 300°C to 700°C, more preferably in the range of 350°C to 600°C, further preferably in the range of 400°C to 550°C, and most preferably in the range of 400°C to 500°C. Within this range, the effect of growing a thin film with excellent film quality while realizing the ALD process characteristics is achieved.

[0107] As an example, the thin film forming method can be implemented at a deposition pressure in the range of 0.1 Torr to 10 Torr, preferably in the range of 0.5 Torr to 5 Torr, and more preferably in the range of 1 Torr to 3 Torr. Within this range, a thin film of uniform thickness can be obtained.

[0108] In the present invention, the deposition temperature and the deposition pressure may be measured as the temperature and pressure formed in the deposition chamber, or may be measured as the temperature and pressure applied to the substrate in the deposition chamber.

[0109] Preferably, the thin film forming method may include the following steps: before adding the thin film precursor compound into the chamber, raising the temperature in the chamber to the deposition temperature; and / or before adding the thin film precursor compound into the chamber, injecting an inactive gas into the chamber for purging.

[0110] As a specific example, the thin film forming method is described. First, a substrate on which a thin film is to be formed is placed in a deposition chamber capable of performing atomic layer deposition.

[0111] The substrate may include a semiconductor substrate such as a silicon substrate or silicon oxide.

[0112] The substrate may further have a conductive layer or an insulating layer formed on an upper portion thereof.

[0113] In order to deposit a thin film on a substrate placed in the deposition chamber, the thin film precursor compound mentioned above is prepared.

[0114] Then, after the prepared thin film precursor compound is injected into the vaporizer, it is changed into a vapor phase, and is transferred to the deposition chamber and adsorbed on the substrate, and the unadsorbed thin film precursor compound is purged.

[0115] In the present invention, as an example, the method of delivering thin film precursor compounds and the like to the deposition chamber can adopt a vapor flow control (Vapor Flow Control, VFC) method of transferring volatile gases using a gas phase flow control (Mass Flow Controller, MFC) method or a liquid delivery system (Liquid Delivery System, LDS) method of transferring liquid using a liquid phase flow control (Liquid Mass Flow Controller, LMFC) method, and the LDS method is preferably adopted.

[0116] At this time, as a transport gas or dilution gas for transferring the thin film precursor compound and the like to the substrate, a gas selected from argon (Ar), nitrogen (N 2 ), helium (He) or a mixture of two or more gases, but not limited to these.

[0117] In the present invention, as an example, an inert gas may be used as the purge gas, and preferably, the transport gas or the dilution gas may be used.

[0118] Then, a reaction gas is supplied. The reaction gas may be any reaction gas conventionally used in the technical field to which the present invention belongs, and preferably 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, the nitriding agent forms a metal nitride thin film, and the oxidizing agent forms a metal oxide thin film.

[0119] Next, the unreacted residual reaction gas is purged with an inert gas, thereby removing not only the excess reaction gas but also the generated by-products.

[0120] As described above, the following steps are taken as a unit cycle: a step of adsorbing a thin film precursor compound onto a substrate, a step of purging the unabsorbed thin film forming composition, a step of supplying a reaction gas, and a step of purging the residual reaction gas; the unit cycle may be repeated to form a thin film of a desired thickness.

[0121] As an example, the number of repetitions of the unit cycle may be 100 to 1000 times, preferably 100 to 500 times, and more preferably 150 to 300 times. Within this range, the desired film properties can be well expressed.

[0122] Under the conditions of 20°C and atmospheric pressure used in the prior art ALD process, when used as a solid molybdenum-based thin film precursor (e.g., MoO 2 Cl 2 ) compounds, since it is difficult to sublimate solids, the reaction gas (e.g., NH 3 ) reaction, resulting in residual process byproducts (such as NH 4 Cl, HCl), resulting in degradation of the substrate performance due to corrosion or degradation. However, when the thin film precursor compound of the present invention is used, the deposition rate is accelerated due to improved thermal stability and the reaction with the reaction gas (e.g., NH 3 ) reaction, so the process by-products (such as NH 4 Cl, HCl) are removed together with the film precursor compounds, thereby preventing corrosion or degradation of the substrate, improving not only the step coverage and uniformity of film thickness, but also the density of the film, and even providing excellent electrical properties.

[0123] According to another embodiment of the present invention, a metal-containing film prepared by the thin film forming method is provided.

[0124] The metal-containing film may be a metal nitride film, a metal oxide film or a metal film according to the reaction gas used, and such a metal-containing film may be a film having high conformity and film uniformity even if having a complex structure with precise thickness control.

[0125] The semiconductor substrate of the present invention is characterized in that it is prepared by the thin film forming method of the present invention. In this case, the deposition rate is improved while removing process by-products in the thin film, thereby having the effect of preventing corrosion or degradation and having very significant step coverage and film thickness uniformity.

[0126] The semiconductor substrate may include a base material such as a wafer and a thin film formed on the base material, and the thin film may be prepared by the method.

[0127] Preferably, the thickness of the prepared film is less than 20 nm, the resistivity is 0.1 μΩ·cm to 400 μΩ·cm, the halogen content is less than 10000 ppm, and the step coverage is more than 90%. Within this range, as a diffusion prevention film, it has significant performance and the effect of reducing corrosion of metal wiring materials, but is not limited to this.

[0128] As an example, the thickness of the thin film may be 5 nm to 20 nm, preferably 10 nm to 20 nm, more preferably 15 nm to 18.5 nm, and further preferably 17 nm to 18.5 nm. Within this range, the film has excellent properties.

[0129] As an example, the resistivity of the film may be 0.1 μΩ·cm to 400 μΩ·cm, preferably 50 μΩ·cm to 400 μΩ·cm, and more preferably 100 μΩ·cm to 300 μΩ·cm. Within this range, the film has excellent properties.

[0130] Preferably, the halogen content of the film may be less than 9000 ppm or 1 ppm to 9000 ppm, preferably less than 8500 ppm or 100 ppm to 8500 ppm, more preferably less than 8200 ppm or 1000 ppm to 8200 ppm. Within this range, the film has excellent properties and has the effect of reducing corrosion of metal wiring materials.

[0131] As an example, the step coverage of the film can be above 80%, preferably above 90%, and more preferably above 92%. Within this range, even a thin film with a complex structure can be easily deposited on a substrate. Therefore, it has the advantage of being applicable to a new generation of semiconductor equipment.

[0132] As an example, the prepared thin film can be a Mo thin film, a MoN thin film, a MoO thin film, a MoS 2 Thin film or MoSe 2 film.

[0133] According to another implementation example of the present invention, a semiconductor device including the semiconductor substrate is provided.

[0134] As an example, the semiconductor device may be a low resistive metal gate interconnects, a high aspect ratio 3D metal-insulator-metal (MIM) capacitor, a DRAM trench capacitor, a 3D Gate-All-Around (GAA), or a 3D NAND.

[0135] Below, preferred embodiments are proposed to help understand the present invention, but those skilled in the art should be aware that the following embodiments are merely illustrative of the present invention, and that various changes and modifications can be made within the scope of the present invention and the technical concept, and these deformations and modifications also fall within the scope of the attached patent claims.

[0136] [Example]

[0137] Synthesis example 1: (tBuN=) 2 MoCl 2 Synthesis of (DME)

[0138] by Na 2 MoO 4 According to the following reaction formula 1, (tBuN=) 2 MoCl 2 DME.

[0139] [Reaction 1]

[0140]

[0141] Specifically, in a dry argon atmosphere, 67 g (486 mmol) of Na 2 MoO 4 , 1 L of 1,2-dimethoxyethane, 180 mL of trimethylamine, 374 mL of trimethylsilyl chloride, and 80 mL of tert-butylamine were added, and the mixture was reacted for 24 hours under reflux at 65° C., and the completion of the reaction was confirmed by NMR.

[0142] Unless otherwise mentioned, the various substances used in the above reaction formulas were synthesized and purified, and high purity products of more than 99% were used. The obtained yellow solution was filtered, washed with hexane and the filtrate was vacuum dried. The obtained solid was repeatedly washed with hexane to obtain 27 g (yield 21 wt%) of (tBuN=) 2 MoCl 2 (DME), and its NMR analysis confirmed that (tBuN=) 2 MoCl 2 Intermediates of DME structure.

[0143] 1 H NMR (in C 6 D 6 )(3.48ppm,s,6H),(3.22ppm,s,4H)(1.42ppm,s,18H).

[0144] Synthesis example 2: (tBuN=) 2 Synthesis of Mo(TBDMAE)(DMA)

[0145] The (tBuN=) obtained in Synthesis Example 1 was used. 2 MoCl 2 (DME), (tBuN=) was synthesized according to the following reaction formula 2 2 Mo(TBDMAE)(DMA).

[0146] [Reaction 2]

[0147]

[0148] Specifically, 95.5 g (239.2 mmol) of (tBuN=) 2 MoCl 2 DME was added to a 1 L Schlenk flask, and then 160 mL of anhydrous toluene was added, and the flask was cooled to -5°C with ethanol and dry ice.

[0149] 12.2 g (239.2 mmol) of lithium dimethylamide [LiDMA] was dissolved in 30 mL of toluene and then added dropwise to the 1 L Schlenk flask via a cannula. The mixture was stirred at room temperature for 2 hours, and the synthesis was confirmed by NMR.

[0150] Next, 38 g of Li-TBDMAE synthesized separately was dissolved in hexane and added dropwise to the 1 L Schlenk flask at -5°C. The abbreviation TBDMAE refers to 1-(tert-butylamino)-2-(dimethylamino)ethane. After the reaction was completed by NMR, the solvent was removed by filtration.

[0151] The obtained synthesis product was purified by a purification tube to obtain 20 g (yield 30 wt%) of pure (tBuN=) 2 After Mo(TBDMAE)(DMA), 1 The results of H NMR analysis are shown in Figure 1 middle.

[0152] As follows Figure 1 As shown, through 1 H NMR analysis confirmed that the synthesized substance was the desired substance (tBuN=) 2 Mo(TBDMAE)(DMA).

[0153] Synthesis example 3: (tBuN=) 2 Synthesis of Mo(TBDMAE)(DMA)

[0154] The (tBuN=) obtained in Synthesis Example 1 was used. 2 MoCl 2 (DME), (tBuN=) was synthesized according to the following reaction formula 3 2 Mo(TBDMAE)(tBuO).

[0155] [Reaction 3]

[0156]

[0157] 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-butyl lithium (n-BuLi) was added at 0°C. After stirring for 30 minutes, 2.41 g (25 mmol) of sodium tert-butoxide was mixed. The abbreviation TBDMAE refers to 1-(tert-butylamino)-2-(dimethylamino)ethane.

[0158] The mixed solution was mixed with 10 g (25 mmol) of (tBuN=) 2 MoCl 2 (DME) and 50 mL of anhydrous toluene were cooled to below 0°C and placed in a 250 mL Schlenk flask, followed by stirring at room temperature for 12 hours.

[0159] 38 g of Li-TBDMAE synthesized separately was dissolved in hexane and then added dropwise to the 250 mL Schlenk flask at -5°C.

[0160] The stirred solution was filtered and the filtrate was decompressed to obtain (tBuN=) 2 Mo(TBDMAE)(tBuO).

[0161] For the obtained crude (tBuN=) 2 Mo(TBDMAE)(tBuO) was purified to obtain 5 g (yield 50 wt%) of brown liquid. 1 The results of H NMR analysis confirmed that the synthesized 2 The compound represented by Mo(TBDMAE)(tBuO) is the substance to be prepared.

[0162] Test Example 1: Confirmation of the properties of thin film precursor compounds

[0163] The properties of the thin film precursor compounds prepared in Synthesis Example 1 and Synthesis Example 2 at 20° C. and 1 atmosphere were confirmed to be liquid and highly volatile.

[0164] Experimental Example 2: Thermogravimetric analysis (TG analysis) of film precursor compounds

[0165] The thin film precursor compounds prepared in Synthesis Example 1 and Synthesis Example 2 were subjected to thermogravimetric analysis (TGanalysis).

[0166] The instrument used in the thermogravimetric analysis (TGA) was a TGA / DSC1STARe system from Mettler Toledo, and an alumina crucible with a capacity of 50 μL was used. The content of all samples used was 8 mg to 11 mg, and the temperature was measured from 30°C to 500°C.

[0167] The measured values ​​of the thermogravimetric analysis are shown in Figure 2 and Figure 3 In. Below Figure 2 is a graph showing the results of the DSC-TG analysis of the film precursor compound synthesized in Synthesis Example 2. Figure 3 This is a graph showing the results of differential scanning calorimetry (DSC) analysis of the thin film precursor compound synthesized in Synthesis Example 2.

[0168] As follows Figure 2 and Figure 3 As shown, it was confirmed that the thin film precursor compound (tBuN=) obtained in Synthesis Example 2 2 Mo(TBDMAE)(DMA) had a T1 / 2 of 118°C and a Tend of 237°C, thus confirming excellent thermogravimetric analysis values. 2 Mo(TBDMAE)(DMA), it can be confirmed that the thin film precursor compound (tBuN=) obtained in Synthesis Example 3 2 The thermogravimetric analysis value of Mo(TBDMAE)(tBuO) is larger.

[0169] In addition, the results of heat flow analysis show that the film precursor compound of the present invention decomposes in a single pattern (see below). Figure 2 (see the blue ink graph in the figure).

[0170] [Example]

[0171] Example 1 to Example 4

[0172] The thin film precursor compounds listed in Table 1 were placed in a tank and supplied to a vaporizer using a liquid mass flow controller (LMFC) at room temperature.

[0173] After the thin film precursor compound vaporized in the vaporizer into a vapor phase is introduced into a deposition chamber loaded with a substrate, the following deposition temperature conditions are used under the deposition temperature conditions listed in Table 1: Figure 4 The deposition apparatus shown in performs atomic layer deposition (ALD) to form a film.

[0174] Specific deposition conditions are further shown in Table 2 below.

[0175] [Table 1]

[0176] distinguish Thin film precursor compounds Deposition temperature (℃) Example 1 <![CDATA[(tBuN=) 2 Mo(TBDMAE)(DMA)]]> 350 Example 2 <![CDATA[(tBuN=) 2 Mo(TBDMAE)(DMA)]]> 400 Example 3 <![CDATA[(tBuN=) 2 I(TBDMAE)(tBuO)]]> 350 Example 4 <![CDATA[(tBuN=) 2 I(TBDMAE)(tBuO)]]> 400

[0177] [Table 2]

[0178]

[0179]

[0180] The film precursor compound was placed in a stainless steel tank and supplied to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using a liquid mass flow controller (LMFC) at room temperature. The precursor injection time from the vaporizer to the chamber was fixed at 2 seconds, the precursor purge time was fixed at 4 seconds, and the NH 3 The injection time is fixed at 3 seconds, NH 3 The purge time was fixed at 6 seconds, and atomic layer deposition was performed (see Table 2). First, 50 wt % hydrofluoric acid (HF) and deionized water (DI) (H 2 O) The silicon wafer is immersed in a 3:2 mixed HF aqueous solution for 1 minute, taken out, and then immersed in a deionized water (DI) solution for 4 minutes to remove the natural oxide film. After preparing the substrate to form a pure silicon surface, it is loaded into a chamber and heated to 300°C to 350°C.

[0181] Next, argon (Ar) with a flow rate of 500 sccm was used as a carrier gas, and after the compound vaporized into a vapor phase by heating was injected into the deposition chamber loaded with the substrate, argon (Ar) was supplied at 500 sccm for 4 seconds to perform argon purge. The pressure in the reaction chamber was controlled at 2.5 Torr.

[0182] And, NH 3 After the gas is injected at 1000 sccm for 3 seconds to form a nitride film, argon (Ar) is supplied at 500 sccm for 6 seconds to perform argon purge. At this time, the substrate on which the metal thin film is to be formed is heated to 300°C to 450°C.

[0183] This process was repeated 200 times to form a MoN thin film as a self-limiting atomic layer.

[0184] Experimental Example 3: Evaluation of film formation by ALD deposition of thin film precursor compounds

[0185] The results of film formation evaluation of the nitride films of Examples 1 to 4 confirmed that the physical properties of the films according to the process temperature showed an ALD window region in the temperature range of 330°C to 370°C, and that the ALD precursor had a constant film growth temperature in this range.

[0186] Specifically, the deposition rate and specific resistance (surface resistance) of the thin films obtained according to Example 1 and Example 2 were measured.

[0187] *Deposition rate (Dep. Rate, GPC) (°C / cycle): GPC is the abbreviation of Growth Per Cycle. The supply of precursors, reactants and purge gases is used as a basis for one cycle, and a thin film is formed after several cycles. After measuring the optical thickness of the formed film using an ellipsometer, the growth rate of the film formed per cycle (1 cycle) is calculated from the total thickness of the formed film and is shown in Table 3.

[0188] * Sheet resistance (Re) (uΩ.cm): Sheet resistance is calculated by measuring the sheet resistance using a 4-point probe and substituting the correction factor.

[0189] Specifically, the MICRONICS CMT-SERIES model is used as a 4-point probe device, and four probes are placed on the surface of the test piece. Current is applied to the outer probes, and the voltage of the middle probe is measured to obtain the resistance value. The resistance value is then read in the CMT-SR1000NH system.

[0190] In addition, the correction coefficient is calculated using three coefficients, namely, sample size, film thickness, and temperature at a specific time. The sample size coefficient is 4.532, which is a value usually used for samples with a diameter of more than 40 mm, and the film thickness coefficient is 1, which is a value usually used when the film thickness is about 400 μm or less. Based on the temperature coefficient of the sample, a value close to 1 is used when the temperature is about 23°C, and the correction coefficient is calculated using the following mathematical formula 1.

[0191] [Mathematical formula 1]

[0192] Correction coefficient (CF) = cf1 × cf2 × cf3.

[0193] The resistance value read from the CMT-SR1000NH system and the correction factor (CF) calculated from the mathematical formula 1 are substituted into the following mathematical formula 2 to calculate the surface resistance in ohm / sq and are summarized in Table 3.

[0194] [Mathematical formula 2]

[0195] Resistance value (ohm) × correction factor (CF) = surface resistance (ohm / sq).

[0196] [Table 3]

[0197]

[0198] As shown in Table 3, it can be confirmed that the thin film precursor compound of the present invention has excellent thermal stability at deposition temperatures of 350°C and 400°C, respectively, thereby providing a high deposition rate when deposited at low temperatures. In addition, at deposition temperatures of 350°C and 400°C, when the resistance value is corrected in consideration of the thickness of the test piece, it can be confirmed that the surface resistance value as a film forming characteristic shows a significant level.

[0199] Furthermore, referring to Table 3 above, by comparing the deposition temperatures of 350°C and 400°C, it can be confirmed that when deposited at 350°C, the deposition rate is When the deposition temperature is increased to 400°C, it can be confirmed that the deposition rate is The increase was close to 144%.

[0200] It can be confirmed that although the deposition rate of Example 2 is increased compared to Example 1, unlike the prior art, the impurities do not increase as the deposition rate increases, but instead the impurities decrease unexpectedly, thus providing another important advantage in terms of throughput.

[0201] Experimental Example 4: Analysis of the thickness of a thin film cross section by ALD deposition of thin film precursor compounds

[0202] The thickness of the cross section of the film obtained in Test Example 3 and the film density were analyzed as follows.

[0203] *Film density (g / cm 3 ): The X-ray reflectivity (XRR) analysis method was used to measure the physical properties of the film, such as thickness, density, surface and interface roughness, by applying the X-ray reflectivity (XRR) analysis method to the film-formed thin film test pieces.

[0204] The measurement results show that in Example 1 measured at 350°C, The average cross-sectional thickness of the embodiment 2 was measured at 400°C and confirmed The average cross-sectional thickness.

[0205] Test Example 5: Confirmation of the thickness and step coverage of the thin film of the thin film precursor compound

[0206] The film thickness and step coverage of the film cross section obtained in Experimental Example 3 were confirmed by taking TEM photographs. Figure 5 The thin film precursor compound synthesized in Synthesis Example 2 was measured by using Figure 4 Transmission electron microscope (TEM) photos of the thickness of the thin film cross-section formed by the deposition equipment. The left picture corresponds to the deposition condition of 350℃, and the right picture corresponds to the deposition condition of 400℃.

[0207] As follows Figure 5 As shown, it is confirmed that the film thickness is uniform. When the film is formed at a specific deposition temperature, excellent step coating, uniform coverage and precise thickness control can be achieved through the self-limiting film growth mechanism.

[0208] In addition, the step coverage of the Mo thin films deposited in Examples 1 and 2 was confirmed by TEM, and it was confirmed that the step coverage was high in both cases.

[0209] Experimental Example 6: Analysis of Carbon Concentration in Thin Films by ALD Deposition of Thin Film Precursor Compounds

[0210] The carbon concentration of the thin film obtained in Test Example 3 was analyzed as follows. The results are shown in Table 4.

[0211] *Carbon concentration: The composition elements, composition ratio and chemical bonding state in the film were confirmed through X-ray photoelectron spectroscopy (XPS) depth profile analysis.

[0212] [Table 4]

[0213]

[0214] As shown in Table 4, the X-ray Photoelectron Spectrometer (XPS) depth profile results of the thin films obtained in Examples 1 and 2 confirmed that they were MoN thin films and provided a significant carbon concentration.

Claims

1. A thin film precursor compound, characterized in that: Represented by chemical formula 2, [Chemical formula 2] <h2 style=";text-align:left;direction:ltr">ML1L2L3L4(L5)<h2 style=";text-align:left;direction:ltr"> h <h2 style=";text-align:left;direction:ltr"> (L6)<h2 style=";text-align:left;direction:ltr"> i The M is selected from molybdenum, tungsten, chromium and The invention relates to a ligand selected from the group consisting of: a cyclopentadienyl group, ...

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 4] In the chemical formula 3 and the chemical formula 4, M is selected from molybdenum, tungsten, chromium and The invention relates to one or more of the group consisting of: 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, dimethylamino, substituted or unsubstituted alkyl having 1 to 7 carbon atoms and substituted or unsubstituted alkoxy having 1 to 7 carbon atoms, and n is an integer from 0 to 2.

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

4. The thin film precursor compound according to claim 3, characterized in that: The ligand is a linear or cyclic saturated hydrocarbon having 3 to 15 carbon atoms and substituted by one or more nitrogen, oxygen, phosphorus or sulfur.

5. The thin film precursor compound according to claim 3, characterized in that: The intermediate is (tBuN=)2MoCl2(DAE), Here, DAE is a dialkoxyethane having 1 to 15 carbon atoms.

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

7. A method for forming a thin film, characterized in that: include: a deposition step of injecting a thin film precursor compound represented by Chemical Formula 2 into the chamber and depositing it on the surface of the loaded substrate, [Chemical formula 2] <h2 style=";text-align:left;direction:ltr">ML1L2L3L4(L5)<h2 style=";text-align:left;direction:ltr"> h <h2 style=";text-align:left;direction:ltr"> (L6)<h2 style=";text-align:left;direction:ltr"> i The M is selected from molybdenum, tungsten, chromium and The invention relates to a ligand selected from the group consisting of: a cyclopentadienyl group, ...

8. The thin film forming method according to claim 7, characterized in that: The deposition step comprises: The step of vaporizing the thin film precursor compound and making it adsorb on the surface of the substrate loaded in the chamber; The step of purging the interior of the chamber using a purge gas; supplying a reaction gas into the chamber; and The step of purging the interior of the chamber using a purge gas.

9. The thin film forming method according to claim 7, characterized in that: In the deposition step, the thin film precursor compound and the reaction gas are simultaneously injected onto the substrate loaded in the chamber.

10. The thin film forming method according to claim 7, characterized in that: The step of depositing is performed by atomic layer deposition, chemical vapor deposition, plasma enhanced atomic layer deposition or plasma chemical vapor deposition.

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

12. The thin film forming method according to claim 7, characterized in that: The film includes a metal nitride film, a metal oxide film or a metal film.

13. A semiconductor substrate, characterized in that: Prepared by the thin film forming method according to claim 7.

14. A semiconductor device, characterized in that: Comprising the semiconductor substrate according to claim 13.

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