Film quality improving agent, thin film formation method using the same, and semiconductor substrate and semiconductor device manufactured therefrom.

Abstract

The present invention relates to a film quality improver, a thin film formation method using the same, and a semiconductor substrate and a semiconductor device manufactured therefrom. A compound having a specific structure is provided as a film quality improver, and a shielding region for a molybdenum-based thin film is formed on a substrate to reduce the deposition rate of the molybdenum-based thin film. By controlling the thin film growth rate, even when a thin film is formed on a substrate having a complex structure using a compound that is solid at room temperature, the step coverage and the thickness uniformity of the thin film can be significantly improved, corrosion and deterioration are reduced, and the crystallinity of the thin film is improved, thereby improving the electrical properties of the thin film.

Description

[Technical Field]

[0001] The present invention relates to a film quality improving agent, a thin film formation method using the same, and semiconductor substrates and semiconductor devices manufactured therefrom. More specifically, the present invention relates to a film quality improving agent that significantly improves the quality of the film, such as step coverage, thickness uniformity, and resistivity, when forming a shielding region for molybdenum-based thin films on a substrate to reduce or increase the deposition rate of the molybdenum-based thin film, appropriately adjusting the thin film growth rate to form a thin film on a substrate with a complex structure, or when forming a thin film using a solid precursor at room temperature. The present invention also relates to a thin film formation method using the same and semiconductor substrates manufactured therefrom. [Background technology]

[0002] Molybdenum (Mo) has excellent chemical and thermal stability, high electrical conductivity, and low electrical resistivity (ρ = 0.57 x 10⁻¹⁰). -5 It has a density of Ω·cm at bulk and has recently attracted attention as a material that meets the demands for miniaturization of devices, low power consumption, and high productivity.

[0003] Specifically, molybdenum (Mo) is used in a variety of semiconductor and display metal processes as an electrode, diffusion barrier, gas sensor, and catalyst. In particular, molybdenum-containing thin films are attracting attention as a two-dimensional semiconductor material that can replace graphene, and research into its applications is progressing rapidly.

[0004] A typical molybdenum compound used to form molybdenum-containing thin films is molybdenum chloride (MoCl5). However, according to Thin Solid Films, 166, 149 (1988), it has been reported to have disadvantages such as low deposition rates, high chlorine content, and film contamination by hydrogen chloride, etc. In particular, it has the disadvantage of being a solid compound that does not cause particle contamination and does not allow for uniform precursor vaporization.

[0005] Furthermore, while imide compounds such as Mo(NtBu)2(NiPR2)2, reported in Chem. Vap. Deposition (2008) 14, 71, are known, they have relatively poor thermal stability, and due to the high stability provided by the π-bond between the molybdenum central metal and nitrogen via the imide ligand, ligand decomposition does not occur well during the process, resulting in the disadvantage of very serious carbon pollution.

[0006] U.S. Patent Publication No. 4,431,708 and J. dePhys. IV2(C2), 865 report on molybdenum-containing thin films produced by vapor deposition using Mo(CO)6 compounds with relatively high vapor pressure. However, due to the non-uniform vaporization characteristics of solid compounds at room temperature, these are likely to result in low thermal stability and particle problems.

[0007] Therefore, there is a need to develop a method for forming thin films that do not contain halogens or other substances that are highly likely to adversely affect semiconductors and display elements, while simultaneously enabling the formation of thin films with complex structures even in a solid state at room temperature, and significantly improving step coverage and thickness uniformity of the thin films, as well as semiconductor substrates manufactured from such films. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] To solve the problems of the conventional technology described above, the present invention aims to provide a film quality improving agent that forms a shielding region for molybdenum-based thin films on a substrate to reduce or increase the deposition rate of the molybdenum-based thin film, thereby appropriately adjusting the thin film growth rate to form a thin film on a substrate with a complex structure, or when forming a thin film using a solid precursor at room temperature, thereby greatly improving the quality of the film, such as step coverage, thickness uniformity of the thin film, or resistivity; a thin film formation method using the same; and a semiconductor substrate manufactured therefrom.

[0009] The present invention aims to improve the density and electrical properties of a thin film by improving its crystallinity.

[0010] All of the above and other objectives of the present invention can be achieved by the present invention as described below. [Means for solving the problem]

[0011] To achieve the above objective, the present invention provides a film quality improving agent for molybdenum-based thin films,

[0012] The aforementioned molybdenum-based thin film contains molybdenum, molybdenum oxide, or molybdenum nitride on a substrate.

[0013] The aforementioned film quality improving agent is defined by the following chemical formula 1

[0014] [Chemical formula 1]

[0015] TIFF0007858054000001.tif6468

[0016] (A is carbon (C) or silicon (Si), and X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I),

[0017] R1 and R3 are independently hydrogen, a C1 to C5 alkyl group, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0018] The present invention provides a film quality improving agent for molybdenum-based thin films, characterized in that R2 independently has hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or a functional group of the formula BR4R5R6, B is carbon or silicon, and R4, R5, and R6 independently have hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0019] The film quality improver may have a refractive index (a) within the range of 1.38 to 1.72, and at the same time, the value (b / a) obtained by dividing the vapor pressure (25 °C, mmHg, b) by the refractive index (a) may be within the range of 0.003 to 0.043.

[0020] The film quality improver is relative to the film quality improver 1 After mixing the film quality improver and the molybdenum precursor in a 1:1 molar ratio and pressurizing, the integral value of the peak apex newly generated in the 1H-NMR spectrum measured 1 The compound may be one in which the integral value of the peak apex newly generated in the 1H-NMR spectrum is less than 0.1%.

[0021] Here, the molybdenum precursor may be solid or liquid under the conditions of 20 °C and 1 bar.

[0022] The film quality improver may provide a shielding region for a molybdenum-based thin film.

[0023] The shielding region for the molybdenum-based thin film may be formed on the substrate on which the molybdenum-based thin film is formed.

[0024] The shielding region for the molybdenum-based thin film does not remain in the molybdenum-based thin film, and the molybdenum-based thin film may contain 1% or less of carbon, silicon, and halogen compounds.

[0025] The molybdenum-based thin film may be used for a diffusion barrier or an electrode.

[0026]

[0027] In addition, the present invention provides the following Chemical Formula 1

[0028] [Chemical Formula 1]

[0029] TIFF0007858054 or 6373

[0030] The present invention provides a molybdenum-based thin film formation method characterized by including the step of injecting a film quality improving agent having a saturated structure represented by (A being carbon (C) or silicon (Si), X being fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R1 and R3 being independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R2 being independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), or having a functional group of the formula BR4R5R6, B being carbon or silicon, and R4, R5, and R6 being independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) into a chamber and injecting it into the surface of a loaded substrate.

[0031] The molybdenum-based thin film formation method may include: ia) vaporizing the film quality improving agent to form a shielding region on the surface of a substrate loaded into the chamber; ii-a) primary purging the inside of the chamber with a purge gas; iii-a) vaporizing a molybdenum precursor and adsorbing it onto the region outside the shielding region; iv-a) secondary purging the inside of the chamber with a purge gas; va) supplying a reaction gas into the inside of the chamber; and vi-a) tertiary purging the inside of the chamber with a purge gas.

[0032] Furthermore, the molybdenum-based thin film formation method may include the steps of: ib) vaporizing a molybdenum precursor and adsorbing it onto the surface of a substrate loaded into a chamber; ii-b) primary purging the inside of the chamber with a purge gas; iii-b) vaporizing the film quality improving agent and injecting it onto the surface of a substrate loaded into a chamber; iv-b) secondary purging the inside of the chamber with a purge gas; vb) supplying a reaction gas into the inside of the chamber; and vi-b) tertiary purging the inside of the chamber with a purge gas.

[0033] The molybdenum precursor may be solid or liquid under conditions of 20°C and 1 bar, and may be a molybdenum precursor having a vapor pressure of 0.1 mTorr to 100 Torr at 30°C.

[0034] The molybdenum precursor may be one or more compounds selected from those represented by the following chemical formulas 2 to 36.

[0035] [Chemical formulas 2 to 19]

[0036] TIFF0007858054000003.tif153164

[0037] [Chemical formulas 20 to 32]

[0038] TIFF0007858054000004.tif107165

[0039] [Chemical formulas 33 to 36]

[0040] TIFF0007858054000005.tif51148

[0041] (In chemical formulas 2 to 36, the lines represent bonds, and the points where bonds intersect (unless other elements are listed) are carbon atoms. The number of hydrogen atoms required to satisfy the valence of the carbon atoms is omitted, and R′ and R″ are hydrogen atoms or alkyl groups of carbon atoms 1 to 5, respectively. R′ may be linked to an adjacent R′ atom.)

[0042]

[0043] The chamber may be an ALD chamber or a CVD chamber.

[0044] The film quality improving agent or molybdenum precursor may include a step of vaporizing and injecting it, followed by plasma post-treatment.

[0045] In steps ii) and iv), the amount of purge gas introduced into the chamber may be 10 to 100,000 times the volume of the introduced film quality improving agent.

[0046] The reaction gas, film quality improving agent, and molybdenum precursor may be transferred into the chamber by VFC, DLI, or LDS.

[0047] The substrate loaded into the chamber is heated to 50 to 400°C, and the ratio of the amount (mg / cycle) of the film quality improving agent to the molybdenum precursor added to the chamber may be 1:1.5 to 1:20.

[0048] The reaction gas may be a reducing agent, a nitriding agent, or an oxidizing agent.

[0049] The molybdenum-based thin film formation method may also involve a deposition temperature of 50 to 700°C.

[0050] The molybdenum-based thin film may be an oxide film, a nitride film, or a metal film.

[0051]

[0052] Furthermore, the present invention provides a semiconductor substrate characterized by being manufactured by the molybdenum-based thin film formation method described above.

[0053] The molybdenum-based thin film may have a multilayer structure of two or three layers.

[0054]

[0055] Furthermore, the present invention provides a semiconductor device including the aforementioned semiconductor substrate.

[0056] The semiconductor substrate may 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) or 3D NAND. [Effects of the Invention]

[0057] According to the present invention, there is an effect of providing a film quality improving agent that reduces the deposition rate of molybdenum-based thin films by forming a shielding region for molybdenum-based thin films on a substrate, thereby controlling the thin film growth rate and improving step coverage even when forming a thin film with a solid compound at room temperature on a substrate having a complex structure.

[0058] Furthermore, during thin film formation, process by-products are more effectively reduced, preventing corrosion and degradation, and improving the crystallinity of the thin film, thereby improving its electrical properties.

[0059] Furthermore, during thin film formation, process by-products are reduced, improving step coverage and thin film density, which in turn provides a thin film formation method utilizing these properties, and a semiconductor substrate manufactured therefrom. [Brief explanation of the drawing]

[0060] [Figure 1] This figure compares the results of Example 6, an experiment in which the film quality improving agent presented in this invention was injected into MoO2Cl2 before and after injection, with an experiment in which the film quality improving agent was not used. The left side shows the resistivity measurement results, and the right side shows the deposition rate measurement results. [Modes for carrying out the invention]

[0061]

[0062] The following describes in detail the molybdenum-based thin film quality improving agent, the method for forming a molybdenum-based thin film using the same, and the semiconductor substrate manufactured therefrom.

[0063] In this document, unless otherwise specified, the term "shielding" means not only reducing, preventing, or blocking the adsorption of molybdenum precursors for forming molybdenum-based thin films onto the substrate, but also reducing, preventing, or blocking the adsorption of process by-products onto the substrate.

[0064] The inventors have confirmed that when using a film quality improving agent that shields the molybdenum precursor for forming a molybdenum-based thin film on the surface of a substrate loaded inside a chamber, a shielding region that does not remain in the molybdenum-based thin film is formed, resulting in a relatively rough thin film. At the same time, the growth rate of the formed thin film is adjusted, ensuring uniformity of the thin film even when applied to substrates with complex structures, and significantly improving step coverage. In particular, it enables deposition at thin thicknesses and improves the amount of residual halides that remained as process by-products, as well as carbon, which was difficult to reduce even with the use of excessive hydrogen gas. Based on this, the inventors have dedicated themselves to research on film quality improving agents that provide shielding regions, leading to the completion of the present invention.

[0065]

[0066] The present invention provides a film quality improving agent for molybdenum-based thin films.

[0067] The molybdenum-based thin film may be provided as one or more precursors selected from the compounds represented by the following chemical formulas 2 to 36, for example, in which case the effects to be achieved in this invention can be fully obtained.

[0068] [Chemical formulas 2 to 19]

[0069] TIFF0007858054000006.tif150159

[0070] [Chemical formulas 20 to 32]

[0071] TIFF0007858054000007.tif110165

[0072] [Chemical formulas 33 to 36]

[0073] TIFF0007858054000008.tif54161

[0074] (In chemical formulas 2 to 36, the lines represent bonds, and the points where bonds intersect (unless other elements are listed) are carbon atoms. The number of hydrogen atoms required to satisfy the valence of the carbon atoms is omitted, and R′ and R″ are hydrogen atoms or alkyl groups of carbon atoms 1 to 5, respectively. R′ may be linked to an adjacent R′ atom.)

[0075] The aforementioned molybdenum-based thin film may be used not only as a diffusion-blocking film for general purposes, but also as an electrode in semiconductor devices.

[0076]

[0077] The aforementioned film quality improving agent is defined by the following chemical formula 1

[0078] [Chemical formula 1]

[0079] TIFF0007858054000009.tif6371

[0080] (A is carbon (C) or silicon (Si), X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R1 and R3 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R2 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or a functional group of formula BR4R5R6, B is carbon or silicon, and R4, R5, and R6 are The compounds are, independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). They are characterized by being saturated compounds represented by ( ), and in such cases, when forming a molybdenum-based thin film, they form a shielding region that does not remain in the molybdenum-based thin film, forming a relatively rough thin film, while simultaneously suppressing side reactions and adjusting the thin film growth rate, reducing by-products in the thin film process, reducing corrosion and degradation, improving the crystallinity of the thin film, and significantly improving step coverage and thickness uniformity of the thin film even when forming a thin film on a substrate with a complex structure.

[0081] In the above chemical formula 1, A is carbon or silicon, and is preferably carbon.

[0082] R1, R2, and R3 are each independently alkyl groups having 1 to 3 carbon atoms, with at least one of them having 2 or 3 carbon atoms. A preferred example is that one of R1, R2, and R3 has 1 carbon atom and the remaining two have 2 or 3 carbon atoms. More preferably, one of R1, R2, and R3 has 1 carbon atom and the remaining two have 2 carbon atoms. Within this range, there is a significant reduction in process by-products, excellent step coverage, improved thin film density, and superior electrical properties of the thin film.

[0083] In the above chemical formula 1, X is a halogen element, preferably fluorine, chlorine, or bromine, and more preferably chlorine or bromine, within which range there is an advantage in reducing process by-products and improving step coverage. In addition, X may be fluorine as an example, in which case there is an advantage in being more suitable for processes requiring high-temperature deposition.

[0084] In the aforementioned chemical formula 1, X may be iodine as another preferred example. Within this range, thin film crystallinity is improved, and there is an advantage in that the effect of suppressing side reactions and reducing process by-products is further enhanced.

[0085]

[0086] The compound represented by chemical formula 1 is a halogen-substituted tert-alkyl compound, and specific examples include 2-chloro-2-methylpropane, 2-chloro-2-methylbutane, 2-chloro-2-methylpentane, 3-chloro-3-methylpentane, 3-chloro-3-methylhexane, 3-chloro-3-ethylpentane, 3-chloro-3-ethylhexane, 4-chloro-4-methylheptane, 4-chloro-4-ethylheptane, 4-chloro-4-propylheptane, 2-bromo-2-methylpropane, 2-bromo-2-methylbutane, and 2-bromo-2-methyl Pentane, 3-bromo-3 methylpentane, 3-bromo-3 methylhexane, 3-bromo-3 ethylpentane, 3-bromo-3 ethylhexane, 4-bromo-4 methylheptane, 4-bromo-4 ethylheptane, 4-bromo-4 propylheptane, 2-iodo-2 methylpropane, 2-iodo-2 methylbutane, 2-iodo-2 methylpentane, 3-iodo-3 methylpentane, 3-iodo-3 methylhexane, 3-iodo-3 ethylpentane, 3-iodo-3 ethylhexane, 4-iodo-4 methylheptane, 4-iodo-4 ethylheptane One or more selected from the group consisting of butane, 4-iodo-4 propylheptane, 2-fluoro-2 methylpropane, 2-fluoro-2 methylbutane, 2-fluoro-2 methylpentane, 3-fluoro-3 methylpentane, 3-fluoro-3 methylhexane, 3-fluoro-3 ethylpentane, 3-fluoro-3 ethylhexane, 4-fluoro-4 methylheptane, 4-fluoro-4 ethylheptane, and 4-fluoro-4 propylheptane, preferably 2-chloro-2 methylpropane, 2-chloro-2 methylbutane, and 3-chloro-3 It is one or more selected from the group consisting of methylpentane, 2-bromo-2methylpropane, 2-bromo-2methylbutane, 3-bromo-3methylpentane, 2-iodo-2methylpropane, 2-iodo-2methylbutane, 3-iodo-3methylpentane, 2-fluoro-2methylpropane, 2-fluoro-2methylbutane, and 3-fluoro-3methylpentane. In this case, it has a great effect of providing a shielding region for molybdenum thin films to regulate the growth rate of the thin film, a great effect of removing process by-products, and excellent effects of improving step coverage and film quality.

[0087]

[0088] The compound represented by chemical formula 1 may, for example, be a saturated compound in which the refractive index (a) is in the range of 1.38 to 1.72, and at the same time, the value obtained by dividing the vapor pressure (mmHg, b) measured at 25°C by the refractive index (a) (b / a) is in the range of 0.003 to 0.043. In such a case, even when forming a shielding region for molybdenum-based thin films on the substrate to reduce the deposition rate of the molybdenum-based thin film and control the thin film growth rate to form a thin film on a substrate with a complex structure, there are advantages in that step coverage and thickness uniformity of the thin film are greatly improved, the adsorption of not only thin film precursors but also process by-products is prevented, the substrate surface is effectively protected, and process by-products are effectively removed.

[0089] In the present invention, the refractive index can be measured by methods known in the art unless otherwise specified. As a specific example, it can be measured at 25°C using an Abbe refractometer based on ASTM D542.

[0090] The compound represented by chemical formula 1 may, as a specific example, be a saturated compound having a refractive index (a) in the range of 1.385 to 1.72, and at the same time, the value obtained by dividing the vapor pressure (mmHg, b) measured at 25°C by the refractive index (a) (b / a) in the range of 0.032 to 0.043. Preferably, it may be a saturated compound having a refractive index (a) in the range of 1.388 to 1.719, and at the same time, the value obtained by dividing the vapor pressure (mmHg, b) measured at 25°C by the refractive index (a) (b / a) in the range of 0.0035 to 0.043. In this case, even when forming a shielding region for molybdenum-based thin films on the substrate to reduce the deposition rate of the molybdenum-based thin film and controlling the thin film growth rate to form a thin film on a substrate with a complex structure, there is an advantage in that step coverage and thin film thickness uniformity are greatly improved, the adsorption of not only thin film precursors but also process by-products is prevented, effectively protecting the substrate surface and effectively removing process by-products.

[0091]

[0092] The reactivity between the film quality improving agent and the molybdenum precursor can be expressed as an impurity content (%) of less than 0.1% when the integral value of the NMR peaks generated by comparing the H-NMR spectrum measured before mixing the film quality improving agent and the molybdenum precursor with the H-NMR spectrum measured after pressurizing a 1:1 molar mixture for 1 hour is taken as the impurity content. This means that when using the film quality improving agent, it is possible to improve step coverage and film quality even when forming a thin film on a substrate with a complex structure by adjusting the deposition rate while reducing process by-products and controlling the thin film growth rate, thereby preventing corrosion and degradation and improving the crystallinity of the thin film, and thereby improving the resistivity and electrical properties of the thin film.

[0093] Due to the aforementioned reactivity, the film quality improving agent has the advantage of easily adjusting the viscosity and vapor pressure of the molybdenum precursor without interfering with the behavior of the molybdenum precursor.

[0094] Examples of film-improving agents exhibiting such reactivity may be halogen-substituted linear or branched alkane compounds or cycloalkane compounds.

[0095] As a specific example, it is one or more selected from the group consisting of 1-iodobutane, 2-iodobutane, 2-iodo-3-methylbutane, 3-iodo-2,4-dimethylpentane, cyclohexyl iodide, cyclopentyl iodide, 1-bromobutane, 2-bromobutane, 2-bromo-3-methylbutane, 3-bromo-2,4-dimethylpentane, cyclohexyl bromide, and cyclopentyl bromide, preferably one or more selected from the group consisting of 1-iodobutane and 2-iodobutane. In this case, it has the advantage of not interfering with the adsorption of the molybdenum precursor, effectively protecting the substrate surface as a film quality improver, and effectively removing process by-products.

[0096]

[0097] The film quality improving agent is characterized by not remaining in the molybdenum-based thin film.

[0098] In this context, "no residue" means that, unless otherwise specified, the element is present in amounts less than 1.0 atom (atom%) of C, less than 1.0 atom (atom%) of Si, less than 1.0 atom (atom%) of N, and less than 1.0 atom (atom%) of halogen elements when analyzed by XPS.

[0099]

[0100] The aforementioned molybdenum-based thin film can be used, but is not limited to, as a diffusion barrier or an electrode.

[0101] The aforementioned film quality improving agent may preferably be a compound with a purity of 99.9% or higher, a compound with a purity of 99.95% or higher, or a compound with a purity of 99.99% or higher. For reference, if a compound with a purity of less than 99% is used, impurities may be formed, so it is preferable to use a substance with a purity of 99% or higher whenever possible.

[0102]

[0103] The compound represented by chemical formula 1 is preferably used in the atomic layer deposition (ALD) process, which has the advantages of not interfering with the adsorption of molybdenum precursors, effectively protecting the substrate surface as a film quality improver, and effectively removing process by-products.

[0104] The compound represented by chemical formula 1 is preferably a liquid at room temperature (22°C) and has a density of 0.8 to 2.5 g / cm³. 3 or 0.8 to 1.5 g / cm³ 3The vapor pressure (at 20°C) may be 0.1 to 300 mmHg or 1 to 300 mmHg, and the solubility in water (at 25°C) may be 200 mg / L or less. Within this range, it effectively forms a shielding region and has the effect of excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0105] More preferably, the compound represented by chemical formula 1 has a density of 0.75 to 2.0 g / cm³. 3 or 0.8 to 1.3 g / cm³ 3 The vapor pressure (at 20°C) may be between 1 and 260 mmHg, and the solubility in water (at 25°C) may be 160 mg / L or less. Within this range, it effectively forms a shielding region and has the effect of excellent step coverage, thin film thickness uniformity, and film quality improvement.

[0106]

[0107] The molybdenum-based thin film formation method of the present invention is as follows:

[0108] [Chemical formula 1]

[0109] TIFF0007858054000010.tif6985

[0110] (A is carbon (C) or silicon (Si), X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R1 and R3 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), R2 is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or a functional group of formula BR4R5R6, B is carbon or silicon, and R4 R5 and R6 are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). The method is characterized by including a step of injecting a film quality improving agent represented by ( ) into the ALD chamber and adsorbing it onto the loaded substrate surface. In such a case, a shielding region for molybdenum-based thin films is formed on the substrate to reduce the deposition rate of the molybdenum-based thin film, and even when the thin film growth rate is controlled to form a thin film on a substrate with a complex structure, it is possible to not only greatly improve step coverage and thickness uniformity of the thin film, but also provide film quality improvement effects such as resistivity improvement.

[0111] In the step of shielding the substrate surface with the aforementioned film quality improving agent, the feeding time of the film quality improving agent per cycle is preferably 0.01 to 5 seconds, more preferably 0.02 to 3 seconds, even more preferably 0.04 to 2 seconds, and even more preferably 0.05 to 1 second. Within this range, there is an advantage of a low thin film growth rate, excellent step coverage, and economic efficiency.

[0112] In this description, the feeding time for the film quality improving agent is based on a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s, and more specifically, on a chamber volume of 18 L and a flow rate of 1 to 2 mg / s.

[0113]

[0114] The thin film formation method may, as a preferred embodiment, include: ia) vaporizing the film quality improving agent and shielding it to the surface of the substrate loaded into the ALD chamber; ii-a) primary purging the inside of the chamber with a purge gas; iii-a) vaporizing the molybdenum precursor and adsorbing it to the surface of the substrate loaded into the chamber; iv-a) secondary purging the inside of the chamber with a purge gas; va) supplying a reaction gas to the inside of the chamber; and via) tertiary purging the inside of the chamber with a purge gas. In this case, steps ia) to vi-a) may be considered as a unit cycle and repeated until a thin film of the desired thickness is obtained. When the film quality improving agent of the present invention is introduced before the molybdenum precursor and adsorbed onto the substrate within one cycle in this way, the thin film growth rate can be appropriately reduced even when deposited at high temperatures, the process by-products generated are effectively removed, the resistivity of the thin film decreases, and the step coverage is greatly improved.

[0115]

[0116] In other preferred embodiments, the thin film formation method may include the steps of: ib) vaporizing a molybdenum precursor and adsorbing it onto the substrate surface loaded into the chamber; ii-b) primary purging the inside of the chamber with a purge gas; iii-b) vaporizing the film quality improving agent and adsorbing it onto the substrate surface loaded into the chamber; iv-b) secondary purging the inside of the chamber with a purge gas; vb) supplying a reaction gas into the chamber; and vi-b) tertiary purging the inside of the chamber with a purge gas. In this case, steps ib) to vi-b) may be used as a unit cycle and the cycle may be repeated until a thin film of the desired thickness is obtained. When the film quality improving agent of the present invention is added to the substrate after the molybdenum precursor within one cycle and adsorbed onto it, the film quality improving agent can act as a growth activator for thin film formation. In this case, the thin film growth rate increases, the density and crystallinity of the thin film increase, the resistivity of the thin film decreases, and the electrical properties are greatly improved.

[0117]

[0118] In the thin film formation method of the present invention, as a preferred example, the film quality improving agent of the present invention may be added to the substrate before the molybdenum precursor within one cycle and adsorbed onto the substrate. In this case, even when the thin film is deposited at high temperature, the thin film growth rate can be appropriately reduced, significantly reducing process by-products, greatly improving step coverage, increasing the crystallinity of the thin film and reducing its resistivity. Furthermore, even when applied to semiconductor devices with a large aspect ratio, the thickness uniformity of the thin film is greatly improved, ensuring the reliability of the semiconductor device.

[0119]

[0120] In the thin film formation method, for example, when the film quality improving agent is deposited before or after the deposition of the molybdenum precursor, the unit cycle may be repeated 1 to 99,999 times as needed, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times. Within this range, the desired thin film thickness can be obtained while fully achieving the effects intended to be achieved in this invention.

[0121] In the present invention, the chamber may, for example, be an ALD chamber or a CVD chamber.

[0122] In the present invention, the film quality improving agent or molybdenum precursor may include a step of plasma post-treatment after vaporization and injection, in which case the growth rate of the thin film can be improved while reducing process by-products.

[0123]

[0124] When the film quality improving agent is first adsorbed onto the substrate and then the molybdenum precursor is adsorbed, or when the molybdenum precursor is first adsorbed and then the film quality improving agent is adsorbed, the amount of purge gas introduced into the chamber at the stage of purging the unadsorbed film quality improving agent is not particularly limited as long as it is sufficient to remove the unadsorbed film quality improving agent. For example, it may be 10 to 100,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times. Within this range, the unadsorbed film quality improving agent can be sufficiently removed to form a thin film evenly and prevent deterioration of the film quality. Here, the amounts of purge gas and film quality improving agent introduced are based on one cycle, and the volume of the film quality improving agent refers to the volume of vaporized film quality improving agent vapor.

[0125] As a specific example, if the film quality improving agent is injected at a flow rate of 1.66 mL / s and an injection time of 0.5 sec (per cycle), and a purge gas is injected at a flow rate of 166.6 mL / s and an injection time of 3 sec (per cycle) during the stage of purging the unadsorbed film quality improving agent, the amount of purge gas injected is 602 times the amount of film quality improving agent injected.

[0126]

[0127] Furthermore, the amount of purge gas introduced into the ALD chamber during the purging stage of the unadsorbed molybdenum precursor is not particularly limited as long as it is sufficient to remove the unadsorbed molybdenum precursor. For example, the amount may be 10 to 10,000 times, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, based on the volume of molybdenum precursor introduced into the ALD chamber. Within this range, the unadsorbed molybdenum precursor can be sufficiently removed to form a thin film evenly and prevent deterioration of the film quality. Here, the amounts of purge gas and molybdenum precursor introduced are based on one cycle, and the volume of the molybdenum precursor refers to the volume of vaporized molybdenum precursor vapor.

[0128]

[0129] Furthermore, in the purging stage performed immediately after the reaction gas supply stage, the amount of purge gas introduced into the ALD chamber may be, for example, 10 to 10,000 times the volume of reaction gas introduced into the ALD chamber, preferably 50 to 50,000 times, and more preferably 100 to 10,000 times, and the desired effect can be sufficiently obtained within this range. Here, the amounts of purge gas and reaction gas introduced are based on one cycle each.

[0130]

[0131] The film quality improving agent and the molybdenum precursor may preferably be transferred into the ALD chamber by the VFC method, DLI method, or LDS method, and more preferably by the LDS method.

[0132] The substrate loaded into the chamber may be heated to, for example, 50 to 700°C, and more specifically, 300 to 700°C. The film quality improving agent or molybdenum precursor may be injected onto the substrate without heating or while heated. Depending on the deposition efficiency, it may be injected without heating first, and then the heating conditions may be adjusted during the deposition process. For example, it may be injected onto the substrate at 50 to 700°C for 1 to 20 seconds.

[0133]

[0134] The ratio of the amount (mg / cycle) of the film quality improving agent to the molybdenum precursor added to the chamber is preferably 1:1.5 to 1:20, more preferably 1:2 to 1:15, even more preferably 1:2 to 1:12, and even more preferably 1:2.5 to 1:10. Within this range, the effect of improving step coverage and reducing process by-products is greatest.

[0135]

[0136] In the present invention, the molybdenum precursor may, for example, be mixed with a nonpolar solvent and introduced into the chamber. In this case, there is the advantage that the viscosity and vapor pressure of the molybdenum precursor can be easily adjusted.

[0137] The nonpolar solvent may preferably be one or more selected from the group consisting of alkanes and cycloalkanes. In this case, while containing an organic solvent with low reactivity and solubility, and easy moisture control, it has the advantage of improving step coverage even when the deposition temperature increases during thin film formation.

[0138] As a more preferred example, the nonpolar solvent may contain C1 to C10 alkanes or C3 to C10 cycloalkanes, preferably C3 to C10 cycloalkanes, which have the advantages of low reactivity and solubility, and easy moisture control.

[0139] In this document, C1, C3, etc., refer to the number of carbon atoms.

[0140] The cycloalkane may preferably be a C3 to C10 monocycloalkane, and among the monocycloalkanes, cyclopentane is preferred in the vapor deposition process because it is liquid at room temperature and has the highest vapor pressure, but is not limited to this.

[0141] The aforementioned nonpolar solvent, for example, has a solubility in water (at 25°C) of 200 mg / L or less, preferably 50 to 400 mg / L, and more preferably 135 to 175 mg / L. Within this range, it has the advantage of low reactivity with the molybdenum precursor and easy moisture control.

[0142] In this description, solubility is not particularly limited by measurement methods or standards commonly used in the art to which the present invention pertains, and as an example, a saturated solution can be measured by HPLC.

[0143] The nonpolar solvent may preferably be present in an amount of 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 40 to 90% by weight, and most preferably 70 to 90% by weight, relative to the total weight of the molybdenum precursor and the nonpolar solvent combined.

[0144] If the amount of the nonpolar solvent added exceeds the upper limit, it induces impurities, increasing resistance and the amount of impurities in the thin film. Conversely, if the amount of the organic solvent added is below the lower limit, it has the disadvantage of having less effect on improving step coverage due to solvent addition and reducing impurities such as chloride (Cl) ions.

[0145]

[0146] In the molybdenum-based thin film formation method, for example, when using the film quality improving agent, the decrease rate of the thin film growth rate per cycle (Å / cycle) calculated by the following formula 1 is -5% or less, preferably -10% or less, more preferably -20% or less, even more preferably -30% or less, even more preferably -40% or less, and most preferably -45% or less, and within this range, it exhibits excellent step coverage and uniformity of film thickness.

[0147] [Formula 1]

[0148] The percentage decrease in thin film growth rate per cycle (%) = [(Thin film growth rate per cycle with film quality improver - Thin film growth rate per cycle without film quality improver) / Thin film growth rate per cycle without film quality improver] × 100

[0149] In the above formula 1, the thin film growth rate per cycle with and without the use of a film quality improving agent represents the thin film deposition thickness per cycle (Å / cycle), i.e., the deposition rate. The deposition rate can be determined, for example, by measuring the final thickness of the thin film using ellipsometry and then dividing it by the total number of cycles to obtain the average deposition rate.

[0150] In the aforementioned formula 1, "when no film quality improving agent is used" means the case in which a thin film is manufactured by adsorbing only a molybdenum precursor onto the substrate during the thin film deposition process. A specific example of this is the case in which a thin film is formed by omitting the steps of adsorbing the film quality improving agent and purging the unadsorbed film quality improving agent in the thin film formation method.

[0151]

[0152] The molybdenum-based thin film formation method provides a residual halogen intensity (c / s) in a 100 Å thin film, measured based on SIMS, which is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less. In a preferred example, it may be 5,000 or less, more preferably 1,000 to 4,000, and even more preferably 1,000 to 3,800. Within this range, the method exhibits excellent protection against corrosion and degradation.

[0153] In this description, the purging is preferably 1,000 to 50,000 sccm (Standard Cubic Centimeter per Minute), more preferably 2,000 to 30,000 sccm, and even more preferably 2,500 to 15,000 sccm. Within this range, the thin film growth rate per cycle is appropriately controlled, resulting in the advantage of single-atomic mono-layer deposition, or deposition close to it, which is advantageous in terms of film quality.

[0154]

[0155] The aforementioned ALD (atomic layer deposition process) is highly advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and offers advantages such as excellent conformality, uniformity, and precise thickness control due to its self-limiting thin-film growth mechanism.

[0156] The aforementioned thin film formation method can be carried out, for example, at an evaporation temperature in the range of 50 to 800°C, preferably in the range of 300 to 700°C, and more preferably in the range of 350 to 650°C. Within this range, it is possible to grow a thin film with excellent film quality while embodying the characteristics of the ALD process.

[0157] The aforementioned thin film formation method can be carried out, for example, with an evaporation pressure in the range of 0.01 to 30 Torr, preferably in the range of 0.1 to 30 Torr, more preferably in the range of 1 to 30 Torr, and most preferably in the range of 5 to 20 Torr. This method has the effect of obtaining a thin film of uniform thickness within this range.

[0158] In this description, the deposition temperature and deposition pressure can 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.

[0159] The molybdenum-based thin film formation method may preferably include the step of raising the temperature inside the chamber to the deposition temperature before introducing the film quality improving agent into the chamber; and / or the step of injecting an inert gas into the chamber to purge it before introducing the film quality improving agent into the chamber.

[0160] Furthermore, the present invention may also include a thin film manufacturing apparatus capable of embodying the molybdenum-based thin film manufacturing method, comprising an ALD chamber, a first vaporizer for vaporizing a film quality improving agent, a first transfer means for transferring the vaporized film quality improving agent into the ALD chamber, a second vaporizer for vaporizing a thin film precursor, and a second transfer means for transferring the vaporized thin film precursor into the ALD chamber. Here, the vaporizer and transfer means are not particularly limited as long as they are vaporizers and transfer means commonly used in the art to which the present invention belongs.

[0161]

[0162] As a specific example, the thin film formation method described above is first positioned in a deposition chamber capable of atomic layer deposition on which the thin film will be formed on top.

[0163] The substrate may include semiconductor substrates such as silicon substrates and silicon oxide.

[0164] The substrate may have a conductive layer or an insulating layer further formed on its upper surface.

[0165] To deposit a thin film onto a substrate located in the deposition chamber, the above-mentioned film quality improving agent and a molybdenum precursor, or a mixture thereof with a nonpolar solvent, are prepared.

[0166] Subsequently, the prepared film quality improving agent is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber where it is adsorbed onto the substrate. Finally, purging is performed to remove any unadsorbed film quality improving agent.

[0167] Next, the prepared molybdenum precursor, or a mixture thereof with a nonpolar solvent (thin film forming composition), is injected into the vaporizer, converted into a vapor phase, and transferred to the deposition chamber where it is adsorbed onto the substrate, and any unadsorbed molybdenum precursor / thin film forming composition is purged.

[0168] In this description, the steps of adsorbing the film quality improving agent onto the substrate and then purging to remove any unadsorbed film quality improving agent, and adsorbing the molybdenum precursor onto the substrate and then purging to remove any unadsorbed molybdenum precursor, can be carried out in any order as necessary.

[0169] In this description, the method for transferring the film quality improving agent and molybdenum precursor (thin film formation composition) to the deposition chamber can, for example, be a method that utilizes a gas flow control (MFC) method to transfer volatilized gas (VFC), or a method that utilizes a liquid flow control (Liquid Mass Flow Controller; LMFC) method to transfer liquid (Liquid Delivery System; LDS), and preferably the LDS method is used.

[0170] At this time, one or more mixed gases selected from the group consisting of argon (Ar), nitrogen (N2), and helium (He) can be used as the carrier gas or diluent gas for moving the film quality improving agent and molybdenum precursor onto the substrate, but are not limited to these.

[0171] In this description, an inert gas can be used as the purge gas, and preferably the carrier gas or diluent gas can be used.

[0172]

[0173] Next, a reaction gas is supplied. The reaction gas is not particularly limited as long as it is a reaction gas commonly used in the art to which the present invention belongs, and preferably contains a reducing agent, a nitride agent, or an oxidizing agent. The nitride agent reacts with the molybdenum precursor adsorbed on the substrate to form a nitride film, the reducing agent reacts with the molybdenum precursor adsorbed on the substrate to form a metal film, and the oxidizing agent reacts with the molybdenum precursor adsorbed on the substrate to form an oxide film.

[0174] Preferably, the nitriding agent may be nitrogen gas (N2), hydrazine gas (N2H4), or a mixture of nitrogen gas and hydrogen gas; the oxidizing agent may be oxygen gas (O2), ozone gas, or a mixture of oxygen gas and ozone gas; and the reducing agent may be hydrogen gas (H2), etc.

[0175] The aforementioned thin film formation method, for example, has a deposition temperature of 50 to 800°C, preferably 200 to 700°C, and specific examples include 250 to 500°C, 250 to 450°C, 380 to 420°C, or 400 to 450°C. Within this range, there is an advantage in that the thin film resistivity, step coverage, etc., are greatly improved.

[0176] 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.

[0177] As described above, the molybdenum-based thin film formation method can be performed by repeating a unit cycle to form a thin film of a desired thickness, with the unit cycle consisting of the steps of shielding the substrate with a film quality improving agent, purging the unadsorbed film quality improving agent, adsorbing the molybdenum precursor / thin film formation composition onto the substrate, purging the unadsorbed molybdenum precursor / thin film formation composition, supplying a reaction gas, and purging residual reaction gas.

[0178] As another example, the molybdenum-based thin film formation method can be described as a unit cycle consisting of the steps of adsorbing a molybdenum precursor / thin film formation composition onto a substrate, purging the unadsorbed molybdenum precursor / thin film formation composition, adsorbing a film quality improving agent onto the substrate, purging the unadsorbed film quality improving agent, supplying a reaction gas, and purging residual reaction gas, and repeating this unit cycle to form a thin film of a desired thickness.

[0179] The aforementioned unit cycle can be repeated, for example, 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and even more preferably 100 to 2,000 times, and within this range, the desired thin film characteristics are well expressed.

[0180]

[0181] The present invention also provides a semiconductor substrate, characterized in that the semiconductor substrate is manufactured by the molybdenum-based thin film formation method described herein, which has the effect of greatly improving the step coverage and thickness uniformity of the thin film, as well as the density and electrical properties of the thin film.

[0182]

[0183] The manufactured thin film preferably has a thickness of 20 nm or less, a resistivity of 0.1 to 400 μΩ·cm based on a thin film thickness of 10 nm, a halogen content of 10,000 ppm or less, and a step coverage rate of 90% or more. Within this range, it exhibits excellent performance as a diffusion-blocking film and has the effect of reducing corrosion of metal wiring materials, but is not limited to this.

[0184] The thin film may have a thickness of, for example, 1 to 20 nm, preferably 1 to 20 nm, more preferably 3 to 25 nm, and even more preferably 5 to 20 nm, and within this range, it has the effect of exhibiting excellent thin film properties.

[0185] The thin film may, for example, have a resistivity of 0.1 to 400 μΩ·cm based on a thin film thickness of 10 nm, preferably 15 to 300 μΩ·cm, more preferably 20 to 290 μΩ·cm, and even more preferably 25 to 280 μΩ·cm, and within this range, the thin film properties are excellent.

[0186] The thin film may have a halogen content of preferably 10,000 ppm or less, or 1 to 9,000 ppm, more preferably 5 to 8,500 ppm, and even more preferably 100 to 1,000 ppm. Within this range, the thin film characteristics are excellent while the thin film growth rate is reduced. Here, the halogen remaining in the thin film is, for example, Cl2, Cl, or Cl - This is also acceptable, and a lower amount of halogen residue in the thin film is preferable as it indicates better film quality.

[0187] The aforementioned thin film, for example, has a step coverage rate of 90% or more, preferably 92% or more, and more preferably 95% or more. Within this range, even thin films with complex structures can be easily deposited onto a substrate, offering the advantage of being applicable to next-generation semiconductor devices.

[0188] In the present invention, unless otherwise specified, the step coverage ratio can be calculated using a method known in the industry. For example, the thickness of the thin film deposited on the upper end (upper deposition thickness) and the thickness of the thin film deposited on the side (side deposition thickness) may be measured, and the value obtained by dividing the upper deposition thickness by the side deposition thickness may be expressed as a percentage.

[0189] The thin film, for example, has a resistivity of 1500 μΩ·cm or less, preferably 1400 μΩ·cm or less, and more preferably 1300 μΩ·cm or less. The smaller the value, the more preferable it is. Within this range, it is possible to provide the electrical properties required by thin films with complex structures, and it has the advantage of being applicable to next-generation semiconductor devices.

[0190]

[0191] The manufactured thin film may include, for example, a molybdenum film, a molybdenum oxide film, or a molybdenum nitride film, in which case it has the advantage of being useful as a diffusion-blocking film or electrode for semiconductor devices.

[0192]

[0193] The thin film may, for example, have a multilayer structure of two or three layers as required. The multilayer film with a two-layer structure may, as a specific example, have a lower layer film - middle layer film structure, and the multilayer film with a three-layer structure may, as a specific example, have a lower layer film - middle layer film - upper layer film structure.

[0194] The lower layer film may, for example, contain one or more selected from the group consisting of Si, SiO2, MgO, Al2O3, CaO, ZrSiO4, ZrO2, HfSiO4, Y2O3, HfO2, LaLuO2, Si3N4, SrO, La2O3, Ta2O5, BaO, TiO2.

[0195] The middle layer film may, for example, contain Ti x N y and preferably TN.

[0196] The upper layer film may, for example, contain one or more selected from the group consisting of W and Mo.

[0197]

[0198] Hereinafter, preferred examples and drawings are presented to assist in understanding the present invention. It should be clear to those skilled in the art that the following examples and drawings are merely illustrative of the present invention, and various changes and modifications are possible within the scope of the present invention and the scope of the technical idea. It is natural that such variations and modifications belong to the scope of the appended claims.

[0199]

[0200] [Examples]

[0201] Examples 1 to 5, Comparative Examples 1 to 3, Reference Example 1

[0202] As the film quality improver and molybdenum precursor used in the experiment, the combinations shown in Table 1 below were selected.

[0203]

Table 1

[0204] Example 1

[0205] From the compounds listed in Table 1 above, t-butyl iodide was prepared as a film quality improver, and the compound represented by chemical formula 34, MoO2Cl2, was prepared as a molybdenum precursor. The prepared film quality improver and thin film precursor compounds were placed in canisters and supplied at room temperature to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller).

[0206] The film quality improving agent and thin film precursor compound, vaporized into a vapor phase using a vaporizer, were each introduced into the deposition chamber loaded with the Si substrate in a 1:1 ratio for 1 second each. Then, argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0207] Next, 1000 sccm of ammonia was added to the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 3 seconds. During this time, the substrates on which the metal thin film would be formed were heated to the temperature shown in Table 2 below (380°C). This process was repeated 200 to 400 times to form a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0208]

[0209] Example 2

[0210] From the compounds listed in Table 1 above, t-butyl iodide was prepared as a film quality improver, and the compound represented by chemical formula 34, MoO2Cl2, was prepared as a molybdenum precursor. The prepared film quality improver and thin film precursor compounds were placed in canisters and supplied at room temperature to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller).

[0211] The film quality improving agent and thin film precursor compound, vaporized into a vapor phase using a vaporizer, were each introduced into the deposition chamber loaded with the Si substrate in a 1:1 ratio for 1 second each. Then, argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0212] Next, 1000 sccm of ammonia was added to the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 3 seconds. During this time, the substrates on which the metal thin film would be formed were heated to 400°C, as shown in Table 2 below. This process was repeated 200 to 400 times to form a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0213]

[0214] Example 3

[0215] From the compounds listed in Table 1 above, t-butyl iodide was prepared as a film quality improver, and the compound represented by chemical formula 34, MoO2Cl2, was prepared as a molybdenum precursor. The prepared film quality improver and thin film precursor compounds were placed in canisters and supplied at room temperature to a vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC (Liquid Mass Flow Controller).

[0216] The film quality improving agent and thin film precursor compound, vaporized into a vapor phase using a vaporizer, were each introduced into the deposition chamber loaded with the Si substrate in a 1:1 ratio for 1 second each. Then, argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge. During this time, the pressure inside the reaction chamber was controlled to 2.5 Torr.

[0217] Next, 1000 sccm of ammonia was added to the reaction chamber as a reactive gas for 3 seconds, followed by argon purging for 3 seconds. During this time, the substrates on which the metal thin film would be formed were heated to 420°C, as shown in Table 2 below. This process was repeated 200 to 400 times to form a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm.

[0218]

[0219] Comparative Examples 1 to 3

[0220] The same process as in Examples 1 to 3 was repeated, except that the film quality improving agent was not included.

[0221] As a result, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed.

[0222]

[0223] Example 4

[0224] In the above-described Example 1, the same process as in Example 1 was repeated, except that the film quality improving agent and thin film precursor compound, vaporized into the vapor phase in a vaporizer, were sequentially introduced into the deposition chamber loaded with the substrate in a 1:1 ratio for 1 second each, and then argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge.

[0225] Specifically, a film quality improving agent vaporized into a vapor phase in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds. Then, a molybdenum precursor vaporized into a vapor phase in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds.

[0226] As a result, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed by repeating the process 200 to 400 times.

[0227]

[0228] Example 5

[0229] In the above-described Example 1, the same process as in Example 1 was repeated, except that the thin film precursor and film quality improver, vaporized into the vapor phase in a vaporizer, were sequentially introduced into the deposition chamber loaded with the substrate in a 1:1 ratio for 1 second each, and then argon gas was supplied at 5000 sccm for 2 seconds to perform an argon purge.

[0230] Specifically, a molybdenum precursor vaporized into a vapor phase in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds. Then, a film quality improver vaporized into a vapor phase in a vaporizer was introduced into the deposition chamber with the substrate loaded for 1 second, followed by argon purging by supplying argon gas at 5000 sccm for 2 seconds.

[0231] As a result, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed by repeating the process 200 to 400 times.

[0232]

[0233] Reference example 1

[0234] In Example 1, the same process was repeated except that t-butyl iodide was replaced with iodobutane as the film quality improving agent.

[0235] As a result, a MoN thin film, which is a self-limiting atomic layer with a thickness of 10 nm, was formed.

[0236]

[0237] [Example of experiment]

[0238] 1) Evaporation evaluation (evaporation rate per cycle, GPC)

[0239] The deposition rate was evaluated by calculating the thickness of the fabricated thin film deposited per cycle by dividing the thickness of the thin film measured using an ellipsometer, a device that can measure optical properties such as the thickness and refractive index of a thin film using the polarization characteristics of light, by the number of cycles. The results are shown in Table 2 below.

[0240]

[0241] 2) Thin film resistance evaluation (resistivity)

[0242] The surface resistance of the manufactured thin film was measured using the four-point probe method to determine the surface resistance. Then, the resistivity (μΩ.cm) was calculated from the thickness of the thin film, and the resulting values ​​are shown in Table 2 below.

[0243] [Table 2]

[0244] As shown in Table 2 above, when the t-butyl iodide of the present invention was used together with a thin film precursor compound as a film quality improving agent (Examples 1 to 3), the resistivity decreased to 919 to 1884 μΩ.cm while providing an deposition rate equivalent to or similar to that when no film quality improving agent was used (Comparative Examples 1 to 3). This confirmed that the thin film growth rate was appropriately controlled and the electrical properties were improved.

[0245] 3) Impurity reduction characteristics

[0246] To compare the impurity reduction characteristics, i.e., process by-products, of the manufactured 10 nm thick thin films, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the elements ia)(Ti), nitrogen (N), Cl (chlorine), carbon (C), and oxygen (O), and the results are shown in Table 3 below.

[0247] [Table 3]

[0248] As shown in Table 3 above, when the film quality improving agent according to the present invention was used simultaneously with the thin film precursor compound (Example 1), it not only showed levels equivalent to or similar to when the film quality improving agent was not used (Comparative Example 1), but also showed a reduction in the intensity of Cl and C to 0.01% compared to when other film quality improving agents were used (Reference Example 1), confirming that the impurity reduction characteristics were superior. In particular, in the case of Comparative Example 1, since no film quality improving agent was added, theoretically carbon should not be detected, but it was confirmed that carbon was detected, which is thought to have originated from trace amounts of CO and / or CO2 contained in the thin film precursor compound, purge gas, and reaction gas. However, in Example 1 of the present invention, even though a film quality improving agent, which is a hydrocarbon compound, was added during thin film deposition, it was confirmed that the carbon intensity was reduced compared to Comparative Example 1, which means that the film quality improving agent of the present invention has superior impurity reduction characteristics.

[0249] In particular, in Reference Example 1, a compound with a halide-based structure similar to the film quality improving agent of the present invention was added, but the impurity intensity was much higher than in Example 1 and, consequently, Comparative Example 1, confirming that there was no film quality improving effect.

[0250]

[0251] Furthermore, the following additional experiments were conducted to confirm the effects of the film quality improving agent at each injection stage.

[0252]

[0253] Example 6

[0254] Using MoO2Cl2 as a Mo precursor, ALD deposition evaluation was performed using a VFC supply method.

[0255] The canister heating temperature for MoO2Cl2 was 90°C, and deposition evaluation temperatures were set to 380°C, 400°C, and 420°C, respectively. The process pressure was 6 torr, and the flow rates of the ammonia reaction gas and Ar purge gas were all 1000 sccm.

[0256] To confirm the improvement in resistivity and GPC, a MoN thin film was deposited and compared.

[0257] Specifically, two experiments were conducted: one in which MoO2Cl2 was injected, followed by Ar purging, then t-butyl iodide was injected, followed by Ar injection, NH3 reaction gas injection, and then Ar injection before ALD deposition (post-injection); and another in which t-butyl iodide was injected, followed by Ar injection, then MoO2Cl2 was injected, followed by Ar injection, then NH3 reaction gas injection, and then Ar injection before ALD deposition (pre-injection). After each experiment, the resistivity and deposition rate were measured using the method presented in the above experimental example. As a control group, the resistivity and deposition rate were also measured in the same manner for MoN thin films manufactured without the addition of a film quality improving agent.

[0258] The measurement results for each are shown in Figure 1 below. Figure 1 below is a diagram comparing the results of the experiment in which the film quality improving agent presented in the present invention was injected into MoO2Cl2 before and after injection, with the results of Example 6, a control group experiment in which the film quality improving agent was not used.

[0259] As can be seen in Figure 1 below, the resistivity shown in the left-hand diagram compared to the control group showed improvement in both pre-injection and post-injection compared to the control group, with pre-injection showing the greatest improvement. The deposition rate shown in the right-hand diagram also showed further improvement with pre-injection, confirming that pre-injection of the film quality improving agent is even more effective than post-injection.

Claims

1. A film quality improving agent for molybdenum-based thin films, The aforementioned molybdenum-based thin film contains molybdenum metal, molybdenum oxide, or molybdenum nitride on a substrate. The aforementioned molybdenum-based film quality improving agent comprises one or more molybdenum precursors selected from the following chemical formulas 2 to 36, and a film quality improving agent which is a saturated compound represented by the following chemical formula 1. The aforementioned film quality improving agents are 2-chloro-2-methylpropane, 2-chloro-2-methylbutane, 2-chloro-2-methylpentane, 3-chloro-3-methylpentane, 3-chloro-3-methylhexane, 3-chloro-3-ethylpentane, 3-chloro-3-ethylhexane, 4-chloro-4-methylheptane, 4-chloro-4-ethylheptane, 4-chloro-4-propylheptane, 2-bromo-2-methylpropane, 2-bromo-2-methylbutane, 2-bromo-2-methylpentane, 3-bromo-3-methylpentane, 3-bromo-3-methylhexane, 3-bromo-3-ethylpentane, 3-bromo-3-ethylhexane, 4-bromo-4-methylheptane, 4-bromo-4-ethylheptane, 4-bromo-4-propylheptane, 2-iodo-2-methylpropane, 2-iod A film quality improving agent for molybdenum-based thin films, characterized by being one or more selected from the group consisting of -2 methylbutane, 2-iodo-2 methylpentane, 3-iodo-3 methylpentane, 3-iodo-3 methylhexane, 3-iodo-3 ethylpentane, 3-iodo-3 ethylhexane, 4-iodo-4 methylheptane, 4-iodo-4 ethylheptane, 4-iodo-4 propylheptane, 2-fluoro-2 methylpropane, 2-fluoro-2 methylbutane, 2-fluoro-2 methylpentane, 3-fluoro-3 methylpentane, 3-fluoro-3 methylhexane, 3-fluoro-3 ethylpentane, 3-fluoro-3 ethylhexane, 4-fluoro-4 methylheptane, 4-fluoro-4 ethylheptane, and 4-fluoro-4 propylheptane. [Chemical formula 1] (A is carbon (C) or silicon (Si), The aforementioned X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), The aforementioned R １ and R ３ These are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). Said R ２ is independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or a functional group of the formula BR ４ R ５ R ６ where B is carbon or silicon, and said R ４ , R ５ and R ６ are independently hydrogen, an alkyl group having 1 to 5 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).) [Chemical formulas 2 through 19] [Chemical formulas 20 to 32] [Chemical formulas 33 to 36]

2. The film quality improving agent for molybdenum-based thin films according to claim 1, characterized in that the refractive index (a) is in the range of 1.38 to 1.72, and the value obtained by dividing the vapor pressure (25°C, mmHg, b) by the refractive index (a) (b / a) is in the range of 0.003 to 0.

043.

3. The molybdenum-based thin film is a film quality improving agent for molybdenum-based thin films according to claim 1, characterized in that the molybdenum-based thin film is used as a diffusion-blocking film or an electrode.

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