Thin film manufacturing method and thin film manufacturing apparatus

Abstract

To provide a thin film manufacturing method that greatly improves step coverage and thickness uniformity of a thin film even when forming the thin film on a substrate having a complicated structure, by suppressing side reactions, lowering a thin film growth rate, and removing process by-products in the thin film.SOLUTION: A thin film manufacturing method includes i) a step for adsorbing a thin film growth inhibitor represented by chemical formula (1) on the surface of a substrate and ii) a step for adsorbing a Ti-based thin film precursor on the surface of the substrate on which the growth inhibitor is adsorbed. AnBmXo (1) (where A indicates carbon or silicon, B indicates hydrogen or an alkyl of 1-3 carbons, X indicates a halogen, n indicates an integer between 1 and 15, o indicates an integer of 1 or more, and m indicates a number between 0 and 2n+1).SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a thin film manufacturing method and a thin film manufacturing apparatus. More specifically, the present invention relates to a thin film manufacturing method and a thin film manufacturing apparatus that suppress side reactions to appropriately reduce the thin film growth rate, prevent corrosion and deterioration by removing in-film process by-products, and greatly improve the step coverage and the thickness uniformity of the thin film even when forming a thin film on a substrate having a complex structure.

Background Art

[0002] The integration degree of memory and non-memory semiconductor devices is increasing day by day. As the structure becomes increasingly complex, the importance of step coverage when depositing various thin films on a substrate is increasing more and more. Thin films for semiconductors are composed of metal nitrides, metal oxides, metal silicides, etc. Examples of metal nitride thin films include titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), etc. The thin films are generally used as diffusion prevention films between a silicon layer of a doped semiconductor and aluminum (Al), copper (Cu), etc. which are used as interlayer wiring materials. However, when depositing a tungsten (W) thin film on a substrate, it is used as an adhesion layer. In order for the thin film deposited on the substrate to obtain suitable and uniform physical properties, high step coverage of the formed thin film is essential. Therefore, the ALD (atomic layer deposition) process that utilizes surface reaction is being utilized rather than the CVD (chemical vapor deposition) process that mainly utilizes gas phase reaction. However, there are still problems in realizing 100% step coverage. In addition, in the case of titanium tetrachloride (TiCl4) used for depositing typical titanium nitride (TiN) among the metal nitrides, process by-products such as chlorides in the manufactured thin film remain, inducing corrosion of metals such as aluminum, and causing deterioration of the film quality due to the problem of generation of non-volatile by-products. Therefore, there is a need to develop a manufacturing method for a thin film that enables formation of a thin film with a complex structure and does not corrode the interlayer wiring material. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Korean Published Patent No. 2006-0037241 [Overview of the project] [Problems that the invention aims to solve]

[0004] To solve the problems of the conventional technology described above, the present invention aims to provide a thin film manufacturing method and apparatus that suppress side reactions to appropriately reduce the thin film growth rate, prevent corrosion and degradation by removing by-products from the thin film manufacturing process, and greatly improve step coverage and thin film thickness uniformity even when forming thin films on substrates with complex structures. 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]

[0005] To achieve the above objectives, the present invention provides i) a growth for forming thin films represented by chemical formula (1). The present invention provides a thin film manufacturing method comprising the steps of: ii) adsorbing an inhibitor onto the substrate surface, and ii) adsorbing a Ti-based thin film precursor onto the substrate surface on which the growth inhibitor has been adsorbed. AnBmXo (1) (In the formula, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is a halogen, n is an integer from 1 to 15, o is an integer greater than or equal to 1, and m is from 0 to 2n+1.) Furthermore, the present invention provides a thin film manufacturing apparatus comprising an ALD chamber, a first vaporizer for vaporizing a thin film formation growth inhibitor, a first transfer means for transferring the vaporized thin film formation growth inhibitor into the ALD chamber, a second vaporizer for vaporizing a Ti-based thin film precursor, and a second transfer means for transferring the vaporized Ti-based thin film precursor into the ALD chamber. [Effects of the Invention]

[0006] The present invention provides a thin film manufacturing method that suppresses side reactions, reduces the deposition rate to appropriately lower the thin film growth rate, prevents corrosion and degradation by removing by-products from the thin film process, and greatly improves step coverage and thin film thickness uniformity even when forming thin films on substrates with complex structures. [Brief explanation of the drawing]

[0007] [Figure 1] This is a process diagram illustrating the conventional ALD process. [Figure 2] This is a process diagram illustrating the ALD process according to one embodiment of the present invention. [Figure 3] This graph shows the change in thin film thickness with increasing ALD cycles for Example 7 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention. [Figure 4] This graph shows the change in deposition rate with respect to the feeding time of the thin film growth inhibitor (SP) per ALD cycle for Examples 7-1 to 7-3 and Comparative Example 1 of the present invention. [Figure 5] These are TEM images of the TIN thin films deposited in Example 1 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention. [Modes for carrying out the invention]

[0008] The inventors of this invention have confirmed that when a halogen-substituted compound having a predetermined structure is adsorbed as a growth inhibitor on the substrate surface loaded into the ALD chamber before adsorbing a Ti-based thin film precursor, the growth rate of the thin film formed after deposition is reduced, the amount of halide remaining as a process by-product is significantly reduced, and step coverage and other properties are greatly improved. Based on this, they have diligently conducted further research and have completed the present invention. The present invention provides a thin film manufacturing method comprising: i) a step of adsorbing a thin film formation growth inhibitor represented by the following chemical formula (1) onto the surface of a substrate; and ii) a step of adsorbing a Ti-based thin film precursor onto the substrate surface on which the growth inhibitor has been adsorbed. AnBmXo (1) (In the formula, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is a halogen, n is an integer from 1 to 15, o is an integer greater than or equal to 1, and m is from 0 to 2n+1.) In such cases, suppressing side reactions during thin film formation reduces the thin film growth rate, and removing by-products from the thin film process reduces corrosion and degradation. This also significantly improves step coverage and thin film thickness uniformity, even when forming thin films on substrates with complex structures.

[0009] i) The step of adsorbing the thin film growth inhibitor onto the substrate surface is preferably performed with a feeding time of 1 to 10 seconds, more preferably 1 to 5 seconds, even more preferably 2 to 5 seconds, and even more preferably 2 to 4 seconds. Within this range, the thin film growth rate is low, and there are advantages in terms of step coverage and cost-effectiveness. In this description, the supply time of the growth inhibitor for thin film formation is based on a chamber volume of 15 to 20 L and a flow rate of 0.5 to 5 mg / s, more specifically, on a chamber volume of 18 L and a flow rate of 1 to 2 mg / s. i) The step of adsorbing the thin film formation growth inhibitor onto the substrate surface preferably includes the step of injecting the thin film formation growth inhibitor into the ALD chamber and adsorbing it onto the loaded substrate surface. In such a case, there is a great effect in suppressing side reactions, slowing down the deposition rate to reduce the thin film growth rate, and removing by-products from the process within the thin film. The i) step of adsorbing the growth inhibitor for thin film formation onto the substrate surface preferably includes purging any remaining growth inhibitor for thin film formation that is not adsorbed onto the substrate surface with a purge gas. In this case, side reactions are suppressed during thin film formation, the thin film growth rate is reduced, and corrosion and degradation are reduced by removing by-products from the process within the thin film. This also has the advantage of greatly improving step coverage and thickness uniformity of the thin film, even when forming a thin film on a substrate with a complex structure. Furthermore, the ii) step of adsorbing the Ti-based thin film precursor preferably includes purging any remaining Ti-based thin film precursor that has not been adsorbed with a purge gas.

[0010] The thin film manufacturing method preferably includes the steps of adsorbing a Ti-based thin film precursor onto a substrate surface, supplying a reaction gas, and purging the reaction byproducts of the Ti-based thin film precursor and the reaction gas with a purge gas. As a preferred embodiment, the thin film manufacturing method includes the steps of: a) vaporizing the growth inhibitor for thin film formation and adsorbing it onto the surface of a substrate loaded in an ALD chamber; b) primary purging the inside of the ALD chamber with a purge gas; c) vaporizing a Ti-based thin film precursor and adsorbing it onto the surface of a substrate loaded in an ALD chamber; d) secondary purging the inside of the ALD chamber with a purge gas; e) supplying a reaction gas to the inside of the ALD chamber; and f) tertiary purging the inside of the ALD chamber with a purge gas. In this case, the thin film growth rate is appropriately reduced, and even if the deposition temperature is high during thin film formation, the process by-products generated are effectively removed, reducing the resistivity of the thin film and greatly improving step coverage.

[0011] The thin film growth inhibitor and the Ti-based thin film precursor are preferably transferred into the ALD chamber, i.e., to the substrate surface, by the VFC, DLI, or LDS method, and more preferably into the ALD chamber by the LDS method. The ratio of the amount (mg / cycle) of the thin-film growth inhibitor to the precursor compound introduced into the ALD 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 rate of reduction of the thin-film growth rate (GPC) per cycle is high, and the effect of reducing process by-products is significant. The Ti-based thin film precursor is not particularly limited as long as it is a Ti-based thin film precursor that is normally used in ALD, but a preferred example is titanium tetrahalide. The titanium tetrahalide is preferably at least one selected from the group consisting of TiF4, TiCl4, TiBr4 and TiI4. For example, TiCl4 is preferable from the aspect of economy, but it is not limited thereto. However, since the titanium tetrahalide has excellent thermal stability and exists in a liquid state without decomposing at room temperature, it can be usefully used for depositing a thin film as a thin film precursor for ALD. As an example, the Ti-based thin film precursor may be mixed with a nonpolar solvent and introduced into the chamber. In this case, there is an advantage that the viscosity and vapor pressure of the Ti-based thin film precursor can be easily adjusted.

[0012] The nonpolar solvent is one or more selected from the group consisting of alkanes and cycloalkanes. In such a case, although it contains an organic solvent with low reactivity and solubility and easy moisture management, there is an advantage that the step coverage improves even when the deposition temperature increases during thin film formation. As a more preferable example, the nonpolar solvent contains an alkane having 1 to 10 carbon atoms or a cycloalkane having 3 to 10 carbon atoms, preferably a cycloalkane having 3 to 10 carbon atoms. In this case, there are advantages of low reactivity and solubility and easy moisture management. In this description, C1, C3, etc. mean the number of carbon atoms. The cycloalkane is preferably a monocycloalkane having 3 to 10 carbon atoms. Among the monocycloalkanes, cyclopentane is a liquid at room temperature and has the highest vapor pressure, which is preferable in the gas phase deposition process, but it is not limited thereto. As an example, the nonpolar solvent has a solubility (25 ° C) in water of 200 mg / L or less, preferably 50 to 200 mg / L, more preferably 135 to 175 mg / L. Within this range, there are advantages of low reactivity with respect to the Ti-based thin film precursor and easy moisture management. In this description, the solubility is not particularly limited according to the measurement methods and standards commonly used in the technical field to which the present invention belongs. As an example, a saturated solution can be measured by HPLC method. The nonpolar solvent is preferably 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 Ti-based thin film precursor and the nonpolar solvent combined. When the content of the nonpolar solvent exceeds the upper limit, it induces impurities, increasing the resistance and the value of impurities within the thin film. When the content of the organic solvent is added below the lower limit, there is a disadvantage in that the effect of improving step coverage due to solvent addition and the effect of reducing impurities such as chloride (Cl) ions are small.

[0013] As an example, the thin film manufacturing method has a decrease rate of -5% or less in the thin film growth rate per cycle (angstroms / Cycle) calculated by the following formula 1, 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. [Mathematics 1] The percentage decrease in the thin film growth rate per cycle (%) = [(Thin film growth rate per cycle when using a thin film growth inhibitor - Thin film growth rate per cycle when not using a thin film growth inhibitor) / Thin film growth rate per cycle when not using a thin film growth inhibitor] × 100 The aforementioned thin film manufacturing method is characterized by a residual halogen intensity (c / s) in the thin film formed after 200 cycles, as measured by SIMS, which is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 7,000 or less, and even more preferably 6,000 or less. Within this range, the method exhibits excellent effectiveness in preventing corrosion and degradation. In this description, purging is preferably 1,000 to 10,000 sccm, more preferably 2,000 to 7,000 sccm, and even more preferably 2,500 to 6,000 sccm. Within this range, the thin film growth rate per cycle is reduced within a favorable range, and the process by-products are reduced.

[0014] The aforementioned ALD is highly advantageous in the fabrication of integrated circuits (ICs) that require high aspect ratios, and in particular, its self-limiting thin film growth mechanism offers advantages such as excellent conformality, uniformity, and precise thickness control. The aforementioned thin film manufacturing method is carried out, for example, at an evaporation temperature in the range of 50 to 900°C, preferably in the range of 300 to 700°C, more preferably in the range of 350 to 600°C, even more preferably in the range of 400 to 550°C, and even more preferably in the range of 400 to 500°C. Within this range, there is a great effect in growing a thin film with excellent film quality while embodying the ALD process characteristics. The aforementioned thin film manufacturing method is carried out, for example, with an deposition pressure in the range of 0.1 to 10 Torr, preferably in the range of 0.5 to 5 Torr, and most preferably in the range of 1 to 3 Torr, and has the effect of obtaining a thin film of uniform thickness within this range. In this description, the deposition temperature and deposition pressure can be measured by the temperature and pressure formed within the deposition chamber, or by the temperature and pressure applied to the substrate within the deposition chamber.

[0015] The thin film manufacturing method preferably includes the steps of raising the temperature inside the chamber to the deposition temperature before introducing the growth inhibitor for thin film formation into the chamber, and / or injecting an inert gas into the chamber to purge it before introducing the growth inhibitor for thin film formation into the chamber. Furthermore, the present invention includes a thin film manufacturing apparatus capable of embodying the thin film manufacturing method, comprising an ALD chamber, a first vaporizer for vaporizing a thin film formation growth inhibitor, a first transfer means for transferring the vaporized thin film formation growth inhibitor into the ALD chamber, a second vaporizer for vaporizing a Ti-based thin film precursor, and a second transfer means for transferring the vaporized Ti-based 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.

[0016] As a specific example, the thin film manufacturing method described above will be explained. First, a substrate on which a thin film can be formed on top is placed inside a deposition chamber capable of atomic layer deposition. The substrate includes semiconductor substrates such as silicon substrates and silicon oxide. The aforementioned substrate may have a conductive layer or an insulating layer further formed on its upper surface. To deposit a thin film onto a substrate positioned in the deposition chamber, the above-mentioned thin film formation growth inhibitor and a Ti-based thin film precursor or a mixture thereof with a nonpolar solvent are prepared, respectively. Subsequently, the prepared thin-film formation inhibitor is injected into the vaporizer, converted to a gas phase, and transferred to the deposition chamber where it is adsorbed onto the substrate. The non-adsorbed thin-film formation inhibitor is then purged. Next, the prepared Ti-based thin film precursor or a mixture thereof with a nonpolar solvent is injected into the vaporizer, then converted to a gas phase and transferred to the deposition chamber where it is adsorbed onto the substrate, and any non-adsorbed thin film forming composition is purged.

[0017] In this description, the method for transferring the thin film formation inhibitor and the Ti-based thin film precursor to the deposition chamber may, as an example, be a method that utilizes a gas flow control (MFC) method to transfer volatile 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. As a carrier gas or diluent gas for transferring thin film formation inhibitors and Ti-based thin film precursors onto the substrate, one or more mixed gases selected from argon (Ar), nitrogen (N2), and helium (He) are used, but are not limited to these. In this description, as an example of a purge gas, an inert gas is used, preferably the carrier gas or diluent gas. 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 includes a reducing agent, a nitride agent, or an oxidizing agent. The reducing agent reacts with the Ti-based thin film precursor adsorbed on the substrate to form a metal thin film, a metal nitride thin film is formed depending on the nitride agent, and a metal oxide thin film is formed depending on the oxidizing agent. Preferably, the reducing agent is ammonia gas (NH3) or hydrogen gas (H2), the nitriding agent is nitrogen gas (N2), and the oxidizing agent is one or more selected from the group consisting of H2O, H2O2, O2, O3, and N2O.

[0018] 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. Thus, the steps of adsorbing a thin-film formation inhibitor onto a substrate, purging non-adsorbed thin-film formation inhibitor, adsorbing a Ti-based thin-film precursor onto a substrate, purging non-adsorbed thin-film formation composition, supplying a reaction gas, and purging residual reaction gas are considered as a unit cycle, and this unit cycle can be repeated to form a thin film of a desired thickness. The aforementioned unit cycle is, for example, 100 to 1000 times, preferably 100 to 500 times, and more preferably 150 to 300 times, and within this range, the desired thin film characteristics are suitably expressed.

[0019] Figure 1 is a process diagram illustrating a conventional ALD process, and Figure 2 is a process diagram illustrating an ALD process according to one embodiment of the present invention. Referring to Figure 1, if the growth inhibitor for thin film formation of the present invention is not adsorbed before the Ti-based thin film precursor (TiCl4) is adsorbed to protect the substrate surface, as in the conventional ALD process, process by-products such as HCl remain on the thin film (TiN) formed by the reaction with the reaction gas (NH3), reducing the performance of the substrate due to corrosion and degradation. However, as shown in Figure 2, if the growth inhibitor for thin film formation (TSI) according to the present invention is adsorbed before the Ti-based thin film precursor (TiCl4) is adsorbed to protect the substrate surface (Surface Protection; SP), process by-products such as HCl generated by the reaction with the reaction gas (NH3) during thin film (TiN) formation are removed together with the growth inhibitor for thin film formation, preventing corrosion and degradation of the substrate. Furthermore, the thin film growth rate per cycle can be appropriately reduced to improve step coverage and uniformity of thin film thickness.

[0020] The growth inhibitor for thin film formation of the present invention is preferably a compound represented by chemical formula (1). AnBmXo (1) (In the formula, A is carbon or silicon, B is hydrogen or an alkyl group having 1 to 3 carbon atoms, X is a halogen, n is an integer from 1 to 15, o is an integer greater than or equal to 1, and m is from 0 to 2n+1.) In such cases, suppressing side reactions during thin film formation reduces the thin film growth rate, and removing by-products from the thin film process reduces corrosion and degradation. This also significantly improves step coverage and thin film thickness uniformity, even when forming thin films on substrates with complex structures. B is preferably hydrogen or methyl, and n is preferably an integer from 2 to 15, more preferably an integer from 2 to 10, even more preferably an integer from 2 to 6, and even more preferably an integer from 4 to 6. Within this range, the effect of removing process by-products is large and the step coverage is excellent. In chemical formula (1), X is one or more elements selected from the group consisting of F, Cl, Br, and I, and is preferably Cl (chlorine). In this case, side reactions are suppressed and process by-products are effectively removed. In chemical formula (1), o is preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2. Within this range, the effect of reducing the deposition rate is significant, which has the advantage of being even more effective in improving step coverage. m is preferably 1 to 2n+1, and more preferably 3 to 2n+1. Within this range, the effect of removing process by-products is large and the step coverage is excellent.

[0021] The compound represented by chemical formula (1) is preferably a branched, cyclic, or aromatic compound. Specific examples include one or more compounds selected from the group consisting of 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, chlorocyclopetan, n-butyl chloride, tert-butyl chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1,4-dichlorobenzene, trimethylchlorosilane, trichloropropane, 2-chloro-2-methylbutane, and 2-methyl-1-pentane. In this case, there is an advantage in that the removal effect of process by-products is significant and step coverage is excellent. The compound represented by chemical formula (1) is preferably used in the ALD process, in which case it has the advantage of effectively protecting the substrate surface as a growth inhibitor without inhibiting the adsorption of the Ti-based thin film precursor, and effectively removing process by-products. The compound represented by chemical formula (1) is preferably a liquid at room temperature (22°C) and has a density of 0.8 to 1.5 g / cm³. 3 It has a vapor pressure (at 20°C) of 1 to 300 mmHg and a solubility in water (at 25°C) of 200 mg / L or less, and within this range it exhibits excellent stepped coverage and thin film thickness uniformity. More preferably, the compound represented by chemical formula 1 has a density of 0.85 to 1.3 g / cm³. 3 Its vapor pressure (at 20°C) is 1 to 260 mmHg, and its solubility in water (at 25°C) is 160 mg / L or less. Within this range, it exhibits excellent stepped coverage and uniformity of thin film thickness.

[0022] The semiconductor substrate of the present invention is manufactured by the thin film manufacturing method described herein. In this case, side reactions are suppressed to appropriately reduce the thin film growth rate, and by removing by-products from the thin film manufacturing process, corrosion and degradation are prevented, resulting in excellent step coverage and uniformity of thin film thickness. The manufactured thin film preferably has a thickness of 20 nm or less, a resistivity of 0.1 to 400 μΩ·cm, a halogen content of 10,000 ppm or less, and a step coverage ratio of 90% or more. Within this range, it exhibits excellent performance as a diffusion-blocking film and has the effect of reducing corrosion of metal wiring materials, but it is not limited to this range. The thin film has a thickness of, for example, 5 to 20 nm, preferably 10 to 20 nm, more preferably 15 to 18.5 nm, and even more preferably 17 to 18.5 nm. Excellent thin film properties are achieved within this range. The thin film has a resistivity of, for example, 0.1 to 400 μΩ·cm, preferably 50 to 400 μΩ·cm, more preferably 200 to 400 μΩ·cm, even more preferably 300 to 400 μΩ·cm, even more preferably 330 to 380 μΩ·cm, and most preferably 340 to 370 μΩ·cm. Excellent thin film properties are achieved within this range. The thin film has a halogen content of more preferably 9,000 ppm or less or 1 to 9,000 ppm, even more preferably 8,500 ppm or less or 100 to 8,500 ppm, and even more preferably 8,200 ppm or less or 1,000 to 8,200 ppm. Within this range, it is possible to reduce corrosion of metal wiring materials while maintaining excellent thin film properties. The aforementioned thin film, for example, has a step coverage rate of 80% or more, preferably 90% or more, and more preferably 92% or more. Within this range, even thin films with complex structures can be easily deposited onto a substrate, which has the advantage of being applicable to next-generation semiconductor devices.

[0023] Examples of the thin films produced include TiN and TiO2 thin films. The following examples and drawings illustrate the present invention, but these are merely illustrative examples, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the invention and the technical concept, and such variations and modifications naturally fall within the scope of the attached claims.

[0024] Examples 1 to 7 The growth inhibitors for thin film formation listed in Table 1 and TiCl4 as a Ti-based thin film precursor were prepared. The prepared growth inhibitors for thin film formation 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). After the growth inhibitors for thin film formation, vaporized into the gas phase in the vaporizer, were introduced into the deposition chamber with the substrate loaded for 3 seconds, argon purging was performed by supplying argon gas at 3000 sccm for 6 seconds. At this time, the pressure in the reaction chamber was controlled to 1.3 Torr. Next, the prepared TiCl4 was placed in a separate canister and supplied at room temperature to a separate vaporizer heated to 150°C at a flow rate of 0.05 g / min using an LMFC. After the TiCl4, vaporized into the gas phase in the vaporizer, was introduced into the deposition chamber for 3 seconds, argon purging was performed by supplying argon gas at 3000 sccm for 6 seconds. At this time, the pressure inside the reaction chamber was controlled to 1.3 Torr. Next, ammonia was added to the reaction chamber as a reactive gas for 5 seconds, followed by argon purging for 10 seconds. During this time, the substrate on which the metal thin film would be formed was heated to 460°C. This process was repeated 200 times to form a TiN thin film, which is a self-limiting atomic layer. [Table 1]

[0025] Comparative Example 1 A TIN thin film was formed on the substrate using the same method as in Example 1, except that a growth inhibitor for thin film formation was not used, and consequently, the step of purging the growth inhibitor for non-adsorbent thin film formation was omitted. Comparative Examples 2 and 3 A TIN thin film was formed on the substrate in the same manner as in Example 1, except that pentane or cyclopentane was used instead of the thin film formation growth inhibitors listed in Table 1 above.

[0026] 1) Vapor deposition evaluation Referring to Table 2, Example 1, which used chloro-2-methylbutane as a growth inhibitor for thin film formation, was compared with Comparative Example 1, which did not contain it. As a result, the deposition rate was 0.20 angstroms / cycle, which was a decrease of more than 55.5% compared to Comparative Example 1. It was confirmed that the deposition rates of the remaining Examples 2 to 7 were similar to those of Example 1. Furthermore, it was confirmed that Comparative Examples 2 and 3, which used pentane or cyclopentane instead of the growth inhibitor for thin film formation according to the present invention, also had the same deposition rates as Comparative Example 1. In this case, the decrease in deposition rate means that the CVD deposition characteristics are changed to ALD deposition characteristics, and can therefore be used as an indicator of improvement in step coating characteristics. [Table 2]

[0027] As shown in Table 3, it was confirmed that the deposition rate decreased steadily in proportion to the amount of chloro-2-methylbutane, a growth inhibitor for thin film formation, injected. Here, Example 1-1 was carried out in the same manner as Example 1, except for the amount of growth inhibitor for thin film formation injected per cycle. [Table 3]

[0028] 2) Impurity reduction characteristics SIMS analysis was performed to compare the impurity reduction characteristics, i.e., the process by-product reduction characteristics, of the TiN thin films deposited in Example 1 and Comparative Example 1, and the results are shown in Table 4. [Table 4] As shown in Table 4, it was confirmed that Example 1, which used the thin-film growth inhibitor according to the present invention, showed a reduction to 1 / 3 of the level compared to Comparative Example 1, which did not use the inhibitor. Figure 3 is a graph showing the change in thin film thickness with increasing ALD cycles for Example 7 (SP-TiCl4) and Comparative Example 1 (TiCl4) of the present invention. In the case of Example 7, it was confirmed that the thickness of the thin film decreased significantly. Figure 4 is a graph showing the change in deposition rate with respect to the feeding time of the thin-film growth inhibitor (SP) per ALD cycle for Examples 7-1 to 7-3 and Comparative Example 1 of the present invention. When the thin-film growth inhibitor according to the present invention was not used, as in Comparative Example 1, the deposition rate per cycle was approximately 0.45 angstroms / cycle. However, in Examples 7-1, 7-2, and 7-3, where the thin-film growth inhibitor according to the present invention was fed for 0.7 seconds, 1 second, and 2 seconds, respectively, the deposition rates were significantly lowered to 0.35 angstroms / cycle, 0.2 angstroms / cycle, and 0.1 angstroms / cycle, respectively. Here, Examples 7-1, 7-2, and 7-3 were carried out using the same method except for the amount of thin-film growth inhibitor fed in Example 7.

[0029] 3) Stepped coating characteristics The TiN thin films deposited in Example 1 and Comparative Example 1 were examined for step coverage using TEM, and the results are shown in Table 5 and Figure 5. [Table 5] As shown in Table 5, it was confirmed that Example 1, which used the growth inhibitor for thin film formation according to the present invention, had a significantly higher step coverage rate compared to Comparative Example 1, which did not use the inhibitor. Furthermore, referring to the TEM image in Figure 5, it was confirmed that the thickness uniformity between the top and bottom of the TIN thin film deposited in Example 1 (SP-TiCl4) was even better in terms of step coating properties compared to the TIN thin film deposited in Comparative Example 1 (TiCl4).

Claims

1. i) A step of adsorbing a thin film formation growth inhibitor, which is one or more compounds selected from the group consisting of 2-chloro-2-methylbutane, n-butyl chloride, 2-chloropropane, and 1,2-dichlorobenzene, onto the substrate surface. ii) A step of adsorbing a Ti-based thin film precursor onto the substrate surface on which a growth inhibitor has been adsorbed. iii) A step of supplying a reaction gas after adsorbing a Ti-based thin film precursor onto the substrate surface, and iv) A step of purging the reaction byproducts of the Ti-based thin film precursor and reaction gas with a purge gas. A method for manufacturing thin films, including the following.

2. The thin film manufacturing method according to claim 1, wherein the step of adsorbing the thin film formation growth inhibitor onto the substrate surface is performed for a supply time of 1 to 10 seconds to the substrate surface.

3. The thin film manufacturing method according to claim 1 or 2, wherein the i) step of adsorbing the thin film formation growth inhibitor onto the substrate surface is performed by injecting the thin film formation growth inhibitor into the ALD chamber and adsorbing it onto the loaded substrate surface.

4. The thin film manufacturing method according to any one of claims 1 to 3, wherein the step of adsorbing the growth inhibitor for thin film formation onto the substrate surface is to purge any remaining growth inhibitor for thin film formation that is not adsorbed onto the substrate surface with a purge gas.

5. The thin film manufacturing method according to any one of claims 1 to 4, wherein the step of adsorbing the Ti-based thin film precursor is to purge any remaining Ti-based thin film precursor that has not been adsorbed with a purge gas.

6. The method for producing a thin film according to any one of claims 1 to 5, wherein the reaction gas is a reducing agent, a nitriding agent, or an oxidizing agent.

7. The thin film manufacturing method according to any one of claims 1 to 6, wherein the thin film growth inhibitor and the Ti-based thin film precursor are transferred to the substrate surface by a VFC method, a DLI method, or an LDS method.

8. The method for producing a thin film according to any one of claims 1 to 7, wherein the ratio of the amount (mg / cycle) of the thin film formation growth inhibitor to the Ti-based thin film precursor added to the substrate surface is 1:1.5 to 1:

20.

9. The aforementioned compound is liquid at room temperature (22°C) and has a density of 0.8 to 1.5 g / cm³. ３ A method for producing a thin film according to any one of claims 1 to 8, wherein the vapor pressure (at 20°C) is 1 to 300 mmHg and the solubility in water (at 25°C) is 200 mg / L or less.

10. The thin film manufacturing method according to any one of claims 1 to 9, wherein the rate of decrease of the thin film growth rate per cycle (angstroms / Cycle) calculated by the following formula 1 is -5% or less. [Mathematics 1] The percentage decrease in the thin film growth rate per cycle is calculated as follows: (%) = [(Thin film growth rate per cycle when using a thin film growth inhibitor - Thin film growth rate per cycle when not using a thin film growth inhibitor) / Thin film growth rate per cycle when not using a thin film growth inhibitor] × 100

11. The thin film manufacturing method according to any one of claims 1 to 10, wherein the thin film obtained by the thin film manufacturing method has a residual halogen intensity (c / s) in the thin film formed after 200 cycles, as measured by SIMS, of 10,000 or less.

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